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ECSS-E-HB-32-20 Part 5A

20 March 2011

Space engineering
Structural materials handbook Part 5: New advanced materials,
advanced
metallic
materials,
general design aspects and load
transfer and design of joints
NOTE:
Thispdffiledoesnotcontainautomaticcrossreferences.Tomakeuseof
thecrossreferencespleaseusetheMSWordversionofthisdocument.

ECSS Secretariat
ESA-ESTEC
Requirements & Standards Division
Noordwijk, The Netherlands

ECSSEHB3220Part5A
20March2011

Foreword
ThisHandbookisonedocumentoftheseriesofECSSDocumentsintendedtobeusedassupporting
materialforECSSStandardsinspaceprojectsandapplications.ECSSisacooperativeeffortofthe
European Space Agency, national space agencies and European industry associations for the
purposeofdevelopingandmaintainingcommonstandards.
ThishandbookhasbeenpreparedbytheECSSEHB3230WorkingGroup,reviewedbytheECSS
ExecutiveSecretariatandapprovedbytheECSSTechnicalAuthority.

Disclaimer
ECSS does not provide any warranty whatsoever, whether expressed, implied, or statutory,
including,butnotlimitedto,anywarrantyofmerchantabilityorfitnessforaparticularpurposeor
anywarrantythatthecontentsoftheitemareerrorfree.InnorespectshallECSSincuranyliability
for any damages, including, but not limited to, direct, indirect, special, or consequential damages
arisingoutof,resultingfrom,orinanywayconnectedtotheuseofthisdocument,whetherornot
baseduponwarranty,businessagreement,tort,orotherwise;whetherornotinjurywassustained
bypersonsorpropertyorotherwise;andwhetherornotlosswassustainedfrom,oraroseoutof,
theresultsof,theitem,oranyservicesthatmaybeprovidedbyECSS.

Publishedby:

Copyright:

ESARequirementsandStandardsDivision
ESTEC,P.O.Box299,
2200AGNoordwijk
TheNetherlands
2011bytheEuropeanSpaceAgencyforthemembersofECSS

ECSSEHB3220Part5A
20March2011

Change log

ECSSEHB3220Part5A

Firstissue

20March2011

ECSSEHB3220Part5A
20March2011

Table of contents
Change log .................................................................................................................3
Introduction..............................................................................................................27
46

Aluminium alloys and their composites .......................................................28


46.1 Introduction............................................................................................................... 28
46.1.1

General....................................................................................................... 28

46.1.2

Conventional aluminium alloys ................................................................... 28

46.1.3

New aluminium alloys................................................................................. 28

46.1.4

MMC - metal matrix composites ................................................................. 29

46.1.5

FML - fibre metal laminates ........................................................................ 29

46.1.6

Material availability ..................................................................................... 29

46.2 Conventional aluminium alloys ................................................................................. 30


46.2.1

General....................................................................................................... 30

46.2.2

Chemical composition ................................................................................ 30

46.2.3

Aerospace alloys ........................................................................................ 36

46.2.4

Properties ................................................................................................... 36

46.3 New aluminium alloys............................................................................................... 37


46.3.1

Developments............................................................................................. 37

46.3.2

Aluminium-scandium alloys ........................................................................ 37

46.4 Al-Li - Aluminium-lithium alloys ................................................................................ 38


46.4.1

Development .............................................................................................. 38

46.4.2

Processing.................................................................................................. 38

46.4.3

Applications ................................................................................................ 39

46.4.4

Producers ................................................................................................... 39

46.4.5

Manufacturing processes ........................................................................... 41

46.5 Al-Li alloys: Characteristics ...................................................................................... 42


46.5.1

General....................................................................................................... 42

46.5.2

Microstructure............................................................................................. 43

46.5.3

Further development .................................................................................. 44

46.6 Al-Li alloys: Properties.............................................................................................. 44

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46.6.1

Data ............................................................................................................ 44

46.6.2

Tensile properties ....................................................................................... 44

46.6.3

Fracture properties ..................................................................................... 46

46.6.4

Fatigue properties....................................................................................... 48

46.6.5

Design values ............................................................................................. 52

46.6.6

Further development alloys ........................................................................ 53

46.7 Al-Li alloys: Stress corrosion cracking...................................................................... 53


46.7.1

General....................................................................................................... 53

46.7.2

Test............................................................................................................. 54

46.7.3

Stress corrosion cracking resistance.......................................................... 54

46.7.4

Recent alloys .............................................................................................. 57

46.8 Al-Li alloys: Manufacturing aspects .......................................................................... 58


46.8.1

General....................................................................................................... 58

46.8.2

Machining ................................................................................................... 58

46.8.3

Welding....................................................................................................... 58

46.8.4

Cost implications ........................................................................................ 59

46.8.5

Applications ................................................................................................ 60

46.8.6

Mass-saving ............................................................................................... 60

46.9 Al-Li alloys: Potential applications ............................................................................ 60


46.9.1

General factors ........................................................................................... 60

46.9.2

Space Shuttle external tank........................................................................ 61

46.9.3

A380 - Floor beams .................................................................................... 63

46.10 Oxide dispersion strengthened (ODS) alloys ........................................................... 64


46.10.1 Type and effect of dispersions.................................................................... 64
46.10.2 Processing.................................................................................................. 64
46.10.3 Cost factors ................................................................................................ 65
46.10.4 Applications ................................................................................................ 65
46.10.5 Properties ................................................................................................... 66
46.11 Rapidly solidified powder (RSP) alloys..................................................................... 72
46.11.1 Processing.................................................................................................. 72
46.11.2 Microstructure............................................................................................. 73
46.11.3 Development .............................................................................................. 73
46.11.4 Ambient temperature .................................................................................. 73
46.11.5 Elevated temperature ................................................................................. 75
46.12 Al-MMCs - Metal matrix composites......................................................................... 77
46.12.1 Introduction................................................................................................. 77
46.12.2 Manufacturing processes ........................................................................... 77

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46.12.3 Reinforcement materials............................................................................. 78
46.12.4 MMC nomenclature .................................................................................... 78
46.12.5 Advantages of MMCs ................................................................................ 79
46.12.6 Material availability ..................................................................................... 79
46.12.7 Sources of further information .................................................................... 80
46.13 Discontinuously reinforced Al-MMCs........................................................................ 81
46.13.1 Features ..................................................................................................... 81
46.13.2 Development .............................................................................................. 81
46.13.3 Matrix alloys................................................................................................ 81
46.13.4 Types of reinforcement............................................................................... 81
46.13.5 Processing.................................................................................................. 84
46.14 Discontinuously reinforced Al-alloys: Properties ...................................................... 86
46.14.1 General....................................................................................................... 86
46.14.2 Powder metallurgy MMCs .......................................................................... 87
46.14.3 MMCs produced by melt infiltration processes .......................................... 93
46.14.4 Spray-formed materials ............................................................................ 100
46.14.5 Further information ................................................................................... 101
46.15 Continuously Reinforced Al-Alloy MMC.................................................................. 102
46.15.1 General..................................................................................................... 102
46.15.2 Fibres........................................................................................................ 102
46.15.3 Matrix alloys.............................................................................................. 105
46.15.4 Characteristics.......................................................................................... 105
46.15.5 Processing................................................................................................ 106
46.16 Continuously reinforced Al-alloy MMC: Properties ............................................... 107
46.16.1 Mechanical properties .............................................................................. 107
46.16.2 Physical properties ................................................................................... 112
46.17 Al-alloy MMC: Potential applications ...................................................................... 112
46.17.1 Benefits of Aluminium-matrix composites................................................. 112
46.17.2 High specific strength and temperature resistance .................................. 113
46.17.3 High specific stiffness and good thermal properties ................................. 113
46.17.4 High conductivity with low thermal expansion .......................................... 114
46.17.5 High specific stiffness and dimensional stability....................................... 114
46.17.6 High specific strength and chemical resistance........................................ 114
46.18 References ............................................................................................................. 114
46.18.1 General..................................................................................................... 114
46.18.2 Sources .................................................................................................... 123
46.18.3 ECSS documents ..................................................................................... 124

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46.18.4 ASTM standards....................................................................................... 124
46.18.5 Other standards........................................................................................ 124

47

Titanium alloys and their composites.........................................................125


47.1 Introduction............................................................................................................. 125
47.2 Conventional alloys ................................................................................................ 125
47.2.1

Material selection factors.......................................................................... 125

47.2.2

Microstructure........................................................................................... 126

47.2.3

Effect of alloy elements ............................................................................ 126

47.2.4

Alloy classes............................................................................................. 127

47.2.5

Alloys for aerospace use .......................................................................... 128

47.2.6

Heat treatment.......................................................................................... 130

47.2.7

Mechanical properties .............................................................................. 130

47.2.8

Physical properties ................................................................................... 136

47.3 New alloys .............................................................................................................. 137


47.3.1

Developments........................................................................................... 137

47.3.2

Processing techniques ............................................................................. 137

47.4 Superplastic forming and diffusion bonding ........................................................... 138


47.4.1

Superplasticity .......................................................................................... 138

47.4.2

Diffusion bonding...................................................................................... 138

47.4.3

SPF/DB fabrication ................................................................................... 138

47.4.4

Materials ................................................................................................... 139

47.5 Discontinuously reinforced Ti-alloys ....................................................................... 140


47.5.1

Difficulties ................................................................................................. 140

47.5.2

Particulate reinforcements........................................................................ 140

47.5.3

Processing................................................................................................ 141

47.5.4

Properties ................................................................................................. 141

47.5.5

Further development ................................................................................ 141

47.6 Continuous fibre reinforced Ti-alloy MMC .............................................................. 141


47.6.1

Composite development........................................................................... 141

47.6.2

Monofilament reinforcements ................................................................... 142

47.6.3

Matrix selection......................................................................................... 143

47.6.4

Composite process technologies.............................................................. 143

47.7 Continuous fibre reinforced Ti-alloy MMC: properties ............................................ 144


47.7.1

Composite optimisation ............................................................................ 144

47.7.2

Tensile strength and stiffness................................................................... 144

47.7.3

Fatigue...................................................................................................... 146

47.7.4

Fracture toughness................................................................................... 147

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47.7.5

Elevated temperatures ............................................................................. 147

47.7.6

Thermo-mechanical fatigue ...................................................................... 147

47.8 Titanium alloys: Effect of hydrogen ........................................................................ 149


47.8.1

Material degradation mechanisms............................................................ 149

47.9 Titanium alloys: Effect of oxygen............................................................................ 150


47.9.1

Oxidation .................................................................................................. 150

47.9.2

Ignition and burning .................................................................................. 151

47.10 Coatings and protection systems ........................................................................... 151


47.10.1 Requirements ........................................................................................... 151
47.10.2 Potential coatings ..................................................................................... 151
47.11 Ti-alloys and MMCs: Potential applications............................................................ 152
47.11.1 Current use............................................................................................... 152
47.11.2 Developments........................................................................................... 152
47.11.3 Aerospace applications ............................................................................ 153
47.12 References ............................................................................................................. 154
47.12.1 General..................................................................................................... 154
47.12.2 ECSS documents ..................................................................................... 157

48

Superalloys and their composites ..............................................................158


48.1 Introduction............................................................................................................. 158
48.1.1

General..................................................................................................... 158

48.1.2

Alloy development .................................................................................... 158

48.1.3

Composites............................................................................................... 158

48.1.4

Service environment................................................................................. 159

48.1.5

Coating systems ....................................................................................... 159

48.2 Conventional alloys ................................................................................................ 159


48.2.1

General..................................................................................................... 159

48.2.2

Alloy groups.............................................................................................. 159

48.2.3

Aircraft engine applications ...................................................................... 160

48.2.4

Spacecraft engine applications................................................................. 168

48.3 New alloys .............................................................................................................. 171


48.3.1

Developments........................................................................................... 171

48.3.2

Directional solidification (DS).................................................................... 172

48.3.3

Single crystal (SC).................................................................................... 172

48.3.4

Powder metallurgy (PM) ........................................................................... 173

48.3.5

Oxide dispersion strengthened (ODS) alloys ........................................... 175

48.4 Discontinuously reinforced composites .................................................................. 177


48.5 Continuously reinforced composites ...................................................................... 178

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48.5.1

Composite development........................................................................... 178

48.6 Tungsten fibre reinforced superalloy (TFRS) composites ...................................... 179


48.6.1

Development ............................................................................................ 179

48.6.2

Matrix alloys.............................................................................................. 180

48.6.3

Mechanical properties .............................................................................. 180

48.6.4

Characteristics.......................................................................................... 186

48.7 Effect of hydrogen .................................................................................................. 186


48.7.1

Degradation mechanisms......................................................................... 186

48.7.2

Hydrogen embrittlement (HE)................................................................... 187

48.7.3

Hydrogen environment embrittlement (HEE)............................................ 188

48.7.4

Material sensitivity .................................................................................... 188

48.7.5

Creep in hydrogen environments ............................................................. 191

48.7.6

Fatigue in hydrogen environments ........................................................... 196

48.7.7

Fracture characteristics ............................................................................ 197

48.8 Effect of oxygen...................................................................................................... 200


48.8.1

Material selection factors.......................................................................... 200

48.8.2

Oxidation .................................................................................................. 200

48.8.3

Oxidation resistance ................................................................................. 200

48.8.4

Ignition and burn....................................................................................... 201

48.9 Coatings and protection systems ........................................................................... 202


48.9.1

Requirements ........................................................................................... 202

48.9.2

Types of coatings ..................................................................................... 203

48.9.3

Coating systems ....................................................................................... 203

48.9.4

Coated components ................................................................................. 203

48.9.5

Hydrogen fuel ........................................................................................... 203

48.10 Diffusion coatings ................................................................................................... 204


48.10.1 Types of coatings ..................................................................................... 204
48.11 Overlay coatings..................................................................................................... 207
48.11.1 Development ............................................................................................ 207
48.12 Thermal barrier coatings (TBC) .............................................................................. 209
48.12.1 Function.................................................................................................... 209
48.12.2 Coating construction................................................................................. 210
48.13 Coating influence on design ................................................................................... 211
48.13.1 Factors...................................................................................................... 211
48.13.2 Effect of coatings on mechanical properties............................................. 214
48.13.3 Chemical interaction ................................................................................. 214
48.13.4 Residual strains ........................................................................................ 216

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48.13.5 Tensile behaviour ..................................................................................... 217
48.13.6 Fatigue resistance .................................................................................... 219
48.13.7 Creep and relaxation ................................................................................ 222
48.13.8 Creep fatigue ............................................................................................ 226
48.14 Coatings: Future developments ............................................................................. 227
48.14.1 Materials ................................................................................................... 227
48.14.2 Service temperature ................................................................................. 228
48.14.3 Hydrogen environments ........................................................................... 228
48.15 Superalloys: Potential applications......................................................................... 228
48.15.1 Conventional alloys .................................................................................. 228
48.16 References ............................................................................................................. 230
48.16.1 General..................................................................................................... 230
48.16.2 ECSS documents ..................................................................................... 234

49

Intermetallic materials..................................................................................235
49.1 Introduction............................................................................................................. 235
49.1.1

Types of intermetallic compounds ............................................................ 235

49.2 Aluminide development .......................................................................................... 235


49.2.1

Features ................................................................................................... 235

49.2.2

Applications .............................................................................................. 236

49.2.3

Property data ............................................................................................ 237

49.2.4

Availability................................................................................................. 237

49.3 Nickel aluminides ................................................................................................... 237


49.3.1

Characteristics.......................................................................................... 237

49.4 Nickel aluminides: Properties ................................................................................. 240


49.4.1

General..................................................................................................... 240

49.4.2

Mechanical properties .............................................................................. 240

49.4.3

Oxidation resistance ................................................................................. 243

49.4.4

Aqueous corrosion.................................................................................... 243

49.4.5

Coefficient of thermal expansion (CTE).................................................... 243

49.5 Titanium aluminides ............................................................................................... 244


49.5.1

General..................................................................................................... 244

49.5.2

Characteristics.......................................................................................... 244

49.5.3

Effect of micro-alloying or doping ............................................................. 245

49.6 Titanium aluminides: Properties ............................................................................. 247


49.6.1

General..................................................................................................... 247

49.6.2

Mechanical properties .............................................................................. 247

49.6.3

Oxidation resistance ................................................................................. 255

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49.6.4

Thermophysical properties ....................................................................... 256

49.7 Iron aluminides ....................................................................................................... 260


49.7.1

Characteristics.......................................................................................... 260

49.8 Processing.............................................................................................................. 263


49.8.1

Development ............................................................................................ 263

49.8.2

Material processing .................................................................................. 263

49.8.3

Joining ...................................................................................................... 266

49.9 Further developments ............................................................................................ 266


49.9.1

Intermetallic compounds........................................................................... 266

49.9.2

Intermetallic matrix composites (IMC) ...................................................... 267

49.9.3

Protective coatings ................................................................................... 268

49.10 Intermetallic matrix composites .............................................................................. 268


49.10.1 General..................................................................................................... 268
49.10.2 Development ............................................................................................ 268
49.10.3 High temperature Ti-based IMC ............................................................... 270
49.11 Intermetallics: Potential applications ...................................................................... 274
49.11.1 General..................................................................................................... 274
49.11.2 Spaceplanes............................................................................................. 276
49.12 References ............................................................................................................. 276
49.12.1 General..................................................................................................... 276

50

Refractory and precious metals ..................................................................280


50.1 Introduction............................................................................................................. 280
50.2 Materials................................................................................................................. 280
50.2.1

General..................................................................................................... 280

50.2.2

Characteristics.......................................................................................... 280

50.2.3

Basic properties........................................................................................ 281

50.2.4

Alloys ........................................................................................................ 282

50.3 Applications ............................................................................................................ 282

51

Beryllium .......................................................................................................283
51.1 Introduction............................................................................................................. 283
51.2 Characteristics........................................................................................................ 283
51.2.1

Features ................................................................................................... 283

51.2.2

Applications .............................................................................................. 283

51.3 Products and facilities ............................................................................................ 284


51.3.1

Source ...................................................................................................... 284

51.3.2

Materials ................................................................................................... 284

51.3.3

Grades...................................................................................................... 284
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51.3.4

Fabrication................................................................................................ 285

51.4 Properties ............................................................................................................... 286


51.4.1

Influence of microstructure ....................................................................... 286

51.4.2

Grades...................................................................................................... 286

51.4.3

Mechanical properties .............................................................................. 287

51.4.4

Effect of temperature ................................................................................ 287

51.5 Health and safety ................................................................................................... 294


51.5.1

Facilities.................................................................................................... 294

51.5.2

Health aspects.......................................................................................... 294

51.5.3

Extraction.................................................................................................. 295

51.6 Potential applications ............................................................................................. 295


51.6.1

Resum .................................................................................................... 295

51.7 References ............................................................................................................. 295


51.7.1

52

General..................................................................................................... 295

Ceramic matrix composites.........................................................................296


52.1 Introduction............................................................................................................. 296
52.2 Continuous fibre composites .................................................................................. 296
52.2.1

Matrix groups............................................................................................ 296

52.2.2

Composite development........................................................................... 298

52.2.3

Technology status .................................................................................... 301

52.2.4

Characteristics.......................................................................................... 301

52.3 Carbon fibre reinforced silicon carbide ................................................................... 302


52.3.1

General..................................................................................................... 302

52.3.2

Fibres........................................................................................................ 303

52.3.3

Matrix........................................................................................................ 303

52.3.4

Characteristics.......................................................................................... 304

52.3.5

C/SiC LPI liquid polymer infiltration process............................................. 306

52.3.6

C/C-SiC LSI liquid silicon infiltration process............................................ 314

52.4 Silicon carbide fibre reinforced silicon carbide ....................................................... 315


52.4.1

Technology status .................................................................................... 315

52.4.2

Applications .............................................................................................. 316

52.4.3

Characteristics.......................................................................................... 316

52.4.4

Manufacturing of SiC-SiC ......................................................................... 316

52.5 SiC-SiC composite: Properties ............................................................................... 317


52.5.1

General..................................................................................................... 317

52.5.2

Mechanical properties .............................................................................. 317

52.5.3

Environment ............................................................................................. 321

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52.6 Whisker reinforced composites .............................................................................. 321
52.6.1

Development ............................................................................................ 321

52.6.2

Properties ................................................................................................. 324

52.6.3

Applications .............................................................................................. 324

52.7 Potential applications ............................................................................................. 324


52.7.1

Resum .................................................................................................... 324

52.7.2

High temperature applications.................................................................. 324

52.7.3

High precision optical structures............................................................... 327

52.8 References ............................................................................................................. 329


52.8.1

53

General..................................................................................................... 329

Glass and glass-ceramic matrix composites .............................................337


53.1 Introduction............................................................................................................. 337
53.2 Continuous fibre composites .................................................................................. 337
53.2.1

Characteristics.......................................................................................... 337

53.2.2

Composite development........................................................................... 338

53.2.3

Manufacture.............................................................................................. 339

53.3 Carbon fibre reinforced composites ....................................................................... 340


53.3.1

Material..................................................................................................... 340

53.3.2

Mechanical properties .............................................................................. 340

53.3.3

Applications .............................................................................................. 343

53.4 Silicon carbide fibre reinforced composites ............................................................ 344


53.4.1

Composite development........................................................................... 344

53.4.2

Effect of in-situ fibre strength.................................................................... 346

53.4.3

Effect of fibre-matrix bonding.................................................................... 346

53.5 Silicon carbide reinforced composites: properties .................................................. 346


53.5.1

LAS matrix composites............................................................................. 346

53.5.2

Mechanical properties .............................................................................. 348

53.6 Potential applications ............................................................................................. 358


53.6.1

Technology status .................................................................................... 358

53.7 References ............................................................................................................. 359


53.7.1

54

General..................................................................................................... 359

Carbon-Carbon matrix composites.............................................................362


54.1 Introduction............................................................................................................. 362
54.1.1

Applications .............................................................................................. 362

54.1.2

High temperature...................................................................................... 362

54.1.3

Dimensional stability................................................................................. 362

54.2 Material description ................................................................................................ 362


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54.2.1

Characteristics.......................................................................................... 362

54.2.2

Manufacturing techniques ........................................................................ 364

54.3 C-C composite: Properties ..................................................................................... 367


54.3.1

Mechanical properties .............................................................................. 367

54.4 Oxidation protection systems ................................................................................. 371


54.4.1

Requirements ........................................................................................... 371

54.4.2

Coating development................................................................................ 371

54.4.3

Matrix modification.................................................................................... 371

54.4.4

Design factors........................................................................................... 372

54.5 Potential applications ............................................................................................. 373


54.5.1

Resum .................................................................................................... 373

54.5.2

Commercial availability............................................................................. 373

54.6 Dimensionally stable structures.............................................................................. 374


54.6.1

Introduction............................................................................................... 374

54.6.2

Material characterisation .......................................................................... 375

54.6.3

Manufacturing process ............................................................................. 375

54.6.4

Sandwich structures ................................................................................. 377

54.6.5

Cylinder structures.................................................................................... 378

54.7 References ............................................................................................................. 380


54.7.1

55

General..................................................................................................... 380

Material availability.......................................................................................383
55.1 Introduction............................................................................................................. 383
55.2 Material forms......................................................................................................... 383
55.2.1

General..................................................................................................... 383

55.2.2

Procurement ............................................................................................. 383

55.2.3

Processing................................................................................................ 383

55.3 Standard product forms .......................................................................................... 384


55.3.1

General..................................................................................................... 384

55.3.2

Wrought metal products ........................................................................... 384

55.3.3

Standard materials for net-shape processing........................................... 384

55.4 Net-shape components .......................................................................................... 385


55.5 Data and product support....................................................................................... 385
55.5.1

Material supply ......................................................................................... 385

55.5.2

Property data ............................................................................................ 386

55.6 Data sources .......................................................................................................... 386


55.6.1

European expertise .................................................................................. 386

55.7 Costs ...................................................................................................................... 388

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55.7.1

56

Relative comparisons of materials............................................................ 388

General design rules ....................................................................................391


56.1 Introduction............................................................................................................. 391
56.2 Mechanical response ............................................................................................. 391
56.2.1

General..................................................................................................... 391

56.2.2

Composite development........................................................................... 391

56.2.3

Material characteristics............................................................................. 392

56.3 Stress-strain response ........................................................................................... 394


56.3.1

Isotropic and anisotropic materials ........................................................... 394

56.4 Fracture characteristics .......................................................................................... 397


56.4.1

General..................................................................................................... 397

56.4.2

Near-isotropic materials with modest ductility .......................................... 397

56.4.3

Anisotropic, fibre reinforced MMCs .......................................................... 397

56.4.4

Anisotropic, fibre reinforced CMCs........................................................... 398

56.5 Residual stresses ................................................................................................... 399


56.5.1

Isotropic materials .................................................................................... 399

56.5.2

Anisotropic materials ................................................................................ 399

56.5.3

Influence on microstructure ...................................................................... 399

56.5.4

Influence on structures ............................................................................. 400

56.6 Defects ................................................................................................................... 400


56.6.1

General..................................................................................................... 400

56.6.2

Defect sources.......................................................................................... 400

56.6.3

Isotropic materials .................................................................................... 400

56.6.4

Anisotropic materials ................................................................................ 401

56.7 Machining ............................................................................................................... 402

57

56.7.1

General..................................................................................................... 402

56.7.2

Isotropic metal alloys ................................................................................ 402

56.7.3

Particulate MMC ....................................................................................... 402

56.7.4

Continuous fibre MMC.............................................................................. 402

56.7.5

Carbon-Carbon composites...................................................................... 403

56.7.6

Ceramic matrix composites ...................................................................... 403

56.7.7

Techniques ............................................................................................... 403

Environmental aspects of design................................................................404


57.1 Introduction............................................................................................................. 404
57.2 Space parameters .................................................................................................. 404
57.2.1

Material selection...................................................................................... 404

57.3 Application specifics ............................................................................................... 406


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57.3.1

Material selection...................................................................................... 406

57.4 Protection systems ................................................................................................. 406


57.4.1

Requirements ........................................................................................... 406

57.4.2

Types of protection systems..................................................................... 407

57.4.3

Evaluation of protection systems.............................................................. 407

57.5 References ............................................................................................................. 408


57.5.1

58

General..................................................................................................... 408

Joint selection factors..................................................................................410


58.1 Introduction............................................................................................................. 410
58.2 Basic considerations .............................................................................................. 410
58.2.1

Material characteristics............................................................................. 410

58.2.2

Joint strength ............................................................................................ 413

58.2.3

Joint design factors................................................................................... 414

58.3 Interlayers............................................................................................................... 414


58.3.1

Function and effect on fused joints........................................................... 414

58.4 Joint consolidation.................................................................................................. 415


58.4.1

Temperature and pressure ....................................................................... 415

58.5 Material compatibility.............................................................................................. 416


58.5.1

Chemical and physical.............................................................................. 416

58.6 Load introduction.................................................................................................... 417


58.6.1

Basic principles......................................................................................... 417

58.7 Operational environment ........................................................................................ 418


58.7.1

Environmental factors............................................................................... 418

58.8 References ............................................................................................................. 418


58.8.1

59

General..................................................................................................... 418

Joints between dissimilar materials ...........................................................419


59.1 Introduction............................................................................................................. 419
59.2 Requirements ......................................................................................................... 419

60

59.2.1

Temperature range................................................................................... 419

59.2.2

Structures ................................................................................................. 419

59.2.3

Loading..................................................................................................... 420

59.2.4

Joining methods ....................................................................................... 420

59.2.5

Joint components ..................................................................................... 421

Fusion joining ...............................................................................................422


60.1 Introduction............................................................................................................. 422
60.2 Joining techniques.................................................................................................. 422

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60.2.1

General..................................................................................................... 422

60.2.2

Liquid-phase processing........................................................................... 423

60.2.3

Solid-phase processing ............................................................................ 424

60.3 Joint configuration and performance ...................................................................... 424


60.3.1

Technology status .................................................................................... 424

60.3.2

Joint strength ............................................................................................ 427

60.4 References ............................................................................................................. 428


60.4.1

61

General..................................................................................................... 428

Mechanical connections ..............................................................................432


61.1 Introduction............................................................................................................. 432
61.1.1

Requirements ........................................................................................... 432

61.2 Versatile joints ........................................................................................................ 433


61.2.1

Applications .............................................................................................. 433

61.2.2

Mechanical techniques ............................................................................. 433

62

(Heading number reserved) .........................................................................435

63

(Heading number reserved) .........................................................................435

Figures
Figure 46.2-1 Aluminium alloys: Chemical composition and temper designation ............... 31
Figure 46.6-1 - Al-Li alloys: Fracture toughness versus yield strength for sheet
materials .............................................................................................................. 48
Figure 46.6-2 - Al-Li alloys: Comparison of fatigue crack growth behaviour for 2024T3 and 8090-T81 ................................................................................................. 49
Figure 46.6-3 - Al-Li alloys: Comparison of fatigue crack growth behaviour for 2024T3 and 2091-T8X................................................................................................. 50
Figure 46.6-4 - Al-Li alloys: Comparison of fatigue crack growth behaviour LITAL A
(8090) forgings at 20C........................................................................................ 52
Figure 46.7-1 - Al-Li Alloys: Influence of temper on stress corrosion cracking initiation
for 8090 plates, S-T direction............................................................................... 55
Figure 46.9-1 - Al-Li alloys: Applications - Space Shuttle external tank, major changes
from LWT ............................................................................................................. 62
Figure 46.9-2 - Al-Li alloys: Applications Airbus A380 floor beams..................................... 64
Figure 46.10-1 - Aluminium ODS alloys: Comparison of elevated temperature tensile
strength for various mechanically alloyed materials with Al-2618........................ 66
Figure 46.10-2 - Aluminium ODS alloys: Comparison of elevated temperature tensile
strength, proof stress and ductility ....................................................................... 67
Figure 46.10-3 - Aluminium ODS alloys: Effect of consolidation method on proof
stress ................................................................................................................... 68
Figure 46.10-4 - Aluminium ODS alloys: Effect of consolidation method on ductility............. 69

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Figure 46.10-5 - Aluminium ODS alloys: Creep response at 400C for 3 stress levels ......... 70
Figure 46.10-6 - Aluminium ODS alloys: Comparison of tensile creep curves at
different stress levels with Al-2618 ...................................................................... 71
Figure 46.10-7 - Aluminium ODS alloys: Comparison of fatigue resistance with Al2024..................................................................................................................... 72
Figure 46.12-1 Al-MMCs: Overview of manufacturing processes ....................................... 78
Figure 46.14-1 Al-MMCs: Typical elevated temperature properties of 2009/SiC-T4
DRA compared with conventional wrought aluminium alloys .............................. 92
Figure 46.14-2 Al-MMCs: Typical room and elevated temperature fatigue properties
of 2009/SiC DRA compared with conventional wrought aluminium alloys........... 93
Figure 46.17-1 Al-MMCs: Comparison between Al-continuously reinforced alumina
fibre composites and other materials................................................................. 113
Figure 47.2-1 - Titanium alloys: Effect of temperature on stiffness ...................................... 132
Figure 47.2-2 - Titanium alloys: Effect of temperature on strength ...................................... 133
Figure 47.2-3 - Titanium alloys: Creep properties ................................................................ 134
Figure 47.2-4 - Titanium alloys: Fatigue strength................................................................. 135
Figure 47.2-5 - Titanium alloys: UTS at elevated temperature for IMI 829 and Ti-1100 ...... 136
Figure 47.4-1 - SPF/DB fabrication: Titanium alloy m-values as a function of strain
rate..................................................................................................................... 140
Figure 47.7-1 - Titanium matrix composites: Fatigue life from in-phase and out-ofphase thermal-mechanical fatigue tests ............................................................ 149
Figure 48.2-1 - Superalloys: Development Curve ................................................................ 160
Figure 48.2-2 - Superalloys: Cooled turbine blade............................................................... 168
Figure 48.2-3 - Operating regimes for Space Shuttle and aero-engine turbines.................. 170
Figure 48.3-1 - ODS superalloys: Comparison of yield strength with casting
superalloys......................................................................................................... 176
Figure 48.3-2 - ODS superalloys: Comparison of tensile elongation with casting
superalloys......................................................................................................... 177
Figure 48.7-1 - Effect of hydrogen on creep rupture of Inconel 718 STA2........................... 192
Figure 48.7-2 - Effect of hydrogen on creep rupture of Inconel 718 STA1........................... 193
Figure 48.7-3 - Effect of hydrogen on creep rupture of Inconel 625..................................... 193
Figure 48.7-4 - Effect of hydrogen on creep rupture of Waspalloy....................................... 194
Figure 48.7-5 - Effect of hydrogen on creep rupture of MAR-M-246 conventionally
cast .................................................................................................................... 194
Figure 48.7-6 - Effect of hydrogen on creep rupture of MAR-M-246 directionally
solidified............................................................................................................. 195
Figure 48.7-7 - Effect of hydrogen on creep rupture of MAR-M-246 single crystal .............. 195
Figure 48.7-8 - Low cycle fatigue (LCF) life of Inconel 718 against temperature................. 196
Figure 48.7-9 - Superalloys: Crack growth rate of IN718 under various stress
intensities and hydrogen environments ............................................................. 198

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Figure 48.7-10 - Superalloys: Crack growth rate of IN718 as a function of cyclic rates
and hydrogen environments .............................................................................. 199
Figure 48.12-1 - Thermal barrier coating: Typical construction materials ............................ 210
Figure 48.13-1 - Coating design: Effect of temperature gradients on diffusion .................... 215
Figure 48.13-2 - Coating design: Example of failure diagram for IN-738LC ........................ 219
Figure 48.13-3 - Coating design: High cycle fatigue characteristics of coated CMSX-2......... 221
Figure 48.13-4 - Coating design: Schematic creep curves for substrate metal and
coating ............................................................................................................... 222
Figure 48.13-5 - Coating design: Schematic creep curves for coated system ..................... 223
Figure 48.13-6 - Coating design: Effect of coatings on stress rupture properties of
CSMX-2 alloy..................................................................................................... 224
Figure 48.13-7 - Coating design: Effect of plasma sprayed coating on stress rupture
properties of Cotac 784 alloy ............................................................................. 225
Figure 48.13-8 - Coating design: Typical creep fatigue effects for cooled gas turbine
blades ................................................................................................................ 227
Figure 48.15-1 - Superalloys: Space applications Hot structure ....................................... 229
Figure 49.6-1 - Titanium aluminides: Effect of temperature on Youngs modulus................ 252
Figure 49.6-2 - Titanium aluminides: Two-phase alloys - Ductility versus temperature ....... 253
Figure 49.6-3 - Titanium aluminides: Comparison of fatigue characteristics with Rene
95 superalloy ..................................................................................................... 254
Figure 49.6-4 - Titanium aluminides: Two-phase alloys Thermal diffusivity versus
temperature ....................................................................................................... 256
Figure 49.6-5 - Titanium aluminides: Two-phase alloys Specific heat versus
temperature ....................................................................................................... 257
Figure 49.6-6 - Titanium aluminides: Two-phase alloys Thermal conductivity versus
temperature ....................................................................................................... 258
Figure 49.6-7 - Titanium aluminides: Two-phase alloys Coefficient of thermal
expansion versus temperature .......................................................................... 260
Figure 49.7-1 - Iron aluminides: Room temperature behaviour of Fe-40Al(at. %) +
boron additions in different conditions ............................................................... 262
Figure 49.7-2 - Iron aluminides: Effect of conditioning and elevated temperature on
strength of Yttria ODS alloy system ................................................................... 263
Figure 49.10-1 - Intermetallic matrix composites: Characteristics of orthorhombic
phase titanium aluminide matrix ........................................................................ 271
Figure 49.10-2 - Intermetallic matrix composites: TiAl/SiC composite - Insamet foilfibre-foil processing steps ................................................................................. 273
Figure 49.11-1 - Intermetallics: Potential applications - Elevated temperature specific
strengths of materials ........................................................................................ 275
Figure 49.11-2 - Intermetallics: Potential applications - Outer skin structures for space
applications........................................................................................................ 276
Figure 51.4-1 - Beryllium S-200 grades: Effect of temperature on 0.2% yield strength ....... 289
Figure 51.4-2 - Beryllium S-200 grades: Effect of temperature on ultimate tensile
strength.............................................................................................................. 289

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Figure 51.4-3 - Beryllium S-200 grades: Effect of temperature on elongation ..................... 290
Figure 51.4-4 - Beryllium: Effect of temperature on thermal conductivity............................. 292
Figure 51.4-5 - Beryllium: Effect of temperature on diffusivity.............................................. 292
Figure 51.4-6 - Beryllium: Effect of temperature on expansion ............................................ 293
Figure 51.4-7 - Beryllium: Effect of temperature on specific heat capacity .......................... 294
Figure 52.2-1 - CMC composite development...................................................................... 298
Figure 52.2-2 - CMC composite development: Material combinations................................. 301
Figure 52.3-1 - Ceramic matrix composites: C-SiC load versus displacement curves
at RT and 1600C .............................................................................................. 305
Figure 52.3-2 - C/SiC LPI (EADS-ST): Manufacturing and inspection flow chart................. 307
Figure 52.3-3 - C/SiC LPI (EADS-ST): Specific heat capacity ............................................. 309
Figure 52.3-4 - C/SiC LPI (EADS-ST): Thermal conductivity ............................................... 310
Figure 52.3-5 - C/SiC LPI (EADS-ST): Surface emittance, with anti-oxidation coating........ 311
Figure 52.3-6 - C/SiC LPI (EADS-ST): Architecture of multi-layer, self-healing OPS .......... 312
Figure 52.3-7 - C/SiC LPI (EADS-ST): Function of layers in OPS ....................................... 313
Figure 52.3-8 - C/C-SiC LSI (DLR): Mechanical properties for XT and XB grades .............. 315
Figure 52.5-1 - SiC-SiC composites: High temperature flexural strength of various
compositions...................................................................................................... 317
Figure 52.5-2 - SiC-SiC composite (bidirectional): Typical tensile stress-strain curve ......... 318
Figure 52.5-3 - SiC-SiC composites: Typical bending strength versus temperature
profiles compared with C-SiC composite........................................................... 319
Figure 52.5-4 SiC-SiC composites: Representative through-thickness fracture
toughness versus temperature compared with C-SiC ....................................... 320
Figure 52.7-1 Ceramic matrix composites: FOLDHOST concept for deployable
decelerator......................................................................................................... 326
Figure 52.7-2 Ceramic matrix composites: Applications X-38 body flaps ...................... 327
Figure 52.7-3 - Ceramic matrix composites: Applications Optical communications
systems.............................................................................................................. 328
Figure 53.5-1 - Glass-ceramic composites: Tensile stress-strain curve for
unidirectional (0) SiC/LAS-II at room temperature ........................................... 347
Figure 53.5-2 - Glass-ceramic composites: Flexural stress-strain curve for
SiC/BMAS-III...................................................................................................... 348
Figure 53.5-3 - SiC reinforced glass-ceramic composite: Flexural strength versus
temperature for unidirectional SiC/LAS ............................................................. 349
Figure 53.5-4 - SiC reinforced glass-ceramic composite: Flexural strength versus
temperature for unidirectional SiC/LAS-III ......................................................... 350
Figure 53.5-5 - SiC reinforced glass-ceramic composite: Compressive stress-strain
response of 0, 0/90, and 45 SiC/LAS-III, at 23C....................................... 351
Figure 53.5-6 - SiC reinforced glass-ceramic composite: Flexural stress-strain data
for 0/45/90 SiC/LAS for a wide temperature range...................................... 351

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Figure 53.5-7 - SiC reinforced glass-ceramic composite: Strengths versus
temperature for monolithic LAS (Pyroceram) and unidirectional LAS/SiC
(Compglas) ........................................................................................................ 352
Figure 53.5-8 - SiC reinforced glass-ceramic composite: Dependence of failure
strengths with temperature and loading mode for 0 Compglas and
monolithic Pyroceram ........................................................................................ 353
Figure 53.5-9 - SiC reinforced glass-ceramic composite: Comparison of flexural
strength under various loading conditions for 0 SiC/LAS at 22C .................... 354
Figure 53.5-10 - SiC reinforced glass-ceramic composite: Comparison of flexural
strength under various loading conditions for 0 SiC/LAS at 600C .................. 355
Figure 53.5-11 - SiC reinforced glass-ceramic composite: Comparison of flexural
strength under various loading conditions for 0 SiC/LAS at 900C .................. 355
Figure 53.5-12 - SiC reinforced glass-ceramic composite: Room temperature fourpoint flexural fatigue of 0 SiC/LAS-II ................................................................ 356
Figure 53.5-13 - SiC reinforced glass-ceramic composite: Room temperature tensile
fatigue of 0 SiC/LAS-III..................................................................................... 357
Figure 53.5-14 - SiC reinforced glass-ceramic composite: Room temperature uniaxial
tensile fatigue of 0/90 SiC/LAS-II and 0/90 SiC/LAS-III ............................... 357
Figure 54.2-1 - Carbon-carbon composites: Schematic diagram of material selection
and processing routes ....................................................................................... 364
Figure 54.2-2 - Carbon-carbon composites: 4-D fibre architecture in SEPCARB 4-D........ 365
Figure 54.2-3 - Carbon-carbon composites: 3-D fibre preforms........................................... 365
Figure 54.2-4 - Carbon-carbon composites: Examples of multidirectional fibre
preforms............................................................................................................. 366
Figure 54.3-1 - Carbon-carbon composites: Predicted modulus values from
conventional theory without a matrix contribution.............................................. 368
Figure 54.3-2 - Carbon-carbon composites: Tensile response of 3-D composite ................ 369
Figure 54.3-3 - Carbon-carbon composites: Tensile response of 4-D composite ................ 370
Figure 54.6-1 Carbon-carbon composites: Manufacturing process equipment................. 376
Figure 54.6-2 Carbon-carbon composites: GOCE gradiometer ........................................ 377
Figure 54.6-3 Carbon-carbon composites: Test cylinders................................................. 379
Figure 54.6-4 Carbon-carbon composites: Pleiades flight cylinder ................................... 379
Figure 56.3-1 - Metals and MMCs: Stress-strain response compared with CFRP............... 395
Figure 56.3-2 - Metals and ceramic-based materials: Stress-strain response ..................... 396

Tables
Table 46.2-1 - Aluminium alloys: Comparison of national specifications for wrought
alloys.................................................................................................................... 33
Table 46.2-2 - Aluminium alloys: Comparison of national specifications for casting
alloys.................................................................................................................... 35
Table 46.4-1 - Al-Li alloys: Commercial sources and products .............................................. 40
Table 46.5-1 - Al-Li alloys: Typical properties compared with 7075....................................... 42

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Table 46.6-1 - Al-Li alloys: Mechanical properties ................................................................. 45
Table 46.6-2 - Al-Li alloys: Fracture properties ...................................................................... 47
Table 46.6-3 - Al-Li alloys: Fatigue crack growth rate of 1441 and 1163 sheet ..................... 51
Table 46.6-4 - Al-Li alloys: Design tensile strengths for extruded 8090 alloys ....................... 53
Table 46.7-1 - Al-Li alloys: Alloy 8090 - Results of stress corrosion tests.............................. 55
Table 46.7-2 - Al-Li alloys: Tentative stress corrosion thresholds for 8090 alloy ................... 56
Table 46.7-3 - Al-Li alloys: Results of stress corrosion test on sheet material, as
performed by NLR ............................................................................................... 56
Table 46.7-4 - Al-Li Alloys: SCC initiation behaviour of 8090 alloy compared with that
of conventional alloys .......................................................................................... 56
Table 46.7-5 - Al-Li alloys: Current commercial alloys summary of corrosion
resistance ............................................................................................................ 57
Table 46.8-1 Al-Li alloys: 2195-T8 plate and weldments - summary of fatigue crack
growth rate........................................................................................................... 59
Table 46.9-1 Al-Li alloys: Applications mass savings in Space Shuttle external
tank ...................................................................................................................... 61
Table 46.11-1 - RSP aluminium alloys: Ambient temperature use - nominal alloy
compositions........................................................................................................ 74
Table 46.11-2 - RSP aluminium alloys: Ambient temperature use -tensile properties ........... 74
Table 46.11-3 - RSP aluminium alloys: Elevated temperature - modified property
goals (minimum values) for shaped extrusions of P/M alloy CZ42 ...................... 75
Table 46.11-4 - RSP aluminium alloys: Room and elevated temperature tensile
properties of planar flow cast alloy FVS-0812 ..................................................... 76
Table 46.11-5 - RSP aluminium alloys: Room and elevated temperature tensile
properties of alloy FVS-1212 ............................................................................... 76
Table 46.11-6 - RSP aluminium alloys: Elastic modulus, density and weight-saving
parameters for thermally stable RS-P/M alloys ................................................... 76
Table 46.12-1 Al-MMCs: Summary of suppliers and capabilities........................................ 80
Table 46.13-1 Al-MMCs: Typical properties of SiB6 silicon hexaboride particulate
reinforcement Hexon ....................................................................................... 83
Table 46.13-2 Al-MMCs: Typical properties of constituents used for MMCC
MetGraf Al/Cf composites ................................................................................ 84
Table 46.14-1 Al-MMCs: Room temperature properties of AMC225xe and
AMC640xa ........................................................................................................... 87
Table 46.14-2 Al-MMCs: Elevated temperature properties of AMC225xe plate................. 88
Table 46.14-3 Al-MMCs: Elevated temperature properties of extruded AMC225xe
compared with Duralcan MMC's ........................................................................ 89
Table 46.14-4 Al-MMCs: Typical room temperature properties of DWA 2009/SiCp
and 6092/SiCp composites.................................................................................. 90
Table 46.14-5 Al-MMCs: Typical room temperature tensile properties of DWA
2009/SiCp extruded composites.......................................................................... 91
Table 46.14-6 Al-MMCs: Typical properties of CPS Al/SiCp composites........................... 94

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Table 46.14-7 Al-MMCs: Typical room temperature properties of TTC Al/SiCp
composites........................................................................................................... 95
Table 46.14-8 Al-MMCs: Typical properties of composites from M Cubed
Technologies ....................................................................................................... 96
Table 46.14-9 Al-MMCs: Typical properties of MMCC METSIC Al/SiCp
composite compared with aluminium and steel ................................................... 97
Table 46.14-10 Al-MMCs: Typical properties of Millenium Materials Carolite SiB6
particulate reinforced composites ........................................................................ 98
Table 46.14-11 Al-MMCs: Typical room temperature properties of MMCC
MetGraf Al/Cf composites ............................................................................... 99
Table 46.14-12 Al-MMCs: Typical properties of MMCC MetGraf Al/Cf composites
compared with other thermal packaging materials ............................................ 100
Table 46.14-13 Al-MMCs: Properties of Osprey CE Al-Si in-situ composite alloys ........ 101
Table 46.15-1 Al-MMCs: Typical properties of continuous reinforcing fibres ................... 103
Table 46.15-2 Al-MMCs: Typical properties of 3M Nextel 610 alumina fibre ................ 104
Table 46.16-1 Al-MMCs: Typical properties of continuously reinforced MMCs ................ 108
Table 46.16-2 Al-MMCs: Typical properties of 3M unidirectional Al-Nextel
composites......................................................................................................... 109
Table 46.16-3 Al-MMCs: Typical properties of 3M MMC push rods ................................. 110
Table 46.16-4 Al-MMCs: Typical properties of TRL MetPreg Al/Al2O3f continuous
fibre composites................................................................................................. 111
Table 47.2-1 - Titanium alloys: Effects of alloying elements on microstructure ................... 127
Table 47.2-2 - Titanium alloys: Influence of processing temperatures on near- alloys ...... 128
Table 47.2-3 - Titanium alloys for aerospace use: Characteristics ...................................... 128
Table 47.2-4 - Titanium alloys: Indicative mechanical properties......................................... 131
Table 47.2-5 - Titanium alloys: Physical properties.............................................................. 137
Table 47.7-1 - Titanium matrix composites: Typical room temperature tensile
properties........................................................................................................... 145
Table 47.7-2 - Titanium matrix composites: Typical strengths of UD SIGMA SiC
reinforced alloys................................................................................................. 146
Table 47.7-3 - Titanium matrix composites: Fatigue properties ........................................... 147
Table 47.8-1 - Titanium alloys: Effect of hydrogen............................................................... 150
Table 47.9-1 - Titanium alloys: Ignition and burn characteristics ......................................... 151
Table 47.10-1 - Titanium alloys: Potential coating systems ................................................. 152
Table 48.2-1 - Superalloys: Property requirements for engine components ........................ 161
Table 48.2-2 - Superalloys: For aero-engine component applications................................. 163
Table 48.2-3 - Superalloys: Typical mechanical properties.................................................. 164
Table 48.2-4 - Superalloys: Comparison of rocket engine and aircraft engine turbine
operation............................................................................................................ 169
Table 48.2-5 - Superalloys: Potential blade materials under evaluation for rocket
engine turbine components ............................................................................... 170

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Table 48.2-6 - Single crystal superalloys: Potential use in rocket engine turbines .............. 171
Table 48.3-1 - Reinforcing phases in directionally solidified (DS) eutectic superalloys ....... 172
Table 48.3-2 - Directionally solidified (DS) superalloys........................................................ 172
Table 48.3-3 - Single crystal (SC) superalloys ..................................................................... 173
Table 48.3-4 - Powder metallurgy of superalloys ................................................................. 174
Table 48.3-5 - Powder metallurgy nickel-based superalloys: Composition.......................... 174
Table 48.3-6 - Oxide dispersion strengthened (ODS) superalloys: Composition................. 175
Table 48.5-1 - Superalloy composites: Reinforcement phases............................................ 178
Table 48.5-2 - Superalloys: Typical mechanical properties of matrix materials for
composites......................................................................................................... 179
Table 48.6-1 - Tungsten fibre reinforced composites: Reinforcement and superalloy
matrix ................................................................................................................. 180
Table 48.6-2 - Tungsten fibre reinforced, nickel-based superalloys: Tensile properties
of development composites ............................................................................... 181
Table 48.6-3 - Tungsten fibre reinforced, cobalt-based superalloys: Tensile properties
of development composites ............................................................................... 182
Table 48.6-4 - Tungsten fibre reinforced, iron-based superalloys: Tensile properties of
development composites ................................................................................... 183
Table 48.6-5 - Tungsten fibre reinforced superalloy: Room temperature tensile
strength of thermally cycled composite.............................................................. 185
Table 48.6-6 - Summary of tungsten fibre reinforced superalloy (TFRS) systems .............. 186
Table 48.7-1 - Established mechanisms of hydrogen degradation in materials................... 187
Table 48.7-2 - Characteristics of hydrogen environment embrittlement (HEE).................... 188
Table 48.7-3 - Sensitivity of superalloys to hydrogen........................................................... 189
Table 48.7-4 - Effect of hydrogen on MAR-M-246 superalloys ............................................ 190
Table 48.7-5 - Effect of crystal anisotropy on RT hydrogen performance of PWA 1480
single crystal alloy.............................................................................................. 190
Table 48.7-6 - Effect of hydrogen on directionally solidified eutectic (DSE) and oxide
dispersion strengthened (ODS) superalloys ...................................................... 191
Table 48.7-7 - Low cycle fatigue (LCF) life degradation of superalloys in hydrogen
environments ..................................................................................................... 197
Table 48.8-1 - Ignition and burn characteristics of materials in oxygen environments......... 202
Table 48.10-1 - Diffusion coatings for superalloys: Various types and use.......................... 205
Table 48.10-2 - Diffusion coatings: Commercially available types ....................................... 207
Table 48.11-1 - Commercially available MCrAlY overlay coatings....................................... 208
Table 48.11-2 - Overlay coatings: Later studies with MCrAlY type coatings and
superalloys substrates ....................................................................................... 209
Table 48.12-1 - Thermal barrier coatings: Material systems ................................................ 210
Table 48.12-2 - Thermal barrier coating technology: Later studies...................................... 211
Table 48.13-1 - Coating design: Factors associated with coating systems for
oxidation and corrosion resistance .................................................................... 212

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Table 48.13-2 - Coating design: Comparison of technical factors for diffusion and
overlay coatings................................................................................................. 213
Table 48.13-3 - Coating design: Tensile properties of coated material systems.................. 218
Table 48.13-4 - Coating design: Fatigue properties of coated material systems ................. 220
Table 48.13-5 - Coating design: Creep properties of coated material systems ................... 226
Table 49.2-1 - Intermetallic compounds: Comparison of aluminide groups ......................... 235
Table 49.3-1 - Nickel aluminides: Characteristics of NiAl and Ni3Al intermetallic
compounds ........................................................................................................ 238
Table 49.3-2 - Nickel aluminides: Compositions (based on Ni3Al) under development ....... 239
Table 49.3-3 - Nickel aluminides: Composition, material designation and sources ............. 239
Table 49.4-1 - Nickel aluminides: Mechanical properties at elevated temperatures
with various conditioning.................................................................................... 241
Table 49.4-2 - Nickel aluminides: Modulus at elevated temperature ................................... 242
Table 49.4-3 - Nickel aluminides: Preliminary fatigue test data for IC218 and IC221 .......... 243
Table 49.4-4 - Nickel aluminides: Coefficient of thermal expansion..................................... 244
Table 49.5-1 - Titanium aluminides: Comparison of characteristics..................................... 245
Table 49.5-2 - Titanium aluminides: Typical compositions................................................... 246
Table 49.6-1 - Titanium aluminides: Mechanical properties for materials processed by
different techniques ........................................................................................... 248
Table 49.6-2 - Titanium aluminides: Indication of creep properties...................................... 255
Table 49.7-1 - Iron aluminides: Characteristics.................................................................... 261
Table 49.7-2 - Iron aluminides: Composition of development materials .............................. 261
Table 49.8-1 - Aluminides: Summary of manufacture and consolidation techniques........... 264
Table 49.9-1 - Further development: Intermetallic compounds............................................ 267
Table 49.10-1 - Intermetallic matrix composites: Summary of compounds and
reinforcements ................................................................................................... 269
Table 49.10-2 - Intermetallic matrix composites: Requirements for a reinforcement
fibre.................................................................................................................... 270
Table 50.2-1 - Refractory and precious metals: Attributes and disadvantages.................... 281
Table 50.2-2 - Refractory and precious metals: Basic physical properties .......................... 281
Table 50.2-3 - Refractory metal alloys: Examples................................................................ 282
Table 51.2-1 - Beryllium: Characteristics ............................................................................. 283
Table 51.3-1 Beryllium: Grades......................................................................................... 285
Table 51.4-1 - Beryllium grades: Composition and tensile properties.................................. 287
Table 51.4-2 - Beryllium grades S-200-F and SR-200-E: Mechanical properties at
various temperatures ......................................................................................... 288
Table 51.4-3 - Beryllium: Effect of temperature on modulus and physical properties .......... 291
Table 52.2-1 - Ceramic matrix composites: Fibre and matrix combinations with
sources of development/investigation................................................................ 299

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Table 52.2-2 - Development continuous fibre reinforced ceramic matrix composites:
Typical properties .............................................................................................. 302
Table 52.3-1 - Ceramic matrix composites: Typical properties of C-SiC composites
produced by different processing methods ........................................................ 305
Table 52.3-2 - C/SiC LPI (EADS-ST): Fabrication and inspection steps.............................. 307
Table 52.3-3 - C/SiC LPI (EADS-ST): Mechanical properties at different temperatures ...... 309
Table 52.3-4 - C/SiC LPI (EADS-ST): OPS used in OLCHOS programme ......................... 313
Table 52.3-5 - C/C-SiC LSI (DLR): Mechanical properties for different grades ................... 314
Table 52.5-1 - SiC-SiC composites: Indicative properties, as measured by SEP
(France) ............................................................................................................. 320
Table 52.6-1 - Ceramic matrix composites: Ceramic whiskers ............................................ 321
Table 52.6-2 - Ceramic matrix composites: Development whisker and matrix
combinations...................................................................................................... 323
Table 53.2-1 - Glass and glass-ceramic matrices ................................................................ 338
Table 53.3-1 - Carbon fibre/borosilicate unidirectional composites: Mechanical
properties........................................................................................................... 341
Table 53.3-2 - Unidirectional and angle-ply tensile data for Hercules HMU carbon
fibre reinforced 7740 borosilicate glass composite............................................ 342
Table 53.3-3 - Mechanical test data for notched 0/90 reinforced HMU/7740
composites......................................................................................................... 343
Table 53.4-1 - SiC reinforced glass-ceramic composites: Comparison of RT
unidirectional (0) properties with SiC fibre reinforced epoxy ............................ 345
Table 54.3-1 - Carbon-carbon composites: Indicative mechanical properties ..................... 367
Table 54.4-1 - Carbon-carbon composites: Requirements for oxidation protection
systems for two applications.............................................................................. 372
Table 54.6-1 Carbon-carbon composites: Basic properties .............................................. 375
Table 55.6-1 - Advanced metals and ceramics: Significant European sources of
expertise ............................................................................................................ 387
Table 55.7-1 - Advanced metals and ceramics: Direct material costs ................................. 389
Table 55.7-2 - Advanced metals and ceramics: Relative costs of components ................... 390
Table 57.2-1 - Advanced metal- and ceramic-based materials: Relevance of space
parameters to material selection........................................................................ 405
Table 58.2-1 - Dissimilar materials for joints ........................................................................ 411
Table 59.2-1 - Joints between dissimilar materials: Representative list of materials ........... 420
Table 60.2-1 - Comparison of jointing and consolidation techniques................................... 423
Table 60.3-1 - Fused joints: Technology review of joints ..................................................... 425
Table 60.3-2 - Fusion joints: Published bond strengths for various joints ............................ 427

26

ECSSEHB3220Part5A
20March2011

Introduction
TheStructuralmaterialshandbook,ECSSEHB3220,ispublishedin8Parts.
Aglossaryofterms,definitionsandabbreviatedtermsforthesehandbooksiscontainedinPart8.

Thepartsareasfollows:
Part1

Overviewandmaterialpropertiesandapplications

Clauses19

Part2

Designcalculationmethodsandgeneraldesignaspects

Clauses1022

Part3

Loadtransferanddesignofjointsanddesignofstructures

Clauses2332

Part4

Integritycontrol,verificationguidelinesandmanufacturing

Clauses3345

Part5

Newadvancedmaterials,advancedmetallicmaterials,
generaldesignaspectsandloadtransferanddesignofjoints

Clauses4663

Part6

Fractureandmaterialmodelling,casestudiesanddesignand
integritycontrolandinspection

Clauses6481

Part7

Thermalandenvironmentalintegrity,manufacturingaspects, Clauses82107
inorbitandhealthmonitoring,softmaterials,hybrid
materialsandnanotechnoligies

Part8

Glossary

27

ECSSEHB3220Part5A
20March2011

46 Aluminium alloys and their


composites
46.1 Introduction
46.1.1

General

Aluminium alloys are established in aerospace, with many years of application and service
experience.
Alloy developments are described that have aimed at improving the mechanical characteristics of
basicaluminiumalloysandthelimitationsonservicetemperature.
The ability to improve dimensional stability by combining alloys with low CTE materials is an
advantageforspaceuse.
Thematerialsdescribedaredividedintothemaingroups:

Conventionalaluminiumalloys.

Newaluminiumalloys.

MMCmetalmatrixcomposites.

FMLfibremetallaminates

46.1.2

Conventional aluminium alloys

In recent years it has become clear that many of the problems associated with conventional
aluminium alloys, e.g. inconsistent fracture properties, were associated with the nature, size,
morphologyand distribution of intermetallic particles, both intended (as the strengthening phase)
and unintended (from tramp elements). Attention has therefore focussed on improving both alloy
chemistry and process technology to give more desirable structures in the finished material. In
additiontoalloymodifications,thishasresultedintheintroductionofmodifiedthermomechanical
treatments (combinations of heat treatments and hot or cold working) with new temper
designations,whichareexpansionsofthebasictempers,[See:46.2].
Specific data on conventional aluminium alloys are not given in this handbook, [See: MMPDS01
andPMP],Ref.[4671],[4672].

46.1.3

New aluminium alloys

Thesecanbegroupedas:

Aluminiumlithium(AlLi)alloys.[See:46.4]

Powdermetallurgy(P/M)alloys:

28

ECSSEHB3220Part5A
20March2011

oxidedispersionstrengthenedalloys(ODS),havingadditionsofsmall,stableparticles,
[See:46.10].

rapidly solidified powder (RSP) powder atomised materials which, due to rapid
cooling,havedifferentalloyingmechanisms,[See:46.11].

46.1.4

MMC - metal matrix composites

Various MMC material combinations are described, with emphasis on their typical mechanical
propertiesandhowtheseareaffectedbyelevatedtemperatures.Thesematerialscanbeclassedas
compositeshaving:

discontinuousreinforcementphases(particlesorshortfibres),[See:46.12],

continuousfibrereinforcement,[See:46.14].

46.1.5

FML - fibre metal laminates

FMLsarelaminatedsheetmaterialscontainingeitheraramidfibres(ARALL),glassfibres(GLARE)
orthenewerderivativeswithcarbonfibres(CARE),usuallybetweenthinsheetsofaluminiumalloy.
Originally developed for aircraft skin structures, the materials and characteristics of interest for
spaceusearedescribed,[See:Chapter100].
NOTE

46.1.6

Many of the materials described are development products;


somearemoreadvancedcommerciallythanothers.Allofthe
propertydataquotedistypicalvalues.

Material availability

After a boom in the development of advanced aluminiumbased materials, there have been some
notable withdrawals of previously commerciallyavailable products, Ref. [4647]. Information on
alternativematerialsispresentedinthehandbook,wherepossible.
Someorganisationsthathavewithdrawnproductsorceasedtradingare:

CedegurPechineyhasbeentakenoverbyAlcan.

ReynoldsMetalshavebeentakenoverbyAlcoa.
NOTE

Alcan and Alcoa are the remaining major suppliers for


aluminiumlithiumalloys.

BPMetalCompositesLtd.(Farnborough,UK)hasclosedtheirsiteandnolongermanufacture
particulate reinforced aluminium alloys. BP continues with SIGMA fibres for titanium
composites.TheFarnboroughsiteisnowoperatedbyAMCLtd.whoofferadvancedalloys
andMMCsproducedbypowdermetallurgy.

AMS Ltd.(previously Cray AdvancedMaterials) have ceased trading. Previously they were
exponents of the use of LPF liquid metal pressure forming for manufacturing continuous
fibreandpreformreinforcedcompositecomponents.Similarprocesstechniquesareinusein
theUSA,[See:46.14].

CosprayLtd.(partofAlcan)hasclosed.PreviouslytheyusedtheOspreyprocesstoproduce
particulate reinforced aluminium alloys. However, a German Osprey licensee, PEAK
Werkstoff(partofErbslhGruppe,D)producesarangeofaluminiumalloysandMMCs.

29

ECSSEHB3220Part5A
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Alcan does not actively market Duralcan particulate reinforced MMCs, but the casting
alloysareavailabletoorder.

Similarly,whilstaverylargenumberofaluminiumalloys,includinganumberofAlLialloys,have
beenregisteredwiththeAluminumAssociation(USA),Ref[4646],[4659],onlyalimitednumberof
alloysareofcommercialsignificanceandreadilyavailable.Likewise,furtherdevelopmentsofalloy
compositions,tempersandprocesstechnologiescontinuetoshowimprovementsinproperties.
It is therefore imperative that the designer consultswith the prospective material suppliersbefore
makinganycommitmenttotheuseofanyparticularmaterial.

46.2 Conventional aluminium alloys


46.2.1

General

Aluminium alloys are established aerospace materials worldwide. Their performance and
limitations, which are known for a wide range of environments, are based on over 40years
accumulatedresearch,development,applicationandserviceexperience.
The European Aluminium Association (EAA) provides details on aluminium alloys, markets and
linkstomaterialsuppliersinvariousmarketsectors,includingaerospace.
Thistopicservesasareferenceforthoseconventionalaluminiumalloysnowfindinguseasmatrix
materialsforthevariousmetalmatrixcomposites,Ref.[461],[462],[463],[4671].

[See:ECSSQ7071fordetailsofaluminiumalloysforspaceuse]

Fordesigndata,seeMMPDS01,Ref[4671]whichhassupersededMILHDBK5,Ref.[463].

46.2.2

Chemical composition

46.2.2.1

General

46.2.1 summarises the basis for classifying aluminium alloy composition under the International
system,Ref.[4660].

30

ECSSEHB3220Part5A
20March2011
Alloy
group

Wrought Alloys

Cast Alloys

Major alloying elements

Alloy
group

Major alloying elements

1XXX

99.00 percent minimum aluminium

1XX.0

99.00 percent minimum aluminium

2XXX

Copper

2XX.0

Copper

3XXX

Manganese

3XX.0

Silicon with added copper and/or magnesium

4XXX

Silicon

4XX.0

Silicon

5XXX

Magnesium

5XX.0

Magnesium

6XXX

Magnesium and Silicon

6XX.0

Unused Series

7XXX

Zinc

7XX.0

Zinc

8XXX

Other Elements

8XX.0

Tin

9XXX

Unused Series

9XX.0

Other Elements

For both cast and wrought alloys, the first digit indicates the main alloying element(s). For cast alloys only the
product form is indicated by the digit after the point; 0 = castings, 1 and 2 = ingot.

Wrought alloys: the second digit,


initially 0, indicates minor
modifications to the basic alloy
composition.

Cast alloys: modifications to the original alloy are


indicated by a serial letter added as a prefix,
starting with A but omitting I, O, Q and X.

Condition (Temper) is indicated by a suffix letter separated by a hyphen. The basic temper can be followed by a
further alpha-numeric code (optional)

Basic temper designations

As fabricated. Products for which there


are no special thermal or strain
hardening processes.

Annealed. Used for cast products to


improve ductility or dimensional
stability and for wrought products to
give lowest strength.

Solution heat treated. Unstable temper,


used only for alloys which
spontaneously age harden at room
temperature.

Strain hardened. For wrought products which are


strengthened by working, with or without thermal
treatments. The H is always followed by one or
more further digits.

Thermally treated to stable temper other than F, O


or H. Used for products thermally treated with or
without strain hardening. The T is always followed
by one or more further digits.
NOTE: The letter P can be used, after the temper
designation, to indicate variations to H, T or O
tempers agreed between supplier and purchaser.

Figure46.21Aluminiumalloys:Chemicalcompositionandtemperdesignation
Specifications and standards exist for aerospace grade aluminium alloys within each country, e.g.
DIN, ISO, DTD, and an International numbering system, based on the American Aluminium
Association(AA)system,iswidelyusedforwroughtalloys,Ref[4659].
The International system has largely replaced the nationallybased alloy designations within
Europe.
Russian wrought alloy designations, although using a 4digit code, are different to the AA
internationalsystem.

31

ECSSEHB3220Part5A
20March2011

46.2.2.2

Cross referencing national standards

Table 46.2.1 and Table 46.2.2 enable comparison of some national specifications for wrought and
castingalloydesignationnumbersrespectively,althoughthisisnotadefinitivelist,Ref.[461].
In addition the UNS system for numbering metals and alloys covers aluminium alloys, with code
numbersfromA00001toA99999,withthelastfourdigitsreflectingtheANSIcodeforthealloy,Ref.
[4661].Conventionalalloyspecifications,plussupplierproductcodes,areprovidedinRef.[4647].
Variations in alloy chemical composition can exist within different specification systems for so
calledequivalentalloys.Careisneededwhencomparingalloysacrossdifferentstandardssystems.

32

ECSSEHB3220Part5A
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Table46.21Aluminiumalloys:Comparisonofnationalspecificationsforwroughtalloys
International

Alloy

UK

France

AA

Type (1)

Old BS

Old NF

Werkstoff

DIN

Old UNI

1050A
1080A
1199
1200
1350
2011

Al99.5
Al99.8
Al99
[Al99.5]
Al Cu6 Bi Pb

A5
A8
A9
A4
A5L A5B
A-U5 Pb Bi

3.0255
3.0205
3.0257
3.1655

Al99.5
Al99.8
Al99
E-Al
Al Cu Pb Bi

2014A

Al Cu4 Si Mg

1B
1A
1
1C, 6L16, 6L17, 4L34
1E, G1E
FC1
H15,
L-grades; DTD.

A-U4 S G

3.1255

2017A

Al Cu4 Mg Si

L93, L94

A-U4 G

2024

Al Cu4 Mg1

2030
2031

[AlCuPbMg]
[AlCu2Ni1 MgFeSi]

2L97, 2L98 DTD-5090,


-5100A, (AMD2433)
H12

2117

Al Cu2 Mg

3L 86

2214

[AlCu4SiMg]

2218
2524

{AlCuNi]
[AlCu4Mg]

6L25
-

2618A

H16, DTD

3103

Al Mn1

3105

Germany

Italy

Sweden

Spain

SIS

UNE

3567
6362

New
UNI
9001/2
9001/4
9001/1
9001/5
9002/5

4007
4004
4010
4355

L-3051
L-3081
L-3001
L-3191

Al Cu Si Mg

3581

9002/3

4338

L-3130

3.1325

Al Cu Mg1

A-U4 G1

3.1355

Al Cu Mg2

3583

9002/4

A-U4Pb
A-U2 N

3.1645
-

AlCuMgPb
-

A-U2 G

3.1305

Al Cu Mg0.5

3577

9002/1

AlCuSiMn

N3, NS3

Air-9048610, -620.
A-U4N
A-U2 G N,
Air-9048-640
A-M1

3.0515

N31, NS31

A-MG05

3.0505

4043
4047
5005

[AlSi5]
[AlSi12]
Al Mg1

5056

Al Mg5

5083

Al Mg4.5 Mn

N21
N2
N41
N6,
2L58, 2L59
N8

A-S5
A-S12
A-G0.6
A-G5,
A-G5M
A-G4.5M C

5086

Al Mg4Mn

3.1924

Switzerland

CIS

EUROPE

CEN (2)
Al99.5
Al99.0
E-Al99.5
Al Cu6 Pb Bi
Al Cu4 Si
Mg

A0
-

L-3160

Al Cu4
Mg1.5
-

D16
1160
-

L-3180

D18

P-2214

7250

L-315
-

1163

3578

9002/6

L-3171

AK4-2

3568

9003/3

4054

L-3811

Al Mn

1400

AW-2618A
P-2618A
AW-3130

L-3140

AW-1050A
AW-1080A
AW-1199
AW-1200
AW-1350
AW-2011
AW-2014A
P-2014A
AW-2017A
P-2017A
AW-2024
P-2024
AW-2030
P-14

3103

9003/5

L-3831

AW-3150

3.2245
3.3315

Al Mn
AlMn0.5Mg0
.5
AlSi12
AlMg1

5764

9005/1

4106

L-3350

1510

3.3555

Al Mg5

4146

L-3320

1550

3.3547

Al Mg4.5 Mn

7790

9005/5

4140

L-3321

Al Mg4.5Mn

AlMg4Mn

5452

9005/4

Al Mg4Mn

AW-5005
AW-5056
P-32
AW-5083
AW-5086
P-5086

33

ECSSEHB3220Part5A
20March2011
5154A

Al Mg3.5(A)

N5

A-G3

3.3535

3.3537
3.3535
3.3206

Al Mg3
Al Mg2
Mn0.3
Al Mg2.7 Mn
Al Mg3
Al MgSi0.5

3574

9005/8

L-3392

AMG3

AW-5154A

5251

Al Mg2

N4

A-G2 M

3.3525

L-3361

AW-5251

5454
5554
5556A
5754
6060

Al Mg3.6
AlMg3Mn(A)
AlMg5.2MnCr
[AlMg3]
AlMgSi

N51
N52
N61
-

A-G2.5M C
A-G3 M
A-GS

7789
3575
3569

9005/3
9006/1

4125
4103

L-3391
L-3390
L-3442

AlMg2.7 Mn
Al Mg3
Al MgSi0.5

Al MgSi1Cu

6170

9006/2

L-3420

AD3

3569

4104

L-3441

AD31

A-SG M0.7

3.2315

Al Mg Si1

3571

9006/4

4212

L-3453

91E
E6, BT R6

A-85GS

3.2307

E-AlMgSi

3570

9006/3
-

4102
4102

L-3431
-

Al Mg Si1
Mn
-

AlZn6MgCu

DTD5130A, DTD5120

3.4394

7014

DTD5104A

Al Zn4.5 Mg

H17

A-Z5 G

3.4335

7791

9007/1

4425

L-3741

7049A

Al Zn8MgCu

Al Zn6 Mg Cu1.5

A-Z8GU
A-Z5 G U
Air-9048
A-4L, A-FeS

7075

2L95, L160,
L161, L162
-

3735

9007/2

L-3710

8011

L-3611

Al Zn4.5
Mg1
Al Zn6 Mg
Cu1.5
-

7020

Al Zn
4.5Mg1
Al Zn Mg
Cu1.5
-

AW-5454
AW-5754
AW-6060
AW-6061
P-6061
AW-6063
AW-6082
P-21, P-6082
AW-7010
P-7010
AW-7020
P-7020
AW-7049A
AW-7075,
P-7075, P-42
AW-8011A

6061

Al Mg1 Si Cu

H20

A-GS U C

3.3211

6063

Al Mg0.5 Si

H9

6082

Al Si1 Mg Mn

H30

6101A
6463

E-AlMgSi(A)
AlMgSi

7010

8011A

AlFeSi

3.4365
3.0915

Key:

(1)OldISOnumber;[CENEN573]

(2)EN573:AWprefixengineeringalloys.ALPprefix:AECMAaerospacealloy

V95

34

ECSSEHB3220Part5A
20March2011

Table46.22Aluminiumalloys:Comparisonofnationalspecificationsforcastingalloys
USA
AA

SAE

ISO

UK
BS/DTD

France

150.1
170.1
222.1 (1)
242.2
295.1, .2
319.2
333.0
336.1
355.1
356.1
A356.2
A360.2
A380.1
384.1
390.0
A413.1
A413.2
A443.1
514.1

34
39
38
326
321
322
323
336
309
306
303
305
35
320

Al99.5
Al99.7
Al Cu10 Si12 Mg
Al Cu4 Ni2 Mg2
Al Cu4
Al Si5 Cu3
Al Si8Cu3Fe
Al Si11 Mg Cu
Al Si5 Cu1 Mg
Al Si7 Mg
Al Si7 Mg
Al Si12 Mg
Al Si8 Cu3 Fe
Al Si10 Cu2 Fe
Al Si17 Cu4 Mg
Al Si12 Cu Fe
Al Si12
Al Si5
Al Mg5

LM0
LM12
4L35
2L91, 2L92
LM4
LM24
LM13
LM16
LM25
2L99
LM9
LM24
LM2
LM30
LM20 / LM2
LM6
LM18
LM5

520.0

324

Al Mg10

LM10

712

310

AlZn5Mg / Al Zn5 Mg Cr

Al Si6 Cu4 Zn
Al Si6 Cu3 Mn
Al Si9 Cu3 Mg
Al Si7 Mg
Al Si19 Cu Mg Ni
Al Si23 Cu Mg Ni
Al Si2 Cu Ni Fe Mg
Al Cu2 Ni Si Fe Mg

Al Si5 Mg

Al Mg8 Zn

Key:

(1) inactive.

LM31,
DTD5008B
LM21
LM22
LM26
LM27
LM28
LM29
3L51
3L52
DTD:716B,
722B
727B, 735B
DTD5018A

Germany

Italy
UNI

Sweden
SIS

3041
3045
7256
3050 / 6250-28
3600
3599
7257
3049
5075
5076
5079
4514
5077
3058

Europe
CEN (2)

Switzerland

CIS

14 4022
14 4231
14 4244
14 4253
14
14 4260
14 4261
-

G-Al99.5
G-Al Cu4 Ti
G-AlSi7 Mg
G-AlSi10 Mg

AL18V
AL6
AL30
AL5
AL9
AL4

3056

AL2
AL28
AL8,
AL27

3650 / 3602

14 4438

AC-71000 / AC-AlZn5Mg

G-Al Si6 Cu4


-

225
225

3052
3050
6251
3046

14 4230
14 4230
-

AL16V
AL6
AL26
-

AC-45000 / AC-AlSi6Cu4AC-45400 / AC-AlSi5Cu3


AC-46600 / AC-AlSi7Cu2
-

3.2341

G-Al Si5 Mg

235

3054

349

AC-51200 / AC-AlMg9

Werkstoff

DIN

A5
A7
A-U4 N T
A-U5 G T
A-S5 U
A-S10 U4
A-S11 UNG
A-S7 G
A-S7 G0.3
A-S10 G
A-S9 U3 Y4
A-S9 U3 Y4
A-S12, A-S12U
A-S13
A-G6

3.1841
3.2151
3.2161
3.2371
3.2371
3.2381
3.2161
3.2582
3.2581
3.3561

G-Al Cu4 Ti
G-Al Si6 Cu4
AlSi8Cu3
G-Al Si7 Mg
G-Al Si7 Mg
G-Al Si10 Mg
G-Al Si8 Cu3
G-Al Si12 (Cu)
G-Al Si12
G-Al Mg5

A-G10, A-G10Y4

3.3591

G-Al Mg10

A-Z5G

A-S5 U Z
A-S5 U
A-S2 U
-

3.2151
-

A-S4 G
-

VDS

225
226

233

231
230
244

AC-45200 / AC-45000
AC-45300 / AC-AlSi5Cu1Mg
AC-42000 / AC-AlSi7Mg
AC-43200 / AC-AlSi10Mg(Cu)
AC-47000 / AC-AlSi12(Cu)
AC-51300 / AC-AlMg5
-

(2) EN1706: AC prefix aluminium cast alloys.

35

ECSSEHB3220Part5A
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46.2.3

Aerospace alloys

46.2.3.1

General

The prime groups of alloys usedare the 2XXX, 6XXX and 7XXX (wrought) and AlSi casting alloys.
Thesematerials,afterspecificconditioning,achievehighstrengths.

46.2.3.2

AECMA EN standards

European standards and specifications (EN) are being developed and adopted. These are
progressivelysupersedingthevariousNationalstandardsinmemberstates,Ref.[4647].
Aerospace EN specification designations are controlled by AECMA and apply to a particular alloy,
conditionandform,e.g.

EN2092Aerospaceseries:AluminiumalloyAlP7075T6orT62:
cladsheetandstripbetween0.4mmand6mm.

ForinformationonAECMAstandards,[See:http://www.aecmastan.org]

46.2.3.3

SAE AMS standards

These are widelyused aerospace standards, published by the Aerospace Division of SAE
International,asAerospaceMaterialsSpecifications(AMS).Theycoveritemssuchasmanufacturing
and assembly processes, heat treatments and protection systems, so are in addition to chemical
compositionsstandards.
[See:http://www.aerospace.sae.org]

46.2.4

Properties

46.2.4.1

Elevated temperatures

Depending on the precise alloy composition and conditioning, mechanical properties decrease with
increasingtemperatureaboveabout100C.
Certainconventionalwroughtalloys,suchas2014A,2031and2618A,havebeendevelopedtoretain
usablepropertiesto200Cand300C,butthesearetheexception,Ref.[461].

46.2.4.2

Low temperatures

In general, the strength, ductility and toughness properties of aluminium increase with decreasing
temperature,Ref.[4648].Thereisnotransitiontemperaturebelowwhichbrittlenessoccurs,Ref.[46
1].
Of the various conventional alloy compositions available, only a few are considered for low
temperatureengineeringapplications,Ref.[4648]:

CPpurealuminium,whichhashighconductivity,e.g.usedforelectricalapplications.

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ECSSEHB3220Part5A
20March2011

AlCu,whichhasreducednotchedtoughnessatlowtemperatures,sonotwidelyused.

AlMn,whichhasmoderatestrength,e.g.tube,platesinheatexchangersapplications.

AlMg,whichisweldable.Coldworkimpairsductility,e.g.storageandtransportationtanks.

AlMgSi, which has moderate strength, is weldable with postweld treatment, e.g. mainly
aerospaceapplications.

AlZnMg,whichhasaseverelossofnotchtoughnessbelowabout77K,soisnotused.

46.3 New aluminium alloys


46.3.1

Developments

Themaindevelopmentsinaluminiumalloyscanbegroupedas:

AlLialuminiumlithiumalloys,[See:46.4].

ODSoxidedispersionstrengthenedsystems,[See:46.10].

MAmechanicallyalloyedsystems,whichareappliedtoAlLiandODSalloys.

RSPrapidlysolidifiedpowdersystems,[See:46.11].

All these materials offer weightsavings through increased specific properties or greater thermal
stabilitythanconventionalalloys.

46.3.2

Aluminium-scandium alloys

There is also interest in aluminiumscandium alloys, seen by some as the next generation of
aluminiumalloys.
Work on scandium additions in Alalloys began in the 70s in Russia, with some US patents issued
aroundthesametime.Inthe80s,ScadditionsinseveralalloysystemswereinvestigatedinRussia,
whichresultedinaseriesofRussianAlalloyswithaminorSccontent.
The effect of the Scaddition depends on the type and composition of the alloy, but the advantages
claimedinclude:

IncreasedstrengthfromAl3Scprecipitates.

Grainrefinementduringcastingorwelding.

Increased resistance to recrystallization and enhanced superplastic properties, which result


fromthegrainboundarypinningbyAl3Scparticles.

ICAA conferences have seen increasing numbers of papers on AlSc alloys over the past 10years.
Currently, the majority of openlypublished information relates to metallurgical studies and
evaluation,Ref.[4686].
Application examples come mainly from the sports and leisure equipment industry, but aerospace
organisationsarealsoinvestigatingAlScalloys,e.g.usedontheMiG29.

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46.4 Al-Li - Aluminium-lithium alloys


46.4.1

Development

46.4.1.1

Chemical composition

Thetwomaingroupsofaluminiumlithiumalloycompositionsare:

Withoutcopper,suchasAlMg,e.g.Russianalloysincluding1420.

Coppercontaining,e.g.2XXXand8XXXseriesalloys.

Only the coppercontaining alloys have so far achieved commercial application, so discussion is
limitedtothese.
Irrespectiveoftheirgroup,thelowfracturepropertiesofearlyAlLialloyswaslinkedtothepresence
oftrampelements,i.e.Na,K,Ca,HandS,whichcannowbecontrolledbytheuseofhighpurityLi
metalsandappropriatemanufacturingprocesses.

ThecurrentgenerationofAlLialloyslimitsomeelementswithincompositionsto,Ref.[4652]:

<0.002wt%Na.

<0.2wt% Fe and <0.1wt% Si, typically: Fe and Si form coarse constituent particles in age
hardeningalloys.

Higher silicon contents have been linked to an increased susceptibility to SCC stress corrosion
cracking.

46.4.1.2

Effect of lithium additions

The addition of lithium to an aluminium alloy reduces the density and increases the stiffness. As a
guide,each1%ofLithiumdecreasesdensitybyapproximately3%andgivesa6%modulusincrease
(foradditionsupto~4%).
Aluminiumlithium alloy development had to overcome many production difficulties and
uncertainties regarding the longlife suitability, in terms of transverse fracture sensitivity. The
anisotropy,mainlyresultingfromthetexturesdevelopedduringprocessing,stillremainsoneofthe
majorobstaclestothewideruseofthesealloysandmuchofthecurrentR&Dactivityisfocussedon
overcomingthisproblem.

46.4.2

Processing

The majority of initial development centred on ingot metallurgy for producing wrought products.
Thiswasfollowedby:

forginggrades,

weldablealloys,

powdermetallurgy,

particulatereinforcedcomposites,

superplasticforming.

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46.4.3

Applications

Aluminiumlithium alloys aim to supersede selected 2XXX and 7XXX series conventional alloys in
aerospacestructures,inparticulartheconventionalalloysusedforspecificcharacteristics,i.e.:

Damagetolerant:

2024T3,2204T3

Mediumstrength:

2014T6,2214T6

Highstrength:

7075T6,7050T6

Corrosionresistant:

Weldablealloy:

2219

7075T73

Anumberofcomprehensivereviewshavebeenundertakenonaluminiumlithiumalloys,Ref.[466],
[4614],[4615],[4649],[4650].ThesestudiesconsideredthecharacteristicsofAlLialloys,alongwith
informationonpotentialapplications.

46.4.4

Producers

Table46.4.1summarisesthecommercialsourcesofprimaryalloyandproductforms,Ref.[4656],[46
59],[4662].

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Table46.41AlLialloys:Commercialsourcesandproducts
Alloy

Composition (a)

Supplier

Cu

Li

Mg

Zr

Ag

Zn

Mn

Forms

Tempers

Target replacements

Standard alloys
sheet; 3-10mm

T83

2024-T3, 7075-T6,
7475-T6

sheet; 6.4-7.7mm

T82P (b)

2024-T62

sheet

T82P (b)

2024-T62

extrusions 1.2-75 mm

T8E65, T8E67

7075-T6511, 7050T76511 2024-T3511,


2026-T3511

0.25

plate 6.4-50mm

T8R78

2219-T87

0.35

0.35

extrusions 1.6-25mm

T8511

7075-T76511

0.05

0.35

plate 35-150mm

T87

2124-T851

0.04-0.16

0.25

0.10

sheet; extrusions/
forgings

T3, T34

0.95

0.08

Plate/sheet, extrusions

T1, T11

2024, 2524

2090

Alcoa

2.4-3.0

1.9-2.6

0.25

0.08-0.15

0.10

0.05

2098

Alcan

3.2-3.8

0.8-1.3

0.25-0.80

0.04-0.18

0.25-0.6

0.35

0.35

2x98

Alcan

2099

Alcoa

2.4-3.0

1.6-2.0

0.10-0.50

0.07-0.13

0.4-1.0

0.10-0.50

2195

Alcan

3.7-4.3

0.8-1.2

0.25-0.80

0.08-0.16

0.25-0.6

0.25

2196

Alcan

2.5-3.3

1.4-2.1

0.25-0.80

Ti+Zr 0.25

0.25-0.6

2297

Alcan

2.5-3.1

0.8-1.3

0.10-0.50

0.04-0.18

8090
Dolgarrog,
Otto Fuchs (c)

1.0-1.6

2.2-2.7

0.6-1.3

1.6

1.7

1441

recent modification to 2098 to give enhanced damage tolerance

VIAM

Special order alloys


2050

Alcan

3.2-3.9

0.7-1.3

0.20-0.6

0.06-0.14

0.20-0.7

0.25

0.20-0.50

2094

Alcan

4.4-5.2

0.7-1.4

0.25-0.80

0.04-0.18

0.25-0.6

0.25

0.25

2095 (d)

Alcan

3.9-4.6

0.7-1.5

0.25-0.80

0.04-0.18

0.25-0.6

0.25

0.25

2097 (e)

Alcoa

2.5-3.1

1.2-1.8

0.35

0.08-0.16

0.35

0.10-0.60

AMC500

AMC

Forgings

T1

Key:

(f)

(a)

A single figure denotes maximum content, except for 1441 where figures are nominal

(b)

Supplied on 'O' temper for subsequent heat treatment

(c)

Dolgarrog produce sheet; Otto Fuchs produce extrusions and forgings

(d)

Similar to 2195 but produced for super-plastic forming (SPF)

(e)

Alcoa alloy similar to 2297

(f)

Dispersion hardened Al-Li alloy made by proprietary powder metallurgy process

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46.4.5

Manufacturing processes

ThevariousprocessingroutesusedforAlLialloyscanbesummarisedas:

Inertatmosphereingotcasting,whichistheprimarysource.

Rolling into sheet or plate, which produces a higher degree of anisotropy compared with
conventionalalloys.

Extrusions, where, again, higher degree of anisotropy achieved. Close tolerances on long
sectionscanbedifficulttoachieve.

Forgings, which are limited to simple shapes as AlLi alloys rely on cold working prior to
ageingtoacquirestrength.8090iswellsuitedforhandforgingand2091forprecisionforging.

Nearnetshape,coveringdevelopmentofforgingandspinformingtechniques,Ref.[4650].

Thermomechanicaltreatment:AlLicanbesolutiontreatedusingmostestablishedtechniques.
Complexnewtempershavebeendevelopedtoimprovetoughnessbyunderageing.Theseare
designatedbytheletterX,e.g.T8XorbytheletterPwherethishasbeennegotiatedbetween
themanufacturerandpurchaser,e.g.T82P.

Welding, e.g. 2195, developing techniques, such as Variable Polarity Plasma Arc (VPPA), gas
tungstenarc,laserbasedandFrictionStirwelding,Ref.[4650].

Superplasticity,wheresuperplasticgradesof8090,2090and2095areavailable.

RSPrapidsolidificationprocesses,suchasLiquidDynamicCompaction(LDC).

Osprey Spray Deposition, used for particulatereinforced 8090 alloys, called COSPRAY by
AlcanandnowcarriedbyPEAKWerkstoff.

Planar Flow Casting, to enhance specific attributes, i.e. high strength or corrosion resistance,
elevated temperature performance or lower density by increased lithium content. Such
materialsaremoreexpensivethanthoseproducedbytheingotroute.

Mechanicalalloyedmaterials,suchasAMC500,whichofferimprovementsinthermalstability
andbetterstresscorrosioncrackingresistancethaningotAlLiproducts.

Mechanical alloying or high energy milling is used for dispersions added to alloys, giving a
discontinuouslyreinforcedmetalmatrixcomposite,[Seealso:46.13forpropertiesofSiCreinforced
alloys].

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46.5 Al-Li alloys: Characteristics


46.5.1

General

Table46.5.1givessometypicalcharacteristicsofAlLialloys.Theiruseisseenasdesirablebecauseof
areduceddensityandincreasedstiffness,enablingmasssaving.

Table46.51AlLialloys:Typicalpropertiescomparedwith7075
Alloy
Properties
Ultimate tensile
strength
(MPa) (1)
Yield stress
(MPa) (1)
Tensile modulus
(GPa)
Density
(kg/m3)
Coefficient of
thermal expansion
(106/K)
Heat capacity
(J/kg/K)
Thermal
conductivity
(W/cmC)
Electrical
conductivity
(% IACS)
Key:

AMC50
0

2090

2098

2099

2195

2196

2297

8090

7075

441531

503510

510600

510615

520540

414441

370480

400-500

400586

386483

470476

430550

470580

470490

379400

265435

300-420

303462

79.4

76

78

76

77.6

75.2

77

77

71.7

2590

2700

2620

2710

2630

2650

2540

2580

2810

23.6

21.4

23.6

1203

930

960

88

95.3

130

1719

19

33

(1)DatafromTable46.6.1orRef[463],andcoverarangeofformsandtempers

To successfully replace accepted 2XXX and 7XXX alloys, other properties need to be matched or
improved,theseinclude:

Strength,

Toughness,and

Fatigueresistance,coupledwith,

Acceptablecorrosionresistance.

Significant alloy development was needed to reach acceptance levels for these, and doubts have
remainedinsomeareasofparticularsensitivity:

Reducedductility,

Lowtransversestrengths,and

Susceptibilitytostresscorrosioncracking.

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Further studies have shown that a combination of a moderate lithium content of between 0.8% to
1.9%Li, depending on the base alloy composition, combined with further alloying additions and
process modifications, can improve the stress corrosion resistance and fracture characteristics, Ref.
[4650].

46.5.2

Microstructure

CharacteristicsspecifictoAlLialloyscanbesummarisedas:

Properties attained by AlLi alloys are strongly dependent on their microstructure. This is
affectedby:

alloychemistry,

processingroute,and

thermomechanicaltreatments.

Additionsofcopperandmagnesiumassistintheformationoffineprecipitates,i.e.Al2CuMg
andAl2CuLi.

Grain refinement in AlLi alloys is achieved by additions of zirconium, which also acts as a
recrystallisationinhibitor.

Most conventional aluminium alloys have an elongated pancake type of grain structure to
provide superior mechanical properties in the longitudinal and longtransverse directions.
However, this is deleterious to AlLi alloys. So, as far as is possible, a recrystallised
microstructure is sought, especially for damagetolerant grades. This can be promoted by an
underaged temper, T8X. However, a recrystallised structure does not give the highest
resistancetostresscorrosioncracking.

AdegreeofoptimisationandcompromiseisnecessarytoproduceanAlLialloywiththenecessary
properties. The higher anisotropy in AlLi alloys as compared to conventional alloys cannot be
avoided.

Furtherstudieshaveshowntheimportanceofalloyingandtraceelementcontrol,Ref.[4650]:

Control of tramp elements (Na, K, Ca, H, S), which are known to reduce fracture toughness,
Ref.[4652].

ControlofSiandFe;Siincreasesthesusceptibilitytostresscorrosioncracking,Ref.[4652].

Control of the LitoCu atomic ratio (to avoid formation of the phase) can produce good
damagetoleranceanddurability(inX2096).

SmallAgadditions(0.25to0.60%,typically)tothebasicAlCuLiMgalloy,Ref.[4651]:

instigatetheformationoffineprecipitates,whichimprovefracturetoughness.

improvestresscorrosionresistance.

ThisworkledtothedevelopmentoftheWeldaliteseriesofAlCuLiMgAgalloys,themost
notablebeing2195whichisnowusedfortheExternalTankfortheNASASpaceShuttle.

Mn additions to the base AlCuLi system with a controlled LitoCu atomic ratio can help
reducestrengthanisotropy.

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46.5.3

Further development

AlLialloyandprocessdevelopmentcontinueswiththeaimofoptimisingthematerialcharacteristics
for supersonic civil transport. For these highertemperature applications, one development alloy
(RX818)hadincreasedvolumefractionofstrengtheningprecipitatesthroughhigherlevelsofCuand
Mgandthermomechanicalprocessingwasusedtodevelopanunrecrystallisedmicrostructure,Ref.
[4663]. Although this alloy showed high strength levels, Ref. [4664] it was later dropped from this
studyduetopoorfracturetoughnessperformance,Ref.[4665].
Higher Cu and Mglevels when coupled with a Mn addition encouraged dispersoid formation and
promotedtherecrystallisationprocess(ML337developmentalloy).Thisgaveagoodcombinationof
thermal stability and mechanical properties (strength and fracture toughness) at temperatures up to
135C,Ref.[4664].InitialworkalsoindicatedthatML337exhibitsmoreisotropicductilityinthethree
directions,soimprovingthesheetformingability,Ref.[4651].
RX818 and ML337 are Reynolds Metals Company (now Alcoa) development alloys, based on the
Weldalitesystem,forNASA.RX818hasundergonefurtherdevelopmentandisnowavailablefrom
Alcan,inatempergivingimprovedmechanicalproperties,asalloy2098T82P,Ref.[4662].

46.6 Al-Li alloys: Properties


46.6.1

Data

Extensive,validatedpropertydataisincreasingfortheserelativelyrecentalloys.Manufacturersdata
sheetsareamainsourceofcomprehensivedata.
Asaresultofanisotropy,theminimumstrengthpropertiesinmostAlLiproductsoccurat60tothe
workingdirection.
Tensile and fracture toughness datafor the shorttransverse(ST) direction isscarce. This is a major
deficiency as the ST properties of AlLi alloys are poor, especially the ductility and fracture
toughness.TheSTfracturetoughnesscanbeaslowas50%ofthatofcomparableconventionalalloys.
However,recentdevelopmentsintheWeldalitefamilybyAlcan(Pechiney)haveresultedinalloy
2x98T82P (based on 2098) which has similar strength but better fracture toughness than the
conventionalaerospacesheetalloy2024T62,Ref.[4662].

46.6.2

Tensile properties

Ingeneral,thestaticstrengthlevelsofAlLialloyscomparewellwithconventionalmediumandhigh
strengthalloys.Theductilityis,however,usuallylower.
Table46.6.1providestypicaltensilepropertiesforthevariousalloytypesandproductforms,Ref.[46
6],[4656],[4657],[4658],[4662].

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Table46.61AlLialloys:Mechanicalproperties
Alloyand
temper

Elong.

Form

Direction(1)
(2)

UTS(MPa)

YS(MPa)

2090-T83

sheet

531

483

2090-T83

sheet

LT

503

455

2090-T83

sheet

45

441

386

2098-T82P

sheet

LT

503

476

2x98-T82P

sheet

LT

510

470

(%)

2099-T8E65

extrusion

600

550

2099-T8E65

extrusion

LT

520

470

2099-T8E67

extrusion

580

520

2099-T8E67

extrusion

LT

510

430

2195-T8R78

plate, 38 - 50mm

555

530

2195-T8R78

plate, 38 - 50mm

LT

575

530

2195-T8R78

plate, 38 - 50mm

45

560

505

2195-T8R78

plate, 38 - 50mm

ST

595

500

3.5

2195-T8R78

plate, 6.4 - 12.7mm

615

580

2195-T8R78

plate, 6.4 - 12.7mm

LT

600

556

11

2195-T8R78

plate, 6.4 - 12.7mm

45

525

490

12

2195-T8

plate, 11.4mm

609

574

8.5

2195-T8

plate, 11.4mm

45

526

490

12.7

2195-T8

plate, 11.4mm

55

510

470

14.7

2195-T8

plate, 11.4mm

60

527

472

14.9

2195-T8

plate, 11.4mm

65

563

492

14.5

2195-T8

plate, 11.4mm

70

567

503

9.2

2195-T8

plate, 11.4mm

LT

589

551

11.2

2196-T8511

extrusion, 1.2 - 6mm

520

470

2196-T8511

extrusion, 6 - 25mm

540

490

plate, 50mm

441

400

10

2297-T87

plate, 75mm

427

393

2297-T87

plate, 100mm

427

393

2297-T87

plate, 125mm

421

386

2297-T87

plate, 150mm

414

379

8090-T652

forging

430

350

8090-T852

forging

480

435

8090-T8151

plate

420

350

8090-T8151

plate

420

320

8090-T8151

plate

ST

370

265

2.5

8090-T81

sheet

420

360

8090-T81

sheet

415

290

11

1441-T1

sheet

415

315

16

1441-T1

sheet

430

325

14

1441-T1

sheet

45

405

280

18

1441-T1

extrusion

450

360

1441-T1

extrusion

475

390

1441-T11

sheet

450

395

9.5

2297-T87

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Elong.

Form

Direction(1)
(2)

UTS(MPa)

YS(MPa)

1441-T11

sheet

455

390

1441-T11

sheet

45

440

380

8.5

AMC500F1-T1

Forgings, 10-50mm

400

300

8-10

AMC500sa-T1

Forgings, 10-50mm

500

420

7-9

Alloyand
temper

Key

(%)

(1)DirectionisdefinedinASTME182305Annex2;
Llong;Ttransverse;
LTlongtransverse;
STshorttransverse;
(2)AngleinplanerelativetoLdirection.

46.6.3

Fracture properties

A summary of the fracture properties for various AlLi alloys and product forms is given in Table
46.6.2,Ref.[466],[4649],[4658],[4662].
Reliable data is still sparse and fracture toughness remains a problem with the high strength AlLi
alloys,butthenewer2x98alloyshowsgoodpromise.
FracturetoughnessdataforsomesheetmaterialsareprovidedinFigure46.6.1,Ref.[466].

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Table46.62AlLialloys:Fractureproperties
AlloyTemper
2090-T83
2098-T82P
2x98-T82P
2099-T8E65
2099-T8E65
2099-T8E67
2099-T8E67
2195-T8R78
2195-T8R78
2195-T8R78
2195-T8R78
2195-T8R78
2297-T87
2297-T87
2297-T87
2297-T87
2297-T87
8090-T8771
8090-T8771
8090-T8771
8090-T81551
8090-T81551
8090-T82551
8090-T82551
8090-T851
8090-T851
8090-T652
8090-T652
8090-T652
8090-T852
8090-T852
8090-T8151
8090-T8151
8090-T8151
8090-T81
8090-T81
1441-T1
1441-T1
1441-T11
1441-T11
Key

Form

Direction(1)

KQMPam

KIcMPam

KcMPam

sheet
sheet (Pechiney)
sheet (Pechiney)
extrusion
extrusion
extrusion
extrusion
plate, 38 - 50mm
plate, 38 - 50mm
plate, 6.4 12.7mm
plate, 6.4 12.7mm
plate, 6.4 12.7mm
plate, 50mm
plate, 75mm
plate, 100mm
plate, 125mm
plate, 150mm
plate
plate
plate
extrusion
extrusion
extrusion
extrusion
extrusion
extrusion
forging
forging
forging
forging
forging
plate
plate
plate
sheet
sheet

L-T
LT
LT
L-T
T-L
L-T
T-L
L
LT

30
27
66
55
37
35

43.9
130
160
-

40

LT

40

45
L-T
L-T
L-T
L-T
L-T
L
T
S-T
L
T
L
T
L
T
L
T
S-T
L
T
L
T
S-T
L
T

27
24
19
36
33
32
20
30
20
23
19
14
35
30
18
-

160
122

sheet (a)
sheet (a)
sheet (a)
sheet (a)

LT
TL
LT
TL

35
35.2
35.2
34.1
33
31.9
22
20
76.5 / 99.2 /
124
73.0 / 98.5 / 76.6 / 99.8 / 76.8 / 102.0 / -

(1)directionisdefinedinASTME182305Annex2;
(a)Sheetthickness1.4mmto1.8mm;widths200mm/400mm/600mm

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Figure46.61AlLialloys:Fracturetoughnessversusyieldstrengthforsheet
materials

46.6.4

Fatigue properties

46.6.4.1

Crack growth

Forsheetandthinplate,resultstodateindicatethatthefatiguecrackgrowthbehaviour(growthrate
vstressintensityfactor)ofAlLialloysisacceptablecomparedwiththatofconventionalalloys.
Figure 46.6.2 and Figure 46.6.3 show evidence of this, although optimisation of heat treatment is
necessaryforeachproductform,Ref.[466].
Alloy2091showninFigure46.6.3isnotcurrentlyofferedbyAlcan(Pechiney)becausealloys2098and
2x98havelargelysupersededit.Sincecomparativedataforthesealloysisnotpublished,thedatafor
2091isincludedhereforinformationonly.

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Figure46.62AlLialloys:Comparisonoffatiguecrackgrowthbehaviourfor
2024T3and8090T81

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Figure46.63AlLialloys:Comparisonoffatiguecrackgrowthbehaviourfor
2024T3and2091T8X

TheRussianalloy1441isunderevaluationbyNASAasafuselagesheetmaterialandshowedbetter
fatigue crack growth resistance than the conventional fuselage sheet alloy 1163 Al (2524 alloy). The
resultsaregiveninTable46.6.3,Ref.[4656].
Alloy2524isavariationofthe2024alloyseries,sotheseresultscangiveanindicationofproperties
comparedwith2024.

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Table46.63AlLialloys:Fatiguecrackgrowthrateof1441and1163sheet
Alloyand
Temper(2)

Direction(1)

KMPam

LT

average

range

18.6
31.0

0.37
2.00

0.28 - 0.40
1.26 - 3.17

18.6

0.29

0.14 - 0.51

31.0

1.50

0.69 - 2.57

18.6

0.79

0.42 - 1.21

LT

31.0

7.30

3.75 - 13.0

TL

18.6
31.0

0.70
3.40

0.68 - 0.73
2.56 - 4.14

18.6

0.78

0.62 - 0.98

31.0

3.85

3.30 - 4.40

18.6

0.92

0.74 - 1.14

31.0

4.70

3.44 - 5.53

1441-T1
TL
1441-T11

LT

1163-T3

TL

Testconditions:

d(2a)/dN,(mm/kcycle)

Testedatamaximumfatiguestressof100MPaandafrequencyof5Hz.Theratioof
minimumfatiguestresstomaximumfatiguestress(R)was0.
Testedonsheet1.2mmto2.0mmthickusingcentrecracktensionspecimensfrom
300mmto400mmwide.

Key:

(1)directionisdefinedinASTME182305Annex2;
(2)1163isaRussiananalogofAA2524

The pronounced material anisotropy of thicker sections, such as in forgings, produces variations in
fatigue crack growth behaviour. As shown in Figure 46.06.4, the shorttransverse direction is
noticeablypoorer,Ref.[466].

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Figure46.64AlLialloys:ComparisonoffatiguecrackgrowthbehaviourLITAL
A(8090)forgingsat20C
46.6.4.2

Strength

Itisnowacceptedthatthefatiguestrength(appliedstressvcyclestofailure)ofAlLialloyscanmatch
that of the equivalent conventional alloys in most product forms. This is also valid for notched
specimens.Publisheddataonfatiguestrengthscanbeconfusinganddependonwhentheworkwas
done, and whether specimens were notched or not. For dynamic mechanical applications, designers
can use only that information on the most commercially developed ingots and their optimised heat
treatments.Fatiguestrengthsinthickersectionshavestrongdirectionality.

46.6.5

Design values

46.6.5.1

General

Designvaluescanonlybestatedforidentifiablecombinationsof:

alloy

productform,and

thermomechanicaltreatment

A and B values are available from the suppliers for many of the other alloys referred to in this
handbook,Ref.[4662].

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46.6.5.2

Extrusions

Table 46.6.4 gives an indication of data for extrusions that reflect the minimum guaranteed values
whichcanbeexpected,Ref.[4614].

Table46.64AlLialloys:Designtensilestrengthsforextruded8090alloys

8090T8511

8090T82

UTS(MPa)

YS(MPa)

UTS(MPa)

YS(MPa)

A-value(1)
B-value(1)
Average
Standard
deviation

505
517
532
10.3

434
449
468
12.9

515
523
534
6.9

441
453
468
9.7

Key:

(1)AandBvaluesareavailablefromthesuppliersformanyoftheotheralloysreferredtoin
thishandbook,Ref.[4662].

46.6.6

Further development alloys

Continued development of AlLi alloys has centred on optimisation and overcoming the known
property limitations of the first generation commercial alloys such that second, and now third,
generation alloys have become available commercially and are covered in this handbook, [See also:
46.5].
Work continues on both alloy chemistry and process technology (including powder metallurgy
techniques)toimprovetheisotropyandtransversefracturetoughnessproperties.

PropertydataformanyexistingandnewerAlLialloysisstillunderevaluation.AandBvaluesare
becomingavailablefromalloysuppliers,whoalsoprovideotheruptodateinformation,Ref.[4662].

Further data on alloy 2090T83 sheet is published in MMPDS Metallic Materials Properties
DevelopmentandStandardization,whichhasreplacedMILHDBK5.

Additionaldataonalloy2297T8R85plateispublishedinthePMPPreliminaryMaterialProperties
Handbook,whichisaprecursortoinclusioninMMPDS,Ref.[4671],[4672].

46.7 Al-Li alloys: Stress corrosion cracking


46.7.1

General

Forspaceapplications,stresscorrosioncrackingisthemostcriticalformofdegradationthatdemands
examinationbecausetheSCCbehaviourofearlierAlLialloyswaspoor.Thesituationhasimproved
withmodificationstoalloychemistry,temperingandageingtreatments.
[Seealso:ECSSQST7036:Materialselectionforcontrollingstresscorrosioncracking].

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46.7.2

Test

TheSCCperformanceofselectedalloysisdeterminedagainstECSSQST7037(ASTMG44andG47)
usingastressedspecimenina3.5%sodiumchloride(NaCl)solution.
AlLialloysareusuallygivenalowresistance(class3)status,indicatingthatvisualcorrosionoccurs
after30daysandspecimenfailuresbefore30daysarenotuncommon.
The ST shorttransverse direction gives the lowest threshold stress for failure at levels as low as
50MPa.
ESAPSS01737hasbeenreplacedbyECSSQST7037.

46.7.3

Stress corrosion cracking resistance

46.7.3.1

Alloy type and temper

For 8090type alloys, the susceptibility to crack initiation is dependent on the copper content,
particularlyforalloyswithlowlevelsofmagnesium.Cracksdonotinitiateincopperfreealloys.The
initiation characteristics are also dependent on alloy temper. Overaged tempers give the best
resistancetoSCCinitiation.Duplexageingtreatmentscanalsoassistinobtainingabalancebetween
strength and SCC resistance. Where possible, the ageing temperature is reduced. Similar effects are
notedin2090alloys,withpeakagedmaterialssurvivinglonger.

ThecorrosionisinfluencedbythepresenceofTi(Al2CuLi)precipitatesatgrainboundarieswhichare
anodic to the matrix and preferentially dissolve causing intergranular cracking. Peakageing causes
precipitationwithinthegrains.
SmallAgadditionstoAlCuLiMgalloysystemshaveshownimprovementsinSSCresistanceover
nonAgcontainingalloys,Ref.[4651].[Seealso:Recentalloys].
Figure46.7.1showstheeffectofageingonSCCbehaviour,Ref.[4617].

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Figure46.71AlLiAlloys:Influenceoftemperonstresscorrosioncracking
initiationfor8090plates,STdirection

AccumulateddataontheSCCperformanceof8090AlLialloyforvariousproductformsisgivenin,
Ref.[4615],[4619],[4618],[466]:

Table 46.7.1, which gives the proposed classification of 8090 alloy in accordance with ECSS
standards,alongwiththeoriginalESAsource.

Table46.7.2givestentativestresscorrosionthresholdsfor8090.

Table46.7.3givesresultsofstresscorrosiontestsfor8090.

Table46.7.4comparestheSCCinitiationbehaviourof8090withconventionalalloys.

Table46.71AlLialloys:Alloy8090Resultsofstresscorrosiontests
ESAMetallurgy
ReportNo.

1338
1474
1631
1632
1798
Key

Materialtype

8090-T651 (25 mm plate)


8090-T8771 (90 mm plate)
8090-T81 damage tolerant sheet (75%
PS)
8090-T81 damage tolerant sheet (50%
PS)
8090-T8 forging

Proposed
classification(1)(2)

class 3
class 3
class 3
class 3
class 3

(1)TestsconductedtoESAPSS01737.ThisspecificationhasbeenreplacedbyECSSQST7037;
(2)Seealso:ECSSQST7036:Materialsselectionforcontrollingstresscorrosioncracking.

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Table46.72AlLialloys:Tentativestresscorrosionthresholdsfor8090alloy
Sheet

Temper

AlloyCategory

LTSCCthreshold,[MPa]

8090
8090

T81
T6/T8

damage tolerant
medium strength

200
> 350

Thinplate

Temper

STthresholdstress,[MPa](Altest3.5%NaCl)

8090
8090

T651
T8771

50-75
140

Forging

Temper

Thresholdstress,[MPa]

8090

T652

200

Table46.73AlLialloys:Resultsofstresscorrosiontestonsheetmaterial,as
performedbyNLR
Alloy

Nominalyield
stress[MPa]

8090-T8

450

8090C-T3

214

8090CT81

341

Lifetime[Days]

SCCtest
stress[MPa]

Initiation

Failure

200
300
200
300
200
300

>42
>42
>42
>42
1
2

>42
>42
>42
>42
>42
>42

Table46.74AlLiAlloys:SCCinitiationbehaviourof8090alloycomparedwith
thatofconventionalalloys
Alloy

8090
8090
8090
2024
2014
7070
7075
Key:

AgeingCondition

S.T.ThresholdStress,[MPa]

UA
PA
OA
T651
UA
PA
OA
T351
T651
T7651
T7351

60
115 (20 day)
230
<50 (20 day)
120 (2 day)
120 (6 day)
120 (29 day)
50 (20 day)
50 (20 day)
150 (20 day)
240 (20 day)

UA=Underaged;PA=Peakaged;OA=Overaged.

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46.7.3.2

Crack propagation

CrackpropagationisassessedusingaDCBdoublecantileverbeamspecimen,whichisnotchedand
fatigue precracked. Findings have been contradictory as to the relative merits of under and over
ageing. Hydrogen embrittlement can also occur in saline environments. All investigations do show
thatfor2090and8090alloys,thethresholdstressintensityK1SCCisreducedbyoverageing.
In general, the SCC behaviour of sheet and extrusion has improved during the alloy development
programmes.However,problemsaremoreacutewiththickersectionplateandforgings.

46.7.4

Recent alloys

Alloy 2195, a member of the Weldalite family and commerciallyavailable from Alcan, has
undergone evaluation of its SCC and fracture characteristics as a replacement for 2219 in welded
cryogenicfueltankapplications,Ref.[4650],[4651].[Seealso:46.9]
Theotheralloysofferedcommerciallyallshowimprovedcorrosionresistance,severalhavingbetter
propertiesthantheconventionalaerospacealloys2024and7075.
Alloy 2297, whilst having lower strength level than some of the other newer AlLi alloys, shows
comparableSCCresistancetoconventional7XXXseriesalloys,eveninheavyplatesectionsupto150
mmthick.
Table 46.7.5 provides a summary of SCC resistance and EXCO exfoliation corrosion susceptibility
dataforcurrentlyavailableplate,sheetandextrusions,Ref.[4662].

Table46.75AlLialloys:Currentcommercialalloyssummaryofcorrosion
resistance
Alloy

2098-T82P
2x98-T82P
2099T8E65
2099T8E67
2195T8R78
2196-T8511
2297-T87
Key:

Form

Direction(1)

SCCresistance(a)
MPa

Duration

EXCO(2)
rating(b)

sheet
sheet

LT
LT

>240
>240

30
30

extrusions

LT

330

P/EA

extrusions

LT

250

P/EA

plate
extrusions
plate

ST

345
207

30
30

EA
EA
EA

(1)DirectiontoASTME1823
(2)EXCOexfoliationcorrosionsusceptibility
(a)toASTMG47
(b)toASTMG34

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46.8 Al-Li alloys: Manufacturing aspects


46.8.1

General

Special attention is given to health and safety, along with handling of AlLi scrap to avoid
contaminationofthatfromconventionalalloys.Therefore,thesameprocessingequipmentcannotbe
usedforbothconventionalandAlLialloys.

46.8.2

Machining

AlLi alloys have machining characteristics similar to those of other aluminium alloys, with small
differencesincuttingspeedsandachievablesurfacefinish.Aspectsofmachiningcanbesummarised
as:

Chemicallyactivedustparticlesaregenerated.ThepresenceofLithiumhydroxidecanirritate
therespiratorysystemifinhaled.

Chemical milling generates more residue, so special equipment is needed for its efficient
removal.

Operationsthatgeneratemoltenmetal,e.g.EDMelectrodischargemachining,arebestavoided
becausemoltenAlLialloyreactsviolentlyinthepresenceofmoisture.

All scrap and swarf needs segregation from other recyclable aluminium alloys to avoid Li
contaminationandpossibledamagetofurnacesnotdesignedforLicontainingalloys.

AlLialloysprobablyneeddedicatedmachiningfacilities.

46.8.3

Welding

Weldalite049wasdevelopedspecificallyforenhancedweldability.Thesubsequentdevelopmentsin
thisfamilyofalloys,andinparticularalloy2195,arecandidatestoreplacetheexistingweldablealloy
2219,Ref.[4650].
2195 behaves well at cryogenic temperatures, especially when given a modified twostep aging
treatment,increasingitspotentialasamaterialforcryogenicfueltanks,Ref.[4667],[Seealso:46.9].
TheLicontentof0.8to1.2%givesamodestmasssaving.

Other AlLi alloys are weldable under suitable conditions and many of the newer alloys now
commerciallyavailableshowexcellentweldability:

Surface layers on the alloy are removed by chemical or mechanical machining, to prevent
porosityintheweld.

TIGweldinghasbeensuccessfullyappliedtoalloy8090,usingAl5Mgfillermetal.Apostweld
ageingtreatmentimprovesthestrength.

For alloy 2090, welds have been achieved with 4047 and 4145 fillers. Postweld solution
treatmentandageingcanincreasetheweldstrengthto80%ofthebasemetalstrength.

Weldments in alloy 2195 made with the VPPA (variable polarity plasma arc) technique have
beenextensivelyexamined,Ref.[4650],[4666].

ThenewertechniqueofFSWfrictionstirweldinghasalsobeenexaminedwithencouraging
results,Ref.[4666].

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Theweldingofalloy2195hasbeenextensivelystudiedaspartoftheSLWTsuperlightweighttank
development programme at NASA. The results of a study into the effects on fatigue crack growth
ratesaresummarisedinTable46.8.1,Ref.[4666].
TheresultsindicatethatbothVPPAandFSWproducedacceptablequalitywelds.
[Seealso:46.6fatigueproperties]

Table46.81AlLialloys:2195T8plateandweldmentssummaryoffatigue
crackgrowthrate
Alloy+
condition

t(mm)3

Orientati
on

K3

Test
temp.3
(C)

6.6

11

22

0.5-1.4
0.3-1.5

4.3- 7.8
2.7-8.0

33.7-78
29.4-77.2

All
All

Specim
enID

(MPam)

2195-T8
plate 1

6.35, 12.7

L-T, T-L

0.1, 0.5

24
93

VPPAW 1

6.35, 12.7

L-T

0.1, 0.5

24

1.0-1.8

9.0-1131

All

FSW 1

6.35, 12.7

L-T

0.5

196
24
94

2.6-2.7

14.8
5.6-11.6
13.3-13.5

98.6-114.2
34.3
-

All
All
All

2195 2

6.35,
31.75

All

0.1, 0.5

196
24

0.07-16.5

0.4-4.4
0.2-55

11-110
-

All
All

Key:

OrientationisdefinedinASTME1823Annex2.
Fatiguecrackgrowthrate,da/dN(106in/cycle).
VPPAWvariablepolarityplasmaarcwelding.
FSWfrictionstirwelding.
ConversionfromImperialunits:MATWEBhttp://www.matweb.com/tools/conversion.asp

1Ref.[4666]
2ResultsfromSLWTdesignallowablesprogram:R.E.ReinmullerSO89818AlLiMaterials
Database,LockheedMartinMannedSpaceSystems,NewOrleans,LA70189
3ConversionfromImperialunits:MATWEBhttp:/www.matweb.com/tools/conversion.asp

46.8.4

Cost implications

Ingeneral,thepriceofbasicAlLiproductforms(sheet,plate,extrusionsandforginggrades)ishigher
thanthatofcomparableconventionalalloys.
Specialdemandsduringproductionincreasecostsfurtheroverconventionalaluminium.Someofthe
contributoryfactorsare:

increasecostsforscrapsegregationandcontrol,

reducedscrapvalue,

increasedhandlingcosts,

increasedtoolwear.

Asproductpricesarenormallyvolumerelated,thesituationislikelytoimprovewiththewideruseof
particulargradesofAlLialloys,[Seealso:46.9].

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46.8.5

Applications

ThecostsindicateadistincthandicapforAlLialloysifoneisseekingtoreplaceestablished2XXXand
7XXXseriesalloys.
Thehigherfinisheditemcostcanonlybeoffsetagainstmasssaving;thereisnootherjustificationfor
usingAlLialloys.Suchmasssavingshavebeenshownforsomeaerospacestructures,[See:46.9]

46.8.6

Mass-saving

46.8.6.1

General

Whilstadirectmaterialsubstitutionapproachispossible,thehighestmasssavingsareobtainedfrom
AlLialloysbyoptimisingthedesign,[Seealso:46.9].

46.8.6.2

Direct material substitution

ForhighLicontainingalloys(8090,2090),amasssavingofabout8%canbeachieved.
Masssavingsintherangeof6%to7%areprobableforalloyswithamoderateLicontent,e.g.2098,
2099,2195,2196and2297,Ref.[4651].

46.8.6.3

Redesigned components

Byredesigningtotakeaccountoftheincreasedmodulus,masssavingsof15%to18%canbepossible,
providedthatstrengthcriteriaaremet.

46.9 Al-Li alloys: Potential applications


46.9.1

General factors

AlLi alloys appear attractive for space use, but the characterisation of stress corrosion cracking
behaviourcanpresentanobstacle,[See:46.7].AlLicanbeusedifacontractordemonstratesthatthe
possibilityofSCChasbeenaddressedforeachindividualapplicationandtheappropriateFailSafeor
SafeLifecriteriaaremet.

[See:ECSSQST7036;ECSSQST7037]

Initially, appropriate components were those needing minimum machining, little or no welding
havingnofatigueloading.Thisimpliedsheetproducts,netshapeforgingsandextrudedsectionsfor
componentssuchasbrackets,panels,strutsandadapterringsforsatellitestructures.
Single launch applications pose fewer problems than reusable, longlife structures. The recent
weldablealloys,e.g.Weldaliteseries,2095and2195havebeenappliedtocryogenictanks.

[See:SuperLightweightTank(SLWT)]

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AnexampleofthegrowingconfidenceinAlLialloysinlonglifestructuresistheiruseincommercial
aircraft applications. Traditionally, evaluation for use in space draws on the experience gained by
contractorswithmaterialsusedwithinaircraft.

[See:A380Floorbeams]

46.9.2

Space Shuttle external tank

46.9.2.1

General

TheETexternaltankistheonlymajornonreusablecomponentoftheSpaceShuttlesystem.TheETis
thesinglelargestelementwithdimensionsof46.94m(154feet)longand8.41m(27.6feet)diameter.

During launch it acts as the structural backbone of the Shuttle and contains the LH and LOX
propellant for the Orbiters 3 main engines. Early versions of the ET used aluminium, steel and
titaniumintheirconstruction.Theneedtoreducemassandsoenableheavierpayloadstobecarried
by the Orbiter, especially for the construction of ISS international space station, resulted in
modificationsintheoriginaldesign;assummarisedinTable46.09.1.

Table46.91AlLialloys:ApplicationsmasssavingsinSpaceShuttleexternal
tank
ETExternalTank

SWT
(Standard Weight Tank)
LWT (2)
(Light Weight Tank)
SLWT (3)
(Super Lightweight Tank)

Mass(kg)

34246 (75 500 lbs)


29710 (65 500 lbs)
26308 (58 000 lbs)

Missions

STS-1 to STS-5 (1)


STS-7
STS-6
STS-8 to STS-90
STS-91 (June 1998)

Key: (1)ETswerepaintedwhiteformissionsSTS1andSTS2.FromSTS3onwards,theywerenolonger
paintedtosaveweightandpreparationcosts.

(2)Materialsanddesignchanges,plusnewfabricationtechniques.

(3)Componentredesignanduseof2195aluminiumlithiumalloy.

46.9.2.2

Super Lightweight Tank (SLWT)

Theuseof2195alloyintheconstructionoftheSLWTisprobablythelargestuseofanAlLialloyin
currentspaceapplications.SLWTfirstflewinJune1998onmissionSTS91.
Theweightsavingofabout3402kgoverthepreviousLWTtankwasachievedbycomponentredesign
and the use of an AlLi alloy, which provides a 30% strength increase and 5% density reduction
comparedwiththepreviousmaterials,Ref.[4653].
DespitethemodificationstothedesignandmaterialsusedintheET,theoverallconceptremainsthe
same.
Figure46.9.1showsthemainETtankcomponentsandthechangesfromthepreviousLWT,Ref.[46
53],[4668].

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Key:

# = lbs.

Figure46.91AlLialloys:ApplicationsSpaceShuttleexternaltank,major
changesfromLWT

ThemainETtankcomponentsare:

LOX liquid oxygen tank, which is an aluminium monocoque structure composed of


preformed, chemicallymilled gores, panels, machined fittings and ring chords which are
assembled by fusion welding. The nose cone reduces drag and acts as a lightening rod. The
mainfeaturesare:

Dimensions:~8.4m(331inches)diameter~15.0m(592inches)long.

Capacity:~553962litres(19563cubicfeet).

Operatingpressure:~145kPa(20to22psi)

LHliquidhydrogentankisanaluminiumsemimonocoquestructureoffusionweldedbarrel
sections;5majorringframeswithforwardandaftellipsoidaldomes.Attheforwardendofthe
LH tank is the ET/Orbiter forward attachment pod strut. At the aft end are 2 ET/Orbiter
attachmentballfittingsandtheSolidRocketBooster(SRB)toETstabilisingstrutattachments.
Themainfeaturesare:

Dimensions(approximate):8.4m(331inches)diameter29.5m(1160inches)long.

Capacity:~1515461litres(53518cubicfeet).

Operatingpressure:~228kPa(32to34psi)

Intertank, which is a semi monocoque cylindrical structure with aluminium mechanically


joinedskin,stringersandmachinedpanels.FlangesoneachendjointheforwardLOXtankand
aft LH tank. It houses the ET instrumentation and provides an umbilical plate that interfaces

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withthegroundfacilityduringprelaunchoperations,suchaspurge,hazardousgasdetection,
H2boiloff.

Dimensions(approximate):8.4m(331inches)diameter6.9m(270inches)long.

The ET external surface has a multilayer thermal protection coating (about 25 mm thick) which
prevents ice forming on the tank structure and protects it from the thermal conditions during
prelaunch,launchandflight.

46.9.3

A380 - Floor beams

46.9.3.1

General

The Airbus A380 represents the latest development in large, widebodied, passenger aircraft. The
overalldimensionsare:

Wingspan:79.80m

Length:73.00m

Height:24.10m

Fuselagediameter:7.14m

The A380 family not only represents the largest civil aircraft built to date, but also provides a
technologyplatformforfuturecommercialaircraftdevelopmentprogrammes.

46.9.3.2

Material selection

Weightsavings were of paramount importance in the selectionof construction materialsin order to


providelowerfuelburn,reducedemissionsintotheatmosphereandloweroperatingcosts.
AlthoughAirbusconsideredtheuseofAlLialloysfortheA340,thefirstgenerationalloys,suchas
8090T8511 and 2091T851, were rejected over issues of thermal stability, anisotropy and crack
deviation. These problems have been resolved with the availability of the thirdgeneration AlLi
alloys.
Airbus has qualified alloys C460 (2099) from Alcoa and 2196 from Alcan in the form of heavy
extrusionsintheT8511temperforthemanufactureoffloorbeams;asshowninFigure46.9.2.
ExtrudedAlLialloyprofilesareusedinthemaindeckfloorbeams(A380800sections13and15),but
aredestinedforuseinbothdecksinthefreighterversion;adaptedtosuitlocalloads,Ref.[4685].
Both alloys exhibit better or equal properties to conventional alloy 7175T73511, with improved
corrosionresistance,andprovidesubstantialweightsavings.
Based on current experience, Airbus considers AlLi alloys as the main competitor to composite
materials for aircraft construction. As a result, other applications for AlLi alloys are under
consideration,suchasbottomwingstringersandfuselageskin,Ref.[4669],[4670].

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Fuselage diameter: 7.14 m

Figure46.92AlLialloys:ApplicationsAirbusA380floorbeams
Airbus also has a cooperative venture with Russia organisations, such as VIAM, to assess potential
uses of Russianorigin AlLi alloys. This programme considers a number of alloys with the aim of
generatingdatatoenableadirectcomparisonbetweenthepropertiesofRussianoriginmaterialswith
currentspecificationwesternmaterials.Theworkincludesprequalificationactivitiesonashortlistof
advancedmaterials,identifiedashavingtruepotential,Ref.[4684].

46.10 Oxide dispersion strengthened (ODS) alloys


46.10.1 Type and effect of dispersions
Dispersion strengthening relies on the distribution of many, very fine particles, usually a ceramic
oxide, throughout a pure metal. These particles are of nanometre size range (2nm to 10nm), and
interactwithdislocationstogivethestrengtheningeffectasstrainoccursinthemetal,Ref.[468].
Cryomilling pure aluminium powder in liquid nitrogen results in dispersion strengthening by the
formation of AlN aluminium nitride particles. After subsequent compaction and degassing, this
materialcanbeextrudedandthencoldrolledtothinsheet,Ref.[4655].

46.10.2 Processing
46.10.2.1 Powder
ODSalloysarepreparedbyapowdermetallurgyroute.Mechanicalalloying(MA)isthemainmethod
ofincorporatingtheoxideparticles,e.g.44mairatomisedaluminiumpowderwith0.05malumina
powder. Both are added to a high energy ball mill under liquid nitrogen (Raufoss A/S process).
Nitrogenprovidesanatmosphereastheattritorbreaksuptheparticlesandconsolidatesthemintothe
aluminium as oxynitrides. Particle content varies, but is under 10% and often nearer 3%. Alumina

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(oxynitride)isthepopularstrengtheningmedium,butothernonshearable,hardparticleswithhigh
meltingpointscanbeused,e.g.Al4C3,TiO2,ZrO2orAl3Ti.

46.10.2.2 Consolidation
Thepowderisconsolidatedeitherby:

hotisostaticpressing(HIP),or

vacuumhotextrusion.

46.10.2.3 Product forming


Theconsolidatedmaterialcanbeworkedfurthertoafinishedproductby:

forging,

extrusion,

swaging,

rollingtosheetorplatematerial.

46.10.3 Cost factors


Thealloysareexpensivetoproduceandtherearepracticallimitsonthesizeofbilletproducibleby
thepowderroute.

46.10.4 Applications
ODSalloysarespecialisedproductsforapplicationsneedingaluminiummaterialswith:

higherthermalstability,

greaterwearresistance,

hardness.

The hightemperature stability is of interest as a possible competitor to titanium in the temperature


range150Cto450C.
Aluminium nitride (AlN) dispersion strengthened materials have been considered for hypersonic
aircraftstructuralelements,duetotheir,Ref.[4655]:

highstrengthupto450C,

creepresistance,

graingrowthstability,

corrosionresistance(purealuminiummatrix),

highthermalconductivity(heatdissipation).

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46.10.5 Properties
46.10.5.1 General
EmphasisisgivenheretoODSalloyswitha3%particleadditionpreparedbyRaufossA/S,(Norway),
Ref.[469].
Aluminiumlithium alloy, AMC500, is also an ODS material produced by mechanical alloying, [See:
46.4,46.5,46.6].

46.10.5.2 Strength
ODSalloysaremediumstrengthmaterials,whichofferusablepropertiesto450C,e.g.proofstresses
ofaround120MPaat400C.
Figure 46.10.1 indicates the better strength retention of various mechanically alloyed systems above
200C compared with a conventional higher temperature alloy, such as 2618, Ref. [469]. However,
Figure46.10.2showsthatthestraintofailureissignificantlyreducedastemperatureincreases.

Figure46.101AluminiumODSalloys:Comparisonofelevatedtemperature
tensilestrengthforvariousmechanicallyalloyedmaterialswithAl2618

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Figure46.102AluminiumODSalloys:Comparisonofelevatedtemperature
tensilestrength,proofstressandductility

Themethodofpowderconsolidationalsoinfluencesmechanicalproperties,Ref.[469]:

Proofstress,asshowninFigure46.10.3.

Ductility,asshowninFigure46.10.4.

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Figure46.103AluminiumODSalloys:Effectofconsolidationmethodonproof
stress

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Figure46.104AluminiumODSalloys:Effectofconsolidationmethodon
ductility

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46.10.5.3 Creep resistance


InviewoftheproposeduseofODSalloysatelevatedtemperatures,creepresistanceisimportant.
Figure46.10.5showsthatat400Clifeexpectancyisreasonableifstressesarebelow100MPa,although
theultimatelimitationisthelowfailurestrain(<1%),Ref.[469].

Figure46.105AluminiumODSalloys:Creepresponseat400Cfor3stresslevels

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Figure46.10.6providescreepdataat250Cwhichindicatesmorestablebehaviourinthestressrange
100MPato160MPa,Ref.[469].

Dispersion content: 3%Al2 O3

Figure46.106AluminiumODSalloys:Comparisonoftensilecreepcurvesat
differentstresslevelswithAl2618

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46.10.5.4 Fatigue
Figure46.10.7showsthatthefatigueperformanceoftheODS3%aluminaalloyisinitiallyhinderedby
amodesttensilestrength,butahigherrunoutstressisreachedathighfrequenciesthanfor2024alloy.
ThissuggestsnofundamentaldeficienciesinthefatigueperformanceofODSalloys,Ref.[469].

Dispersion content: 3%Al2O3

Figure46.107AluminiumODSalloys:ComparisonoffatigueresistancewithAl
2024

46.11 Rapidly solidified powder (RSP) alloys


46.11.1 Processing
RSP powders are made by breaking molten metal into small droplets which are solidified very
rapidly.Thiscanbeachievedby:

atomisation,

splatcooling,or

meltspinning.

AswithODS[See:46.10],RSPmaterialsavoidsomeofthelimitationsofmeltingotmetallurgy,Ref.
[462].

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46.11.2 Microstructure
TheRSProuteproducesamicrostructuralgrainrefinement.Thesmallerthemeanfreepathbetween
obstaclestodislocationmovement(grainboundaries),thegreaterthestrengthening.Inaddition,finer
microstructuralfeaturesarelessapttoserveasfractureinitiatingflaws,therebyincreasingtoughness.
Grain size is reduced because of the short time available for nucleation and growth during
solidification.
InRSPprocessing,thenormalalloyinglimitsinaluminiumcanbeexceededasaresultofincreased
supersaturation. This enables greater precipitation hardening without harmful segregation effects,
which can arise in overalloyed ingot metallurgy alloys. Moreover, elements that are essentially
insoluble in the solid state, but have significant solubility in liquid aluminium, can be uniformly
dispersedinparticlesundergoingveryrapidsolidification.
In this way novel alloy compositions and strengthening phases can be produced which are not
achievablewithconventionalingotmetallurgy.

46.11.3 Development
Theprincipalpropertieswhichareenhancedbyrapidsolidificationprocessingare:

highambienttemperaturestrength,

corrosionandstresscorrosioncrackingresistance,

elevatedtemperatureproperties.

46.11.4 Ambient temperature


46.11.4.1 Alloys
ThemostsuccessfulmaterialsdevelopedhavebeenintheAlZnMgsubsystem(7XXXalloys).
In more highly alloyed 7XXX alloy variants, dispersed transitionmetal intermetallic phases were
achieved.Themostnotablealloydevelopmentshavebeen:

Cobaltcontainingalloys:7091and7090.

NickelandZirconiumcontainingalloy:CW67,Ref.[4611].

ThealloycompositionsaregiveninTable46.11.1.

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Table46.111RSPaluminiumalloys:Ambienttemperatureusenominalalloy
compositions
Alloy

Composition(wt%)

Zn

Mg

Cu

Co

Zr

Ni

Cr

Li

0.15

0.2

1.3

Rapidsolidification

7090
7091
CW67
7064

8.0
6.5
9.0
7.4

2.5
2.5
2.5
2.4

1.0
1.5
1.5
2.1

1.5
0.4
0.14
0.75 0.3

0.1
-

Mechanicallyalloyed

Al-9052
AMC500 (1)

4.0
4.0

Key:

AluminiumLithiumalloy,AMC500.[Seealso:46.4].

Approximatevalues.

0.5
1.1
0.4 (2) 1.1 (2)

46.11.4.2 Mechanical properties


Table46.11.2givestheambienttemperaturemechanicalpropertiesofthevariousalloys.

Table46.112RSPaluminiumalloys:Ambienttemperatureusetensileproperties
Alloy

7091
7090
CW67
7064
Al-9052
Key:

Temper

TE192
T7
T6511
T7
T7X1
T6
T7
F
F

UTS

YS

Elongation

(MPa)(1)

(MPa)(1)

(%)(1)

640
595
675
620
614
683
650
450
635

600
545
640
580
580
635
621
380
630

13
11
10
9
12
12
9
13
4

(1)Longitudinalpropertiesfromexperimentalextrusions.

46.11.4.3 Stress corrosion resistance


TheSCCresistanceof7090and7091isbetterthanI/M7XXXalloys.SCCresistancegenerallyincreases
with cobalt contents between 0% and 1.6%, Ref. [4612]. For ambient use, CW67 offers the best
combinationofstrengthandSCCresistance.

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46.11.4.4 Fatigue
The effect of P/M processing on the fatigue behaviour of Al alloys is complex. In general, the
resistance to fatigue crack initiation is improved, but resistance to fatigue crack propagation can be
reduced.
A further alloy, 7064 (formerly PM64) is in part strengthened by Zr, Cr and Cocontaining
dispersions. It also has good combinations of strength and SCC resistance, and has shown
superplasticity.

46.11.5 Elevated temperature


46.11.5.1 Alloys
Mostofthesuccessfulalloysdevelopedcontainiron,e.g.AlFeCealloycompositions,suchasCU78
andCZ42fromAlcoa.
Some further RSP/M materials are AlFeVSi composition alloys, of which Allied Signal FVS0812
and FVS1212 are made by planar flow casting, Ref. [4679], and AMC Calidus 350xq is made by
atomising,Ref.[4673].

46.11.5.2 Mechanical properties


Thecharacteristicsofeachgroupofalloyscanbesummarisedas:

AlFeCealloys,asshowninTable46.11.3,CZ42possessgoodstrengthsto315C,Ref.[4613].

AlFeVSi alloys, such as Calidus 350xq, FVS0812 and FVS1212, have usable strengths to
425C; as shown in Table 46.11.4 and Table 46.11.5. Furthermore, they contain a large
proportionofveryfinesilicidesthatincreasethemodulusandsoofferpotentialmasssavings
overTialloys,forexample;asshowninTable46.11.6.

Table46.113RSPaluminiumalloys:Elevatedtemperaturemodifiedproperty
goals(minimumvalues)forshapedextrusionsofP/MalloyCZ42
Temperature(1)
(C)

RT
166
232
260
316
Key:

TS
YS
(MPa) (MPa)

448
365
310
283
221

379
345
296
262
200

E
(GPa)

78.6
68.9
64.1
62.1
56.5

Elongation(%)

FractureToughness,
K1C(MPam)

5.0

L-T: 23, T-L: 18

(1)Valuesatstatedtemperature;AtRTto316C.

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Table46.114RSPaluminiumalloys:Roomandelevatedtemperaturetensile
propertiesofplanarflowcastalloyFVS0812
Temperature

YS

UTS

Elongation

(C)

(MPa)

(MPa)

(%)

(GPa)

24
149
232
316
427

413
345
310
255
138

462
379
338
276
155

12.9
7.2
8.2
11.9
15.1

88.4
83.2
73.1
65.5
61.4

Table46.115RSPaluminiumalloys:Roomandelevatedtemperaturetensile
propertiesofalloyFVS1212
Temperature

UTS

YS

Elongation

(C)

(MPa)

(MPa)

(%)

(GPa)

24
150
230
315

559
469
407
303

531
455
393
297

7.2
4.2
6.0
6.8

95.5
-

Table46.116RSPaluminiumalloys:Elasticmodulus,densityandweightsaving
parametersforthermallystableRSP/Malloys
E

(GPa)

(kg/m3)

Al-5Cr-2Zr
Al-5Cr-2Zr-1Mn
Al-8.3Fe-4.0Ce
Al-7.0Fe-6.0Ce
Al-8Fe-2Mo
Al-8.5Fe-1.3V-1.7Si
Al-2.4Fe-1.2V-2.3Si

80.8
86.5
79.6
80.0
86.2
88.4
95.5

2820
2860
2950
3010
2910
3020
3070

28.7
30.2
27.0
26.6
29.6
29.3
31.1

1.53
1.55
1.46
1.43
1.52
1.48
1.49

Al-Fe-V-Si

80

2990

27.6

1.49

Al-7.5Cr-1.2Fe
Al-6.3Cu-0.3Mn0.06Ti-0.1V-0.18Zr

89.0

2890

30.8

1.54

73.0

2860

25.5

1.46

Alloy(1)

Composition

CU78
CZ42
FVS-0812
FVS-1212
Calidus
350xq
RAE 72
I/M 2219
Key:

E/(2)

E1/3/(3)

(MNm/kg) (N1/3m7/3/kg)

(1)Sources:CUandCZfromAlcoa;FVSseriesfromAlliedSignalsInc.;CalidusfromAMC;others
unknown;
(2)E/Specificmodulus;
(3)E1/3/Bucklingparameter.

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46.12 Al-MMCs - Metal matrix composites


46.12.1 Introduction
There are many reasons for the interest in metal matrix composites. Initial developments were
stimulated by applications which needed improved mechanical properties compared with the
unreinforcedmatrixalloys,i.e.:

Increasedstrengthatroomorelevatedtemperature.

Increasedstiffness.

Sincetheoverallpropertiesofthecompositearelargelydeterminedbythoseofthereinforcingphase,
this has lead to further applications that take advantage of the physical properties of the
reinforcement,e.g.:

LowCTEcoefficientofthermalexpansion.

Highthermalconductivity.

Goodwearresistance.

VariousMMCmaterialcombinationsaredescribed,withindicationsoftheirtypicalmechanicaland
physicalproperties.Thesematerialscanbeclassedascompositeswitheither:

discontinuousreinforcementphases(particles,shortfibresorwhiskers),[See:46.13].

continuousfibrereinforcement,[See:46.15].

Just as with polymer matrix composites, most aluminiummatrix composites are part of a family of
materialswhosepropertiescanbetailoredbymodifyingthevolumeofreinforcingphaseorthematrix
alloy.

46.12.2 Manufacturing processes


A wide range of processes have been employed for the manufacture of MMC components, utilising
solid,liquidandvapourphasetechniques.Severaloftheseprocesstechnologiesaresuitableforboth
discontinuouslyandcontinuouslyreinforcedmaterials.

AnoverviewofthevariousprocessesisillustratedinFigure46.12.1.
FurtherinformationontheprocessesusedforcommerciallyavailableMMCisalsoprovided.

[See: 46.13 for discontinuously reinforced aluminiummatrix composites; 46.15 for continuously
reinforcedmaterials]

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Figure46.121AlMMCs:Overviewofmanufacturingprocesses

46.12.3 Reinforcement materials


Informationonthevariousmaterialsusedasthereinforcingphaseispresented.
[See:46.13discontinuouslyreinforcedMMCs;46.15continuouslyreinforcedMMCs]

46.12.4 MMC nomenclature


AstandardisednomenclatureforaluminiummatrixcompositeshasbeenestablishedbytheAmerican
National Standards Institute (ANSI) Committee H35 on Aluminium and Aluminium alloys under
standardANSIH35.5.
Thenomenclatureisbestillustratedbyanexample,e.g.:
2009/SiC/15pT4
where:
2009

indicates the matrix alloy and is the four-digit number registered with the
Aluminum Association

SiC

indicates the composition of the reinforcement material

15

indicates the volume percentage of reinforcement

code letter that indicates the form of the reinforcement, where p is particulate, w
is whisker and f is fibre.

NOTE
-T4

f is usedfor both continuousfibresand choppedfibres,i.e.a


discontinuousreinforcement.
indicates the temper designation of the matrix alloy (suffix, where appropriate)

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46.12.5 Advantages of MMCs


Compared with polymer matrix composites, aluminium MMCs offer a number of advantages,
including:

Highertransversestiffnessandstrength.

Highertemperaturecapability.

Reducedflammabilityrisk.

Higherthermalconductivities.

Electricalconductivity.

Betterradiationresistance.

Betterresistancetofuelsandsolvents.

Nomoistureabsorption.

Nooutgassing.

Suitableforfrictionandwearresistantapplications.

Component manufacture from discontinuouslyreinforced MMCs using conventional


metalworkingequipment.

46.12.6 Material availability


Whilstsomealuminiummatrixcompositematerialsarewellestablishedforsomeapplications,such
as brake discs, the industry is still relatively newand composedmainly of technology development
companies. This inevitably leads to the introduction of new companies and closures of others.
IdentifyingcurrentsuppliersofAlMMCmaterialscanthereforepresentdifficulties.
Table46.12.1 summarisesthe capabilities of the main suppliers (as of mid2005), together with their
geographiclocationsandtheirwebsiteaddressesforfurtherinformationandcontactdetails.

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Table46.121AlMMCs:Summaryofsuppliersandcapabilities
Supplier(location)

Reinforcements

Matrixalloys

AMC (UK)

SiC, p (a)

2124, 6061

CMT (UK)

Al2O3 , f

Al, Al-Cu2, ?

Electrovac (D)

SiC, p

AlSi7Mg

Sandvik-Osprey (UK)

Si

3M (US)

Al2O3 , f (a)

Al
Al, Al-Cu2,
?(b)

Ametek (US)

SiC, p

n.s (c)

CPS (US)

SiC, p
SiC, p ; Al2O3 ,
f

A356

pressure
infiltration
melt infiltration

3xx, 6061

melt stirring

Duralcan (Canada)

Process

powder
metallurgy
pressure
infiltration
pressure
infiltration
spray forming
melt infiltration

DWA-DRA (US)

SiC, p

2009, 6069, ?

M Cubed (US)

SiC, p

Al, AlSi

powder
metallurgy
melt infiltration

MC 21 (US)

SiC, p

3xx

melt stirring

Millenium Materials
(US)

SiB6 , p

cast alloys ?

melt stirring

MMCC

C, f

AlSi

PCC-AFT (US)

SiC, p

cast alloys ?

PEAK (D)

SiC, p

wrought
alloys

Triton Systems (US)

SiC, p

cast alloys ?

TRL (US)

Al2O3 , f

Al

TTC (US)

SiC, p

Al, AlSi

Key:

pressure
infiltration
pressure
infiltration
spray forming
pressure
infiltration
continuous melt
infiltration
melt infiltration

(a):f=fibre,p=particulate;(b):?=otheralloysavailable;(c):n.s.=notspecified

46.12.7 Sources of further information


Somefurtherinformationsourcesinclude:

MILHDBK174, Ref. [4674]: The American Department of Defense Composite Materials


HandbookhasavolumeonMetalMatrixComposites.
NOTE

IssueAonlyhaslimitedinformationonaluminiumMMCs.

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MMCAssess, Ref. [4675]: This was a European Brite Euram III thematic network project
coordinated by the University of Vienna and run from 1998 to 2001 to exchange and assess
information on MMCs. The website is still maintained and updated and contains a large
amountofdataonMMCmaterialsandprocesstechnologyandalistofpotentialsuppliers.
NOTE

The list is updated with names of new suppliers but does not
appeartobecheckedforthosenolongertrading.

D.B.Miracle; Metal Matrix Composites for Space Systems: Current Uses and Future
Opportunities, Ref [4676]. The author is with the US Air Force Research Laboratories which
sponsors much of the US (restricted) R&D on MMCs. However, a number of unrestricted
publicationsareavailablefordownloadfromthesitestated,Ref.[4676].

46.13 Discontinuously reinforced Al-MMCs


46.13.1 Features
The discontinuous nature of the reinforcement means that these composites are ideally suited to
applicationsneedingmultidirectionalproperties,i.e.inshapedcomponents.Thishasresultedinthe
availability of materials that can be formed by casting or metalworking processes such as rolling,
forgingorextrusion,andsubsequentlymachined.Componentsfrommostofthematerialscanalsobe
joined using conventional welding, soldering or brazing techniques in addition to mechanical
assembly.

46.13.2 Development
Manytypesofdiscontinuousreinforcementshavebeencombinedwithaluminiumalloysoverthelast
20 years. The objective is to improve both the mechanical and physical properties of the base alloy.
Somearenowestablishedascommercialmaterialswhilstfurtherdevelopmentcontinues.
Whilst initial interest was primarily in improved mechanical properties, there is now a significant
growth in the development of aluminiumbased MMCs as lightweight materials with high rigidity
andgoodthermalconductivity,coupledwithlowthermalexpansion.Thesearedestinedapplications
suchasthermalmanagementofhighpowersemiconductordevicesandsubstratesforspacemirrors.

46.13.3 Matrix alloys


Thematrixalloyshavebeenpowdermetallurgy,purealuminium,wroughtandcastingalloys.
Thewroughtalloystendtobefromthe2XXX,6XXXand7XXXseriesandthecastalloysfromthe3xx
seriesorsimplercleaneraluminiumsiliconalloys.

46.13.4 Types of reinforcement


46.13.4.1 General
Discontinuousreinforcementsareusuallygroupedas:

Particulate,e.g.Siliconcarbide

Shortorchoppedfibre,e.g.Aluminaorcarbon.

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Whisker,e.g.Siliconcarbide.

Whilst a variety of reinforcement materials and product forms have been studied only a limited
number have, so far, proved technically or commercially viable. The most popular is particulate
silicon carbide or chopped carbon fibres.Particulatesilicon hexaboride (SiB6)also hasa commercial
presence.
There does not appear tobe any commercialuse ofalumina oraluminosilicate particulates, mainly
due to difficulties in achieving good bonding with the matrix, or whisker materials due to the high
cost.Thesematerialshavethereforebeenexcludedfromthissection.
An alternative material is the family of highsiliconAlSialloys processed by spray forming. Whilst
strictly alloys, they are also described as insitu composites that contain a dispersion of silicon
particles in an aluminiumsilicon matrix, since the resulting product could not be made through
conventionalingotcastingtechniques.

46.13.4.2 Silicon carbide


Particulatesiliconcarbideiswidelyavailableinarangeofgrades.Ultrafine,FEPA1000or1500grits
(micron sized) particles are preferred for highstrength MMCs, primarily manufactured by powder
metallurgyroutes.
Slightlycoarserabrasivegritgrades,FEPA400to600(from10mto40m,typically)arefavouredfor
thermal management and wear resistant MMCs, which are generally produced via liquid metal
techniques.
Thepropertiesofsiliconcarbideofparticularinterestare,Ref.[4682]:

Lowdensity;3210kg/m3.

Highelasticmodulus;430GPa.

Highcompressivestrength;2800MPa.

Highhardness;2480Knoop.

Highthermalconductivity;1320W/mK.

Lowthermalexpansioncoefficient;3.4ppm/K.

Goodbondingwithaluminiummatrix.

[Seealso:43.12siliconcarbidetechnicalceramics]

46.13.4.3 Silicon hexaboride


An alternative particulate material has been put forward recently by Millenium Materials for some
applicationsnotdemandingthehighthermalconductivityofsiliconcarbide.
Silicon hexaboride (SiB6) has similar strength and hardness to silicon carbide but its lower density,
closertothatofmoltenaluminiumalloys,meansthatitismoreeasilydispersedbythemeltstirring
processandremainsinsuspensionfacilitatingshapecastingtechniquesandrecyclingofrunners.The
mainpropertiesarelistedinTable46.13.1.

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Table46.131AlMMCs:TypicalpropertiesofSiB6siliconhexaborideparticulate
reinforcementHexon
Appearance

Black Powder

Chemical formula

SiB6

Density

2430 kg/m3

Crystallographic structure

Orthorhombic

Hardness

2572 kg/m2

Melting point

1950C

Thermal coefficient of expansion

4.6 10-6/C

Modulus of elasticity

290 GPa

Oxidation resistance

Stable in air to 1550C

Electrical conductivity

6.5 to 200 ohm.cm (RT to 800C)

Thermal conductivity

9 W/m/K

MOR (1) strength

225 MPa

Key:

Suppliersdata
HexonSiB6isaregisteredtradenameofMillenniumMaterials
(1)ModulusofRupture

CaroliteisaproprietaryMMCfromMillenniumMaterials(USA)reinforcedwithsiliconhexaboride.

[Seealso:46.14propertiesofCarolitecomposites]

46.13.4.4 Chopped carbon fibres


Some gradesof pitchbased carbon fibres can be given a graphitising heat treatment. This results in
extremely high thermal conductivity in the axial (longitudinal) direction. Coupled with very low
(possibly negative) thermal expansion, low density and high modulus such reinforcements are of
interestforthermalmanagementcomposites.
Thechoppedfibresareobtainedbymillingtheprecursorresinfibrestoaround300mlengthbefore
thecarbonisationtreatment.TypicalpropertiesaregiveninTable46.13.2,Ref.[4681].
[Seealso:46.14propertiesofMetGrafAl/Cfcomposites]

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Table46.132AlMMCs:TypicalpropertiesofconstituentsusedforMMCC
MetGrafAl/Cfcomposites
Youngsmodulus
[GPa]

Material
(1)

CTE
[ppm/K]

Thermal
Conductivity

Density
[kg/m3]

L(4)

T(5)

L(4)

T(5)

[W/mK]

758

6.9

1.45

10

550

2140

6.9

1.45

10

900 to1100

2150

(3)

931 to
965

Al-Si alloy

69

69

23

23

155

2660

Fibres:
A and B (a)
(2)

Fibres:
C and D (b)

Key

(1)MMCCsuppliersdata;Allarepitchbasedproductsandaremilledbeforecarbonising;
(2)MilledfibresAandBareproducedfromthesameresinasCytecP120;
(3)MilledfibresCandDareproducedfromthesameresinasCytecK1100;
(4)LLongitudinal(listedasaxialinsuppliersdata);
(5)TTransverse

46.13.5 Processing
46.13.5.1 General
Particulate reinforced aluminium alloys can be manufactured by numerous routes, [See: Figure
46.12.1].

46.13.5.2 Occupational health and safety


ManytypesofceramicwhiskersandpolycrystallinefibreshavebeenevaluatedbytheWorldHealth
Organisations International Agency for Research on Cancer (Monograph 43, 1988) as possibly
carcinogenic to humans, and are subject to occupational health and safety risk control measures in
somejurisdictions.
Exposuretorespirabledustscontainingthesematerialsshouldbeavoided.Suchdustsarenotlikelyto
bereleasedfromMMCsintheirnormalhandlinganduse,butcontrolmeasuresneedtobetakenifthe
materialsaremachined,cutorsubjecttoabrasion.
RefertomanufacturersandsuppliersSafetyDataSheetsforfurtherinformation.

46.13.5.3 Powder metallurgy


Powdermetallurgyprocessesstartwithfineconstituentparticleswhichareblendedbyhighenergy
milling before compacting to billets by vacuum hot pressing or hot isostatic pressing (HIPing),
followedbythermomechanicallyprocessingtoafinishedproduct;similartoconventionalalloys.

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46.13.5.4 Liquid state


Liquidstateprocessingmethodsinclude,

meltstirringorstircasting,

pressurecastingorsqueezecasting,

infiltration,

sprayforming.

46.13.5.5 Stir casting


Thisisawellestablishedmethodinwhichaceramicpowder,usuallyparticulateSiC,ismixedintoa
molten aluminium alloy under controlled conditions. The process has been used to produce the
DuralcanseriesofAlbasedMMCswhicharesoldiningotorbilletformforsubsequentfabrication
bycastingrollingorextrusion.

The nature of the process limits the amount of reinforcement that can be incorporated to usually a
maximum of 20 volume percent. The usual matrix alloys are 3xx AlSi alloys, which both assist
manufactureandsubsequentcastingprocessesandalsocontributetothemechanicalpropertiesofthe
composite.
An advantage of these materials is that they can be shaped using conventional gravity or pressure
diecastingequipment.Themainapplicationsforthesematerialshavebeenforwearresistance,such
asbrakediscsformotorsportandforhighspeedtrains.

Animprovedhighspeedmixingprocess,recentlyannouncedbyMC21(USA),claimstheabilityto
incorporateupto40volumepercentoflowcostSiCparticulateinashortprocesscycletime.Thisis
said to enable the manufacture of cast composite products at lower cost than alternative processes.
Theprocesscanbeusedforcastingcomponents,directlyafterthestirringhasbeencompleted,orthe
moltencompositecanbecastintoingotsforsubsequentremeltingandcasting;asforDuralcantype
materials.

46.13.5.6 Pressure-assisted or squeeze casting


This process utilises a preform of ceramic particles or fibres which is placed in the cavity of a
conventionalmetaldiebeforethematrixalloyismechanicallyforcedintotheintersticesunderhigh
pressure.
Theadvantagesoftheprocessinclude:

Highproductionspeed,

Abilitytoproducecomponentsthatareselectivelyreinforced.

These advantages can reduce cost and enable the component to be machined or joined using
conventionaltechniques.Themainapplicationareahasthereforebeenintheautomotiveindustry.

46.13.5.7 Infiltration
InfiltrationtechniquesarenowwidelyusedforaluminiumbasedMMCsbecausetheyarecapableof
incorporatinghighvolumeloadingsofreinforcement.Thereareanumberofvariationsonthegeneral
principle, mainly depending on whether or not it is gas pressureassisted and the degree of
pressurisation.

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Gaspressureinfiltrationutilisesapreform(usuallyofSiC)whichiscastormouldedtonearnetshape
beforeintroductionintothecompositeproductiontooling.Thisprocessisalsousedforchoppedfibre
reinforcedcompositeswhichforsome,predominantlyflat,applicationsarepreformedwiththefibre
axesrandomlyalignedinoneplanetogiveenhancedthermalproperties.

Apressurelessprocess,knownasPrimex,wasdevelopedbytheformerLanxideCorporationandis
nowoperatedbylicensees(includingMCubedandTTC).Thisprocessusesmatrixalloyscontaining
magnesium,whichreactswithnitrogengasintheproductiontooling,togivespontaneouslyreduced
pressurewhichdrawsthemoltenmatrixintothepreform.Thisenablesloadingsofupto70volume
percent SiC reinforcement to be produced. In a variant of the process an infiltrated bed of SiC is
dispersedintoafurthervolumeofmatrixalloytogivecompositeswithlowerreinforcementloadings
whichcanbecastbyconventionaltechniques.
Thelowerpressurescomparedwithpressureorsqueezecastingmeanthatmorecomplexgeometries
can be produced, there is less tendency for damage to the performs and lower cost tooling can be
used,whichmakestheprocessmoresuitableforlowerproductionrates.

46.13.5.8 Spray forming


Sprayformingusesgaspressuretoatomisemoltenmetalintoastreamofsmalldroplets,whichare
thenrapidlysolidifiedonacontinuouslywithdrawnsubstrate.
Powdered reinforcement particles can be introduced into the stream of molten metal to produce
MMCswithfinematrixgrainsize.Thesecompositesaremainlyusedforwearresistantapplicationsin
theautomotiveindustry.
Alternatively, high siliconcontaining aluminium alloys can be spray formed to produce insitu
composites which contain higher silicon contents than that possible by conventional processing
techniques.Theseproductsareusedprimarilyfortheirlowerthermalexpansioncoefficientsthatare
tailoredaccordingtothealloycomposition.

46.14 Discontinuously reinforced Al-alloys: Properties


46.14.1 General
Owing to the differences in process methods and test conditions between products from different
manufacturers,thedatapresented(fromsuppliers)isgenerallygroupedaccordingtomaterial,i.e.:

Powdermetallurgy.

Meltinfiltrationprocesses.

Sprayformedmaterials.

Thetextattemptstodrawcomparisonsbetweenmaterials,wherepossible.

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46.14.2 Powder metallurgy MMCs


46.14.2.1 General
Products made by PM powder metallurgical processes are aimed primarily at highstrength and
elevatedtemperatureapplications.Datafromsuppliersofmaterialsinthiscategory,AMCandDWA,
ispresented.
WhilstmostofPMmaterialsareaimedatapplicationsinthermalmanagement,takingadvantageof
their high conductivity and low expansion, several materials suitable for structural applications are
alsoproducedthisway.

46.14.2.2 AMC225xe and AMC640xa


TheseAMCmaterialsareproducedfrom:

AMC225xe:2124alloywith25vol.%2mto3mSiC.

AMC640xa:6061alloywith40vol.%2mto3mSiC.

The products are available as plate, extrusions or forgings and typical room temperature properties
aregiveninTable46.14.1.

Table46.141AlMMCs:RoomtemperaturepropertiesofAMC225xeand
AMC640xa
Properties

AMC225xe*

AMC640xa*

Matrix alloy

2124

6061

Reinforcement

SiCp

SiCp

Volume (%)

25

40

Product form

plate

extrusion

extrusion

Heat treatment

T4

T6

T1

Orientation

Ultimate tensile strength (MPa)

650

570

560

Yield stress (MPa)

480

480

440

Fatigue Strength, 107 cycles, (MPa)


Elongation (%)

310
5

230
2.5

Youngs modulus (GPa)

115

140

140

Density (kg/m3)
Thermal conductivity, (W/mK)

2880

2900

150

130

Coefficient of thermal expansion,


(ppm/K)
Electrical conductivity (%IACS)

15.5

13.4

21

21

Suppliersdata

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TheeffectsoftemperatureonthetensilepropertiesofAMC225xeplatearegiveninTable46.14.2,and
on both tensile and fatigue properties of extruded material in Table 46.14.3, which also includes
results for two Duralcan materials tested under the same conditions. The good temperature
resistanceandstabilityofthesematerialsmakesthemsuitableforapplicationssuchasnozzleguide
vanesandcontrolvalveblocks.

Table46.142AlMMCs:ElevatedtemperaturepropertiesofAMC225xeplate
ThermalCycling

Temper

T4
As heat treated
T1

T4
After 200 thermal
cycles, 50C to
200C
T1

Temperature

UTS

YS

(C)

(MPa)

(MPa)

150

616

474

200

530

448

260

194

128

350

65

48

150

428

321

200

358

276

260

200

102

350

65

48

150

442

369

200

343

265

260

193

125

350

59

45

150

348

269

200

265

187

260

150

92

350

56

46

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Table46.143AlMMCs:ElevatedtemperaturepropertiesofextrudedAMC225xe
comparedwithDuralcan MMC's
Material

225xe - T4
(1)

225xe - T1
(1)

W2F20A-T6
(2)

F3S20S T6 (3)

Key

Temp.

UTS

YS

(C)

(MPa)

(MPa)

(GPa)

Fatiguestrength,107
cycles,(MPa)

24

633

486

116.2

410

150

616

474

110.9

330

200

530

448

108.3

203

250

194

128

106.6

100

24

477

328

115.2

290

150

428

321

111.1

200

200

358

276

109.2

160

250

200

102

107.3

105

24

369

286

97.3

280

150

345

267

92.1

195

200

314

236

89.9

150

250

228

213

87.3

110

24

331

282

104.9

180

150

264

225

99.8

110

200

230

201

97.2

95

250

150

122

94.6

70

(1)AMC225xe(2124+25%SiCpextrudedbar);
(2)DuralcanW2F20AT6(2618+20%Al2O3pextrudedbar);
(3)DuralcanF3S20ST6(A359+20%SiCpforgeddisc).

46.14.2.3 DWA 2009/SiC and 6092/SiC


DWA is one of the longest established suppliers of powder metallurgy based AlMMCs to the
aerospace industry. Most of their products utilise FEPA F1000 (measured around 6 m) SiC
particulatesalthoughthefinerF1500grade(around2m)isbeingevaluated.
Themostcommonlyusedproductsarebasedon2009and6092aluminiumalloyswithreinforcement
loadingsupto25%.
Table 46.14.4 gives room temperature properties of 2009/SiC/15.5 extrusion together with data for
6092/SiCextrusionswithtwodifferentSiCcontentsandonematerialinplateform.

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Table46.144AlMMCs:TypicalroomtemperaturepropertiesofDWA
2009/SiCpand6092/SiCpcomposites
2009/SiC
/15.5p

Properties(1)

Form
Temper
Thickness (mm)
Density (kg/m3)
Tensile
strength
(MPa)
Compressive
strength
(MPa)
Shear
strength
(MPa)
Flexural
strength
(MPa)
Flexural
yield
strength
(MPa)
Yield stress
(MPa)
Elongation
(%)
Elastic
modulus
(GPa)
Compressive
modulus
(GPa)
CTE(ppm/K)
Key:

L
LT

6092/SiC
/17.5p

extrusio extrusio
n
n
T-42
T-6
95.3
2.3
2823
2796
552
510
510

6092/SiC
/17.5p

6092/SiC/
25p

sheet
T-6
2.5
2796
462
455

extrusio
n
T-6
18.8
2823
517
483

L
LT

462
-

407
386

427
407

L
LT

303
-

290
290

310
290

L (E/d=1.5)
L (E/d=2.0)
LT (E/d=1.5)
LT (E/d=2.0)
L (E/d=1.5)
L (E/d=2.0)
LT (E/d=1.5)
LT (E/d=2.0)
L
LT
L
LT
L
LT

372
345
7
6
95
92

793
1000
703
827
448
7
105
-

731
958
758
958
689
855
696
841
393
365
8
7
101
101

703
945
696
910
683
834
683
834
421
400
5
4
121
114

L
LT

105
-

100
100

121
113

L
LT

16.4
-

15.3
16.9

(1)Suppliersdata

Furtherdataon2009/SiCextrusionsisgiveninTable46.14.5,whichshowstheeffectsofvariationsin
particlecontentandsize,matrixtemperandextrusionratio.

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Table46.145AlMMCs:TypicalroomtemperaturetensilepropertiesofDWA
2009/SiCpextrudedcomposites
Matrix
alloy

SiCp
(vol.
%)

SiCp
d50
Value
(m)

Temper

Extrusion
ratio

Directio
n

YS
(MPa)

UTS
(MP
a)

Elongation
(%)

E
(GPa
)

2009

T4

20:1 (1)

255

358

10.0

71

2009

6.43

T4

496: 1 (2)

400

531

10.0

79

2009

15

6.43

T4

14:1 (3)

LT

348

483

5.2

94

2009

15

6.43

T6

14:1 (3)

383

530

8.5

100

2009

15

6.43

T4

496:1 (2)

424

594

9.8

105

424

608

3.7

20:1

(1)

2009

20

6.43

T4

2009

25

6.43

T4

14:1 (3)

LT

372

496

1.7

112

2009

25

1.92

T4

14:1 (3)

LT

421

545

1.8

114

2009

25

1.92

T4

LT

427

586

1.8

117

2009

25

1.92

T4

448

662

2.4

121

2009

25

6.43

T4

496:1 (2)

462

669

5.1

119

2009

25

1.92

T4

496:1 (2)

483

669

3.2

123

Key:

14:1 +
forge (4)
14:1 +
forge (4)

Suppliersdata.SiCpd50valuemeasuredbyDWAACusingCoulterlaserdiffraction;
Extrudedmaterialssizes:(1)12mmthickrectangularbar;(2)16mmdiameterroundbar;(3)95mm
diameterroundbar;(4)95mmdiameterroundbarforgedto25mmthickrectangularbar

The effects of elevated temperature on tensile andfatigue properties of 2009/SiC with 15%and 25%
particulate loadings are shown in Figure 46.14.1 and Figure 46.14.2 with comparative data for
conventionalaluminiumalloysineachcase.
The higher properties are obtained from composites based on finer (F1500) particulates. These
materials have been used for aerospace applications needing stability and hightemperature
resistance,suchascontrolvalveblocksandnozzleguidevanes.

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Figure46.141AlMMCs:Typicalelevatedtemperaturepropertiesof2009/SiCT4
DRAcomparedwithconventionalwroughtaluminiumalloys

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Figure46.142AlMMCs:Typicalroomandelevatedtemperaturefatigue
propertiesof2009/SiCDRAcomparedwithconventionalwroughtaluminium
alloys

46.14.3 MMCs produced by melt infiltration processes


46.14.3.1 General
Current melt infiltration techniques are capable of producing aluminiummatrix composites with
particulate loadings of up to 70 volume percent. By incorporating reinforcements with high
conductivity and low expansion coefficient, these composites are finding wide use as lightweight
materialsforpackagingofsemiconductordevicesforaerospaceapplications.
In addition, particularly at lower reinforcement loadings, many materials produced this way offer
goodcombinationsofmechanicalandthermalpropertiesandtheabilitytobecasttonearnetshape,
whichmakesthemsuitedtostructuralspaceapplications.

46.14.3.2 CPS AlSic-series materials


AlSic materials, from CPS Ceramic Process Systems, are made using a gas pressure infiltration
technique enabling SiC loadings up to 63 vol.%. The SiC preforms are moulded to near netshape,
which reduces the extent of subsequent machining necessary. Some typical properties for AlSic
materialsaregiveninTable46.14.6.
Whilst both matrix and particulates contribute to the high thermal conductivity, which gradually
increases with SiC content, the low expansion coefficient of SiC results in composites with
significantlylowerthermalexpansionathigherparticulatecontents.

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Table46.146AlMMCs:TypicalpropertiesofCPSAl/SiCpcomposites
Properties

AlSiC9

AlSiC10

AlSiC12

Matrix Alloy A 356.2

37 vol.%

45 vol.%

63 vol.%

Reinforcement SiC (electronic grade)

63 vol.%

55 vol.%

37 vol.%

Strength (MPa) a-bar 4pt-bend

488

450

471

Youngs Modulus (GPa)

188

167

167

Shear Modulus (GPa)

76

67

69

Density (kg/m3)

3010

2960

2890

30C to 100C

9.77

10.9

30C to 150C

8.37

10.16

11.2

30C to 200C

8.75

10.56

11.7

Specific Heat (J/kgK) @ 25C

741
200 typ. /
190 min
20.7

786
200 typ. /
190 min
20.7

808
180 typ. /
170 min
20.7

Thermal Expansion, CTE, (ppm/C):

Thermal Conductivity (W/mK) @25C


Electrical Resistance (ohm.cm)

Suppliersdata.

46.14.3.3 MCX-series Al/SiC materials


ThePrimexpressurelessinfiltrationprocessdevelopedbyLanxideisnowusedbyThermalTransfer
Composites(TTC)toproducearangeofthermalpackagingmaterials.
TheMCXxxxseriesusesnearnetshapeSiCpreformstoproducecomponentswithhighcontentsof
particulatetogivelowthermalexpansioncoupledwithhighthermalconductivity.
TheMCXxxxxseriesusesthePRIMEXCASTprocessinwhichabedofinfiltratedSiCparticulates
isdilutedwithmoltenmatrixalloytoenablethe(lessviscous)compositetobecastusingconventional
techniques.HavinglowerSiCcontents,thesematerialshaveintermediatevaluesofthermalexpansion
coefficient, around half that of the unreinforced matrix alloy but, since they can be cast to near net
shape,theyaresuitedtocontrolledexpansionstructuralapplications.
TypicalpropertiesofanumberofMCXxxxandMCXxxxxmaterialsaregiveninTable46.14.7.
Whilst the actualSiC contents are not stated by thesupplier, they can be estimated from the values
given for density since SiC has a value of about 3.20kg/m3 compared with about 2.70kg/m3 for
aluminiumalloys.

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Table46.147AlMMCs:TypicalroomtemperaturepropertiesofTTCAl/SiCp
composites
1:PRIMEX

Properties

MCX693

MCX686

MCX696

MCX724

MCX947

Flexural strength,
4pt-bend (MPa)

300

480

517

330

530

Young's modulus
(GPa)
Poisson's ratio

255

235

262

235

196

0.24

0.22

0.25

0.23

0.25

Density (kg/m3)

2980

3000

3010

2940

2950

Coefficient of
thermal expansion
(ppm/K)
Specific heat
(J/kg.K)
Thermal
conductivity
(W/mK)
Electrical
resistivity
(ohm.cm)

6.4

6.8

6.9

7.2

9.4

720-760

720-760

720-760

720-760

720-760

180

175

192

165

179

30 - 50

30 - 50

30 - 50

30 - 50

30 - 50

Suppliersdata.

2:PRIMEXCAST

Properties

MCX
1195

MCX1405 MCX1605

Ultimate tensile
strength (MPa)

226

239

295

Young's modulus
(GPa)
Poisson's ratio

151

125

106

0.28

0.29

0.31

Density (kg/m3)

2870

2800

2770

Coefficient of
thermal expansion
(ppm/K)
Specific heat
(J/kg.K)
Thermal
conductivity
(W/mK)

11.9

14

16.2

763

830

890

183

165

132

Suppliersdata.

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46.14.3.4 ASC-xxx Al/SiC series materials


TheLanxideprocessisalsousedbyMCubedTechnologiestoproducearangeofcompositeswithSiC
loadingsfrom30%to70%,byvolume.ThepropertiesoftheseASCxxxmaterialsaregiveninTable
46.14.8 and, as expected from the similar process technology, are similar to those of the MCXxxxx
PRIMEX CAST materials from TTC. These materials are also of interest for both thermal
managementandstructuralapplications.

Table46.148AlMMCs:TypicalpropertiesofcompositesfromMCubed
Technologies
Materialdesignation
Properties

Matrix
Particle
Reinforcement
Content (% vol.)
Matrix (Heat
Treatment)
UTS, (MPa)
Flexural strength,
(MPa)
Modulus, (GPa)
Poissons ratio
Fatigue Limit, 107
cycles:
R = 0.1 (MPa)
R = 1 (MPa)
Fracture
Toughness
(MPam)
Density, (kg/m3)
CTE, 25C to100C,
(ppm/K)
Thermal
Conductivity
(W/mK)
Specific heat (J/kg
K)
Knoop hardness,
500g load (kg/mm2)
Key:

ASC
301(1)

ASC
303

ASC
401(1)

ASC
551(1)

Al
SiC

SiC

ASC
701(1)

HSC
702E(2)

Al-Si
SiC

30
30
40
Al-10SiAl-10SiAl
1Mg
1Mg
AA359
(T6)
(T6)
370
300
370

SiC

SiC

SiC

55
Al-SiMg
(F)
340

70
Al-SiMg
(F)
230

75
Al70Si
-

270

125
0.29

120
0.29

150
0.28

200
0.24

270
0.22

345
0.19

15

11

10

5.5

2780

2780

2870

2950

3010

3040

14

15

12

10

6.2

4.1

160

146

170

180

170

210

820

750

730

700

165

343

647

1609

190
130

Suppliersdata.
(1)ASCmaterialsproducedunderLanxidelicenses;
(2)reactiveinfiltrationtechniqueofpreform

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The material designated HSC702E is produced using a reactive infiltration technique in which a
preformofSiCcontainingfreecarbonisinfiltratedwithanAlSialloy.
TheSifromthemeltreactswiththefreecarbontoproduceadditionalSiC,assistingthebondingofthe
finalmaterial,whichcanbeconsideredasanaluminiumtoughenedSiCratherthananAl/SiCMMC.
However,itisincludedintheTable,forcomparison,wherethehigherhardnessandlowerexpansion
coefficientareapparent.

46.14.3.5 METSIC Al/SiC


Metal Matrix Cast Composites Inc (MMCC) has adapted rapid prototyping technology to the
preparation of complex shaped reinforcement preforms directly from CAD files. These are then
infiltratedwithmoltenaluminiumalloyusingaproprietarypressureinvestmentcastingprocess.
TheprocessisaimedatstructuralapplicationsandtypicalpropertiesofanAl/SiC/40pcompositeare
giveninTable46.14.9,togetherwith6061aluminiumalloyand1010steelforcomparisonpurposes.

Table46.149AlMMCs:TypicalpropertiesofMMCCMETSICAl/SiCp
compositecomparedwithaluminiumandsteel
Material

Properties

METSIC

Al6061T6

1010Steel

Matrix

Al

Reinforcement (%)
Ultimate tensile strength
(MPa)

40 SiC

300-400

310

365

Youngs modulus (GPa)

150

69

205

Density (kg/m3)

3000

3000

8000

Thermal expansion (ppm/K)


Thermal conductivity
(W/m.K)

10-12

23.6

12.2

185

167

49

Suppliersdata.

46.14.3.6 Carolite Al/SiB6 materials


As an alternative to SiC reinforcements, Millenium Materials has published limited information on
Al/SiB6reinforcedcomposites.Itisclaimedthatwhilstthisreinforcementofferssimilarstrengthand
stiffness enhancements to that obtained with SiC, its lower density makes it easier to disperse, and
remain suspended, in molten aluminium alloys. This is said to make casting, using conventional
techniques,morepracticableandalsoenablethematerialtoberecycled,soreducingcosts.However,
the low thermal conductivity of SiB6 means the composites incorporating this material are aimed
primarilyatcaststructuralcomponents.
Preliminary data for Carolite composites is given in Table 46.14.10. Most of the data presented is
calculated using the rule of mixtures for Al/SiC composites. Only the property values with grey
backgroundareactualdata

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Table46.1410AlMMCs:TypicalpropertiesofMilleniumMaterialsCarolite
SiB6particulatereinforcedcomposites
Hexon
SiB6
(vol.%)

Ultimate
tensile
strength(2)
(MPa)

0
10
15
20
30
40
50
60
70

228
259
345
352
372
386
407
427
448

165
221
310
324
345
359
379
400
421

MatrixalloyA356A356
62
69
131
97
138
103
145
117
159
145
172
154
186
193
200
214
207
241

151
146
120
110
100
95
85
75
65

21.5
15.5
14.9
14.3
12
9.7
8.9
8
7.1

0
10
15
20
30
40
50
60
70

310
352
469
476
503
524
552
579
607

276
317
434
441
469
490
517
545
572

Matrixalloy6061T6
62
69
131
97
138
103
145
117
159
145
172
165
186
193
200
214
207
241

201
194
160
146
133
126
113
100
86

23.5
16.9
16.2
15.6
13.1
10.6
9.7
8.7
7.7

Key

Yield
Fatigue
Elastic
(2)
(2)
stress strength modulus(3
)(GPa)
(MPa)
(MPa)

Thermal
Thermal
(3)
conductivity expansion(3
)(ppm/K)
(W/mK)

Suppliersdata.
(1)Valueswithgreybackgroundareactualdata;
(2)StrengthdataestimatedfromdatainliteratureforMMCscontainingSiC.Duetothesimilarity
ofHexonSiB6andSiC,similarreinforcementeffectsareexpected;
(3)Estimatedfromruleofmixturesorafittoactualdata.

46.14.3.7 MetGraf Al/Cf


In addition to high tensile strength and modulus, some grades of graphitised pitchbased carbon
fibres have extremely high thermal conductivity (around 500 W/mK to 1000W/mK) in the axial
direction. This is coupled with low density and low coefficient of thermal expansion, which in the
transverse direction can be negative, although transverse thermal conductivity is low (around 2.4
W/mK).
By incorporating chopped fibres, randomly oriented in a felted preform, Metal Matrix Cast
Composites (MMCC) have produced aluminiummatrix composites with high thermal conductivity
coupledwithlowexpansioncoefficientinthexydirectionsandthermalpropertiesreflectingthoseof
thematrixmaterialinthezdirection;asshowninTable46.14.11.

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Table46.1411AlMMCs:TypicalroomtemperaturepropertiesofMMCC
MetGrafAl/Cfcomposites
MetGraf

MetGraf

4230

7200

Al/Si

Al/Si

103

93

Ultimate compressive strength (MPa)

203

203

Flexural strength (MPa)

186

159

Yield stress, compression (MPa)

110

110

Youngs modulus (GPa)

98

89

2400

2500

24

24

230

200

120

125

Electrical resistivity (.ohm.cm)

6.89

Hardness (Rockwell E)

60-80

Properties

Matrix alloy
Ultimate tensile strength (MPa):

In-plane (xy)
Thickness
(z)

Density (kg/m3)
Thermal expansion, average
value of 55C to +125C
(ppm/K):
Thermal conductivity (W/mK):

In-plane (xy)
Thickness
(z)
In-plane (xy)
Thickness
(z)

Suppliers data.

The special feature of these materials of interest for space applications is the very low density
comparedwithconventionallowexpansionthermalpackagingmaterials;giveninTable46.14.12.
The chopped fibre reinforcement also imparts good strength and modulus making these materials
suited to applications needing a combination of good thermal management together with structural
stiffnessanddimensionalstability,suchasspacemirrors.

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Table46.1412AlMMCs:TypicalpropertiesofMMCCMetGrafAl/Cf
compositescomparedwithotherthermalpackagingmaterials

MetGraf MetGraf
7200
4230

Kovar

Al/SiC

CuMo
8020

CuMo
8515

CuW
9010

CuW
8515

Thermal
conductivit
y
(W/mK)

200

230

17

180

160

140

160

175

Thermal
expansion
(ppm/K)

7.5

4.0

5.9

6.7

7.2

6.5

6.1

6.7

Density
(kg/m3)

2460

2400

8300

3200

9800

9900

1770

1630

Suppliersdata.

46.14.4 Spray-formed materials


46.14.4.1 Osprey CE alloys
The sprayforming process, developed by Osprey, was a bulk rapid solidification process for the
manufactureofenhancedconventionalalloys.Theprocesswasexpandedtoenabletheincorporation
of reinforcement particulates. The German licensee, Peak Werkstoff, is understood to be supplying
wearresistantAlMMCstotheautomotiveindustry.
OspreyarenowconcentratingonthemanufactureofAl/Silowexpansionmaterials.Theseareinsitu
composites in that the second phase material (in this case Si) is precipitated in fine form from a
supersaturatedhightemperaturemoltenalloybyrapidsolidification.
Theprocesscanbeusedformaterialscontainingfromzeroto70%Siwhichmeansthelowexpansion
coefficientofsiliconcanbeutilisedtotailorthecompositepropertiestoanyvaluebetweenthatofthe
basealuminiumtoaround8ppm/Kforthe70%Sialloy.
The main advantages of these materials over alternative thermal packaging MMCs is their low
density, because Si has lower density than SiC, and their ability to be machined using conventional
equipment.TypicalpropertiesofthestandardrangeofalloysaregiveninTable46.14.13.

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Table46.1413AlMMCs:PropertiesofOspreyCEAlSiinsitucomposite
alloys
Ospreystandardalloys

Properties
CE7

CE9

CE11

CE13

CE17

CE17M

70
2400

60
2450

50
2500

42
2550

27
2600

27
2600

100

134

138

176

236

380

143
100
129
51
0.26

140
134
124
49
0.25

172
125
121
49
0.25

213
155
107
42
0.27

210
183
92
36
0.28

92
36
0.28

7.6

11.6

25C to 100C

7.4

9.0

11.0

12.8

16.0

16.0

25C to 200C

8.3

9.9

12.7

13.6

17.0

17.0

25C to 300C

8.5

10.5

13.1

14.4

17.7

17.7

25C to 400C

8.2

10.8

13.7

15.0

17.5

17.5

25C to 500C

7.7

10.1

14.4

15.2

16.8

16.8

Thermal conductivity
(W/mK):
100C

180

50C

140

0C

125

25C

120

129

149

160

177

147

100C

110

125

132

200C

100

108

122

151

147

Silicon content (%)


Density (kg/m3)
Ultimate tensile strength
(MPa)
Bend strength (MPa)
Yield stress (MPa)
Youngs modulus (GPa)
Shear modulus (GPa)(1)
Poissons ratio
Coefficient of thermal
expansion (ppm/C):
60C to 200C

Key:

Suppliersdata:Osprey(http://www.smt.sandvik.com/)
(1)SupplierquotedRigiditymodulus

46.14.5 Further information


Owingtothemannerinwhichdiscontinuouslyreinforcedmaterialsareproduced,thereisscopefor
varying the properties to suite the specific needs of the user. The suppliers listed therefore tend to
haveadditionalinformation,whichispublishedopenly.

[Seealso:46.12;Table46.12.1forsupplierdetails]

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46.15 Continuously Reinforced Al-Alloy MMC


46.15.1 General
Onlythosecontinuouslyreinforcedaluminiumcompositesproducedbymeltinfiltrationprocessesare
described.
Materials produced mechanically by solid state bonding processes are described separately under
FMLFibreMetalLaminates,[See:Chapter100].

46.15.2 Fibres
46.15.2.1 General
ContinuousreinforcementsstudiedforaluminiumMMCsinclude,[Seealso:42.6].

Aluminafibres,

Aluminosilicatefibres,

Boronfilament,

Carbonfibres,

Siliconcarbidefilamentsandfibres,

Whilst boron and silicon carbide fibres received some attention, mainly for specialised military
applications, these reinforcements have not been developed for wider spread use, so are not
considered of current interest for space applications. Problems associated with these materials were
bothtechnicalandeconomic.
Table 46.15.1 gives typical properties of those continuous reinforcement fibres which are of greatest
interest for use with aluminium matrix alloys. Whilst activity continues on the development carbon
fibrereinforcedmaterials(muchoftheworkiscoveredbyUSmilitaryrestrictions),onlyNextel610
fibreshaveachievedsignificantcommercialstatus,Ref.[4679].

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Table46.151AlMMCs:Typicalpropertiesofcontinuousreinforcingfibres
Al203

Carbon

Carbon

Carbon

Al203:SiO2

HT

IM

HM

Altex

Nextel
610

> 99% C

> 99% C

100% C

15% Si02

99%
Al2O3

1800

1800

1800
2200

3300

3900

4000-5000
Young's modulus (GPa):

5300-6400

1900-4400

1800

3000

290-300

380-930

210

380

15

15

210

380

7.9

Fibre
type(1)/Name

Composition
Density
(kg/m3)
Properties(2):

Strength
(MPa):
L

230-235

15
Thermal expansion (ppm/K):
L

0.1 to 0.4

n.a.
Thermal conductivity (W/mK):

Key:

n.a.

1.2 to
1.5
9.5 to12.5

0.1 to 0.4

9 to 17

32 to 35

69 to 1050

<30

low

low

low

<30

(1)HThightenacity;IMintermediatemodulus;HMhighmodulus
(2)Llongitudinal;Ttransverse
AltexisatradenameofSumitomo;Nextelisatradenameof3M

46.15.2.2 Alumina Nextel 610


Nextel 610 is a continuous alumina fibre, classed as high-tensile high-modulus, from 3M and supplied in a
roving form (fibre bundles). Fibres have a coating (size) that is removed at temperatures above 550C, i.e. at
melt infiltration temperatures. TypicalpropertiesforNextel 610 are summarised in Table 46.15.2.

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Table46.152AlMMCs:Typicalpropertiesof3MNextel610aluminafibre
Nextel610(1)

Properties

Composition, -alumina, Al2O3 (%)

>99

Filament tensile strength, 25mm gauge (MPa)

3100

Filament tensile modulus of elasticity (GPa)

379

Filament:

Roving:
Sizing (%)(1)
Sized denier(2)

2.0
3000

Filament diameter (m)

12

Filament count

750

Filament density (kg/m3)

3.90

Surface area (m2/gm)


Roving tensile breaking load, 150mm gauge (N)

<1
89

Creep rate (69MPa) at temperature:

Key:

1000C

2.0 10-9/s

1100C
1200C

1.8 10-7/s
1.7 10-5/s

Coefficient of thermal expansion (ppm/K)

8.0

Dielectric constant (9375 MHz)

9.0

(1)Suppliersdata.Nextelisatradenameof3M;
(2)Percentagebymassoffibrecoating;
(3)Gramsper9000mofmaterialwithsizing(coating)applied.

46.15.2.3 Carbon fibres


Carbonfibresareavailableinthreemaintypes:

HM high modulus, where fibres are either pitchbased or hightemperature treated PAN
based.

HThightenacity,whicharelowtemperaturetreatedPANbased.

IMintermediatemodulus,whicharePANbased,withaspecificheattreatment.

Althoughthefibresusedforcontinuousreinforcementofaluminiumalloysarethesameasthoseused
forCFRPcomposites,onlyalimitednumberhavebeenevaluatedforMMCs,e.g.ThornelHMtypes
P100,P120andK1100fromCytec.

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46.15.3 Matrix alloys


ManyaluminiumalloyshavebeenconsideredforuseasMMCmatrixphases.Sincevariationsofthe
melt infiltration process are used to incorporate the aluminium matrix, this influences the choice of
alloy.Themainconsiderationsare:

fluidityofthemelt,

fibrematrixinterfacebonding,

preventionofmeltfibreinteractions.

Owing to these factors, the most commonly used matrix material is commercially pure aluminium
(99.85%).OthermatrixmaterialsusedincludeAl2%Cu,3xxcastingalloysand6061wroughtalloy.
Theuseof3xx(Al/Si)castingalloysissaidtoovercometheproblemsofaluminiumcarbideformation,
whichotherwisecausesfibredegradationandpoorfibretomatrixbonding,Ref.[4681].

46.15.4 Characteristics
46.15.4.1 Carbon fibre reinforced composites
Initialworkwithcarbonfibrereinforcedaluminiumcompositeswasunsuccessfulbecauseofproperty
degradation arising from the formation of aluminium carbide at fibrematrix interfaces and surface
tensionproblemsresultinginincompletepenetrationofthefibrebundle.

Suchproblemshavebeenresolvedbyusingsiliconcontainingalloys,whichresultsintheformation
of a barrier layer of SiC at the fibrematrix interface. The solubility of carbon is also because of the
alloy silicon content, Ref. [4681]. A remaining problem with carbon fibre reinforced aluminium,
whichislimitingextendedapplication,isthesusceptibilitytogalvaniccorrosion.
The densities of carbon fibres are around half that of alumina fibres, which makes carbon fibre
reinforcedcompositesofparticularinterestwhereweightsavingisaprimeconsideration.

46.15.4.2 Alumina fibre reinforced composites


The addition of alumina fibres to aluminium is a natural combination because of the chemical
compatibilityandthefreedomfromgalvaniccorrosion;aknownproblemwithcarbonreinforcements.
The most widely used, 3M Nextel 610, fibres have similar strength and modulus to many carbon
fibres,[See:Table46.15.1],andcanalsobeusedaspreformswithcomplexshapesandtightradii.This
makesthemsuitableforshapedcomponentsinadditiontounidirectionalreinforcements.
In addition to useful mechanical properties at elevated temperatures, this group of materials are
perceivedashavingbenefitsoverotherMMCsinsituationswherecorrosioncanbeaproblem.

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46.15.5 Processing
46.15.5.1 General
Processingroutesfallintotwobroadcategories:

continuouslengthsofmaterials(prepregsandshapes).

discreteproducts,usingpreforms.

Bothtypesofproductsareprocessedusingliquidmetalinfiltrationtechniques.

46.15.5.2 Continuous infiltration


TRL Touchstone Research Laboratory (USA) use a process similar to pultrusion of polymer
composites,forthemanufactureoftheirMetPregcontinuouslyreinforcedtapes.Thesearegenerally
basedonNextel610aluminafibresinapurealuminiummatrix,althoughtheuseofglassorcarbon
fibreshasalsobeenstudied,Ref.[4682].

Aswellasabasicthintape,whichisutilisedasaprepregmaterialforlayups,filamentwindingor
other fabrication techniques, the process is also suitable for producing continuous tubes, angles or
channels,[Seealso:46.16typicalproperties].

46.15.5.3 Preform infiltration


Preform infiltration processes used for continuous reinforcements are similar to those used for
discontinuouslyreinforcedcomposites,[See:46.13].
Infiltration is achieved through applied gas pressure, usually with prior evacuation of the mould
cavity.Thepreformscanconsistofloosebundlesoffibres,wovenclothsorfilamentwoundstructures
suitableformanufactureofcylindricalortubularcomponents.
A number of different processes are used, including pressureassisted investment casting and gas
pressureinfiltration.
LPFliquidpressureformingisaprocessdevelopedbyCMT(CompositeMetalTechnologies),which
hassimilaritieswiththelowpressurediecastingprocessusedforaluminiumalloys.
Thepreformisplacedinaheatedmetaldiewhichisevacuatedbeforeliquidaluminiumisintroduced
byatwosteppressurisationprocess.Aftercompletionoftheinfiltration,themeltisconsolidatedbya
higherpressureappliedbyhydraulicpistons.

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46.16 Continuously reinforced Al-alloy MMC:

Properties

46.16.1 Mechanical properties


46.16.1.1 General
Continuously reinforced composites, in particular unidirectionally reinforced materials, tend to be
anisotropicinthatthepropertiesinthelongitudinaldirectionarehighlydependentuponthoseofthe
reinforcement whilst in the transverse direction the properties of the matrix alloy have a greater
influence.
Since the properties of shaped compositesare highly dependentupon the specific orientation of the
reinforcement only data for unidirectionally reinforced materials is given here as guidance to the
propertiesthatcanbeexpected.
Composites with bidirectional reinforcement, either from a woven, layup or filament wound fibre
reinforcement,areavailablebutthereisnopropertydatapublishedopenly.
An estimation of property values can be made using established techniques or by comparison with
thoseforfibrereinforcedpolymers.
Typical room temperature properties of a number of continuously reinforced aluminiummatrix
compositesaregiveninTable46.16.1,Ref.[4679].

46.16.1.2 Alumina fibre reinforced composites


The greatest activity on continuously reinforced aluminiummatrix composites has been in the
developmentofNextel610aluminareinforcedmaterials.
Thefibresarereadilyavailableandthecompositesdonotposetheriskofgalvaniccorrosionwhichis
presentwithcarbonfibrereinforcedaluminium.

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Table46.161AlMMCs:TypicalpropertiesofcontinuouslyreinforcedMMCs
Fibre(1)

Vol
%

Matrix

Process
(2)

Density
(kg/m3)

Direction
(3)

UTS
(MPa)

E
(GPa)

Carbon
(M40,Toray)

60

Al99.8
5

GPI

2200

1500

L
Carbon
(EHMS,
Courtaulds)

Aluminosilicate
Al2O3:SiO2
(Altex)

Aluminosilicate
Al2O3:SiO2
(Altex)
Alumina
Al2O3 (Nextel
610)
Alumina
Al2O3 (Nextel
610)
Alumina
Al2O3 (Nextel
610)

Key:

60

50

50

Al99.8
5

Al99.8
5

AlZnM
g

GPI

GPI

PAIC

CTE(ppm/K)
50C
150C

50C
300C

240

0.2

1000

230

0.6

0.2

100

30

17.0

1050

130

7.5

6.6

130

115

14.0

17.0

1000

135

200

85

18.7

2200

3000

7.3

3000

50

AlZnM
g

PAIC

3200

1200

240

60

Al99.8
5

GPI

3300

2000

260

n. a.

1600

240

120

130

60

Al99.8
5

3M

3400

16

(1)Reinforcementfibre(material,name/code,source);
(2)GPIgaspressureinfiltration;PAICpressureassistedinvestmentcasting;
(3)Llongitudinal;Ttransverse.

46.16.1.3 Infiltrated composites


TypicalroomtemperaturepropertiesofNextel reinforced pure aluminium and Al-2%Cu alloy are given in
Table 46.16.2.

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Table46.162AlMMCs:Typicalpropertiesof3MunidirectionalAlNextel
composites
Matrix

Properties(3)

Fibre reinforcement
Fibre volume (%)
Ultimate tensile strength (MPa):

PureAl

Al2%Cu(1)

Nextel
60

Nextel
60

1600

1500

1700

3400

70

140

140

280

240

240

130

160

48-57
3400

45-56
3400

7
16

9
16

Ultimate compressive strength (MPa):


L
Shear strength, at 2% strain (MPa)
Transverse strength, at 1% strain (MPa):
T
Young's Modulus (GPa):

Shear Modulus

(2)

(GPa)

(kg/m3)

Density
Coefficient of thermal expansion, average
value 25C to 500C (ppm/K):
L
T
Key:

Suppliersdata.
(1)weightpercent;
(2)measuredparallelandacrossfibres;
(3)Llongitudinal;Ttransverse.

The influence of the stronger Al2%Cu matrix can be seen in the transverse, compressive and shear
properties.
Thegoodelevatedtemperatureresistanceofaluminafibresprovidesenhancedelevatedtemperature
tensilepropertiestotheAlNextelcomposites.
Forthecompositebasedonpurealuminiumwith60volume%Nextelfibres,thepropertiesat3000C
are:

Longitudinaltensilestrength:1400MPa(RT1600MPa),

LongitudinalYoungsmodulus:200GPa(RT240GPa).

For many aerospace applications, good axial strength and stiffness coupled with light weight are of
high importance. These properties of alumina fibrereinforced aluminium, together with the good
elevatedtemperatureproperties,havebeenexploitedinpushrodsformotorsportengines.

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Typicalpropertiesofthebasematerialandof226mmlong9.5mmdiameterpushrodsaregivenin
Table46.16.3.Datafor4130steelisincludedforcomparisonpurposes.

Table46.163AlMMCs:Typicalpropertiesof3MMMCpushrods
Material
Properties

Al/Nextel

4130Steel

Stiffness (GPa)

221

205

Ultimate Compressive Strength (MPa)

2400

1500

Application:Pushrods(1);9.5mmdiameter226mmlong

Key:

Properties

Al/Nextel

4130Steel

Bending stiffness (Nm2)

84

74

Compressive failure load (kN)

132

72

Critical buckling load (kN)

16.29

14.28

First bending resonance (Hz)

630 Hz

Suppliersdata.Nextelisatradenameof3MCorp.
(1)Highperformancemotorsportenginecomponent

46.16.1.4 Prepreg-based composites


Composite with unidirectional reinforcement, produced by filament winding or layup can also be
produced from continuously infiltrated prepreg, such as MetPreg Alalumina fibre material, [See:
46.15].
Typicalpropertiesforthebasictapematerial,9.5mmwide0.5mmthick,aregiveninTable46.16.4,
Ref.[4682].
Thepropertiesareclosetothosepublishedby3Mforsimilarmaterials.

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Table46.164AlMMCs:TypicalpropertiesofTRLMetPregAl/Al2O3f
continuousfibrecomposites
MetPregaluminareinforcedaluminiumprepregtape
Characteristics:

Matrix

Pure Al

Reinforcement fibre

Nextel 610

Fibre content (Volume %)

50

Thickness (mm)

0.5

Width (mm)

9.5

Density (kg/m3)

3300
Properties:

Tensile strength, at RT (MPa)

1500

Tensile modulus, at RT (GPa)

215

Compressive strength, at RT (MPa)

2070

Elongation (%)

0.7

Maximum use temperature(1) (C)

400

Thermal expansion (ppm/C)

Thermal conductivity (W/mK)

115

Electrical resistivity (ohm.cm)

Key:

MetPregisatradenameofTRLTouchstoneResearchLaboratory(USA).
Nextelisatradenameof3MCorp.
(1)85%oftheroomtemperaturetensilestrength.

46.16.1.5 Carbon fibre reinforced composites


Since carbon fibre reinforced aluminium is susceptible to galvanic corrosion, there has been less
commercialactivityonthesematerials.
Companies, including MMCCMetal Matrix Cast Composites, have been working in this area, but
publicationoftheresultsisrestrictedunderUSDoDandothersecurityregulations.Throughtheuse
of siliconcontaining alloys, MMCC claim to have overcome the melttofibre interface reaction that
resultedinaluminiumcarbideformation,whichalsoposedproblemsintheconsolidatedcomposites.
This approach has been used for producing discontinuously, chopped carbon fibrereinforced
aluminiumcomposites,Ref[4681].[See:46.14].

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46.16.2 Physical properties


Allthecontinuouslyreinforcedaluminiummatrixcompositeshavelowdensities,withcarbonfibre
reinforced materials offering the greatest potential benefits. These materials also offer high thermal
conductivities and low thermal expansion coefficients, properties of importance for long term
dimensionalstabilityandheatdissipationpropertiesinaerospaceapplications.
Aswiththemechanicalproperties,theenhancedthermalpropertiesresultingfromthereinforcement
arefoundmainlyinthelongitudinaldirection.
Whereavailable,physicalpropertiesaregivenfor:

Thermal expansion: Carbon (Toray M40), aluminosilicate (Altex) and alumina (Nextel)
reinforcedaluminiumalloys,[See:Table46.16.1;Table46.16.2;Table46.16.4].

Electricalpropertiesandthermalconductivity:MetPregaluminareinforcedaluminium,[See:
Table46.16.4].

46.17 Al-alloy MMC: Potential applications


46.17.1 Benefits of Aluminium-matrix composites
Traditionally aluminium alloys are the main group of materials used in aircraft and spacecraft
constructionforoperationaltemperaturesupto150C.
Whilstaluminiumhasbeenreplacedbyadvancedpolymercomposites,e.g.CFRP,andfibrelaminate
materials,e.g.GLARE,advancesinaluminiumbasedMMCshaveresultedinarangeofmaterials
that offer substantial benefits compared with polymer matrix composites for specific applications in
spacecraftandlaunchvehicles.Thesebenefitscanbesummarisedas:

Highspecificstrength,

Highspecificstiffness,

Highthermalconductivity,

Lowthermalexpansion

Goodlongtermdimensionalstability,

Electricalconductivity,

Betterradiationresistance,

Nooutgassing,

Betterresistancetofuelsandsolvents

Reducedflammabilityrisk.

AsanexampleofthegoodspecificpropertiesofAlMMCs,Figure46.17.1showsapropertymapof
continuouslyreinforcedaluminafibrealuminiummatrixcompositestogetherwiththepropertiesfor
competitivematerials.
Someexamplesofapplicationsbasedusesincludethosedemanding:

Highspecificstrengthandtemperatureresistance.

Highspecificstiffnessandgoodthermalproperties.

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Highconductivitywithlowthermalexpansion.

Highspecificstiffnessanddimensionalstability.

Highspecificstrengthandchemicalresistance.

Figure46.171AlMMCs:ComparisonbetweenAlcontinuouslyreinforced
aluminafibrecompositesandothermaterials
Someexamplesofcasehistoriesarealsoavailablefrom:

Supplierswebsites,[See:Table46.12.1],

MMCAssess,Ref.[4675].

Anextensivereviewofthecurrentandpotentialspaceapplicationsforaluminiummatrixcomposites
isgiveninRef.[4676].

46.17.2 High specific strength and temperature resistance


Discontinuously reinforced Al/SiCp composites are being used for hydraulic control block for
helicopters and nozzle guide vanes for gas turbine engines. This indicates potential applications for
highdutyapplicationsinlaunchers.

46.17.3 High specific stiffness and good thermal properties


The antenna waveguide for the Hubble Space Telescope was initially made from carbon fibre
infiltrated with 6061 alloy. This was eventually replaced by discontinuously reinforced AlMMC at
lower cost, whilst still maintaining high stiffness combined with good heat dissipation and good

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dimensionalstabilityresultingfromthelowthermalexpansioncoefficient.Thesepropertieshavealso
beenexploitedinthermalradiatorpanelsonotherspacecraft.

46.17.4 High conductivity with low thermal expansion


Al/SiCp discontinuously reinforced composites and Al/Si CE alloys are being used for thermal
management of semiconductor devices. The electrical conductivity of AlMMCs also offer electronic
andradiationshieldingforsensitivecomponentstogetherwithasignificantweightsavingcompared
withtraditionalelectronicspackagingmaterials.

46.17.5 High specific stiffness and dimensional stability


AluminiumbasedMMCsarebeingevaluatedassubstratesandcarriersforspacemirrors.Inaddition
to light weight, this application needs high stiffness and excellent, uniform dimensional stability;
propertieswhicharefacilitatedbythelowthermalexpansionandhighthermalconductivityoffered
bydiscontinuouslyreinforcedaluminiummatrixcomposites.

46.17.6 High specific strength and chemical resistance


Propellant tanks are often made from aluminium alloys, but continuously reinforced aluminium
compositesofferfurtherpotentialforweightreductionasaresultofthehigherspecificstrength.
Suchcomponentsarecandidatesforfilamentwoundorlayupmethodsofconstructionusingeither
liquidinfiltrationoraluminiumprepregmaterials.

46.18 References
46.18.1 General
[461]

ALFEDAluminiumFederation,Birmingham,UK
ThePropertiesofAluminiumanditsAlloys
9thEdition,August1993

[462]

PropertiesandSelection:NonferrousAlloysandSpecialPurpose
Materials.MetalsHandbook,10thEdition,Volume2
ASMInternational.ISBN0871703785(V.2),1990

[463]

MILHDBK5F:MetallicMaterialsandElementsforAerospace
VehicleStructures.November1990

NOTE

ReplacedbyMMPDS01,Ref.[4671]

[464]

J.T.Staley
AdvancedAluminiumAlloysandAluminiumPolymerComposite.
AAS86381,33rdAnnualMeetingAerospace

[465]

M.Hamiuddin
HighStrengthAluminiumLithiumSiCP/MCompositesAReview.
PowderMetallurgyInternational,Vol.19,No.5,1987

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[466]

B.OBrien:BHPLaboratoriesLtd,Eire
ApplicationofAluminiumLithiumBasedAlloys
ESAContract7807/88/NL/PH.FinalReport,September1991.

[467]

W.R.Mohn&D.Vubobratovich:AdvancedCompositeMaterials
Corporation,USA
RecentApplicationsofMetalMatrixCompositesinPrecision
InstrumentsandOpticalSystems
JournalofMaterialsEngineering.Vol.10.No3.p224235,1988

[468]

E.Hellum&M.J.Luton
OxideDispersionStrengthenedAluminiumPropertiesandUse.
ESASP303,SpaceApplicationsofAdvancedStructuralMaterials.21
23March,1990

[469]

E.Hellum:RaufossA/S,Norway
StudyonAdvancedMetallicSystemsODSAlloys
ESTECContract7090/87/NL/PPWorkOrderNo14

[4610]

I.B.MacCormacketal:BNFMetalsTechnologyCentre,UK
AdvancedP/MLightAlloysandtheAssociatedPowderTechnology.
BNFReport.R579/11,April1989

[4611]

G.J.Hildemanetal
MicrostructuralMechanicalPropertyandCorrosionEvaluationsof
7XXXP/MAlloyCW67
HighStrengthPowderMetallurgicalAluminiumAlloysII
G.J.HildemanandM.J.Koczak(eds.),TMS1986,p2543

[4612]

J.R.Pickens&L.Christodoulou
TheStressCorrosionBehaviourofHighStrengthAluminiumPowder
MetallurgyAlloys
Metall.Trans.A,Vol.18A,Jan.1987,p135149

[4613]

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116

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C.A.J.R.Vermeerenetal
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H.F.Wu&J.F.Dalton
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J.Cook&M.Donnellan
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ALCOAAerospaceEngineering,December1987,p.3340

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StaticStrengthofAdhesivelyBondedARALL1Joints
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[4641]

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OntheBearingStrengthofFibreMetalLaminates
JournalofCompositeMaterials,Vol.26,No.17/1992

[4642]

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ManufacturingofComponentsofFibreMetalLaminates:An
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[4643]

A.I.Pendusetal.
DesignEvaluationofGLARELaminateLayups
Symposium.AdvancedMaterialsforLightweightStructuresESTEC,
Noordwijk,2527March1992
ESASP336,p301306

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C.A.J.R.Vermeerenetal.
HybridMaterialsforUseatElevatedTemperatures
Symposium.AdvancedMaterialsforLightweightStructuresESTEC,
Noordwijk,2527March1992
ESASP336,p7178

[4645]

J.L.Verolme:T.U.Delft,NL
TheCompressivePropertiesofGLARE
T.U.Delft,reportLR666,November1991

[4646]

StorkProductEngineering,NL
PossibilitiesforFMLApplicationsinSpaceVehicles
ESTECContract7090/87/NL/PPWorkOrderNo.27

[4647]

B.Hussey&J.Wilson:RJTechnicalConsultants,UK
LightAlloysDirectory&Databook
Chapman&Hall(1998).ISBN0412804107

[4648]

N.Waterman&M.Ashby(Editors)
TheMaterialsSelector
Chapman&Hall(2ndedition1997)
ISBN0412615509(3volumes)

[4649]

R.K.Birdetal:NASALangley,USA/VIAM,Moscow
AlLialloy1441forFuselageApplications
MaterialsScienceForumVols.331337(2000),p907912

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AluminiumLithiumAlloysforAerospaceApplicationsWorkshop

118

ECSSEHB3220Part5A
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NASACR3287(December1994)
[4651]

A.Choetal:ReynoldsMetalsCompany,USA
AlLiDevelopmentatReynoldsMetalsCompanyforAerospace
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NASACR3287(December1994),p1722.

[4652]

E.A.Starkeetal:Uni.Virginia/GeneralElectricCorp.,USA
AluminiumLithiumAlloys
NASACR3287(December1994),p616.

[4653]

MichoudOperations:LockheedMartin,USA
ExternalTankDescription,(January2003)
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M.NivetLutzetal:AlcatelEspaceIndustries,F
MMCTubesforDimensionallyStableStructures
ProceedingsofEuropeanConferenceonSpacecraftStructures,
Materials&MechanicalTesting.Braunschweig,Germany46
November,1998
ESASP428,p321325

[4655]

W.Radtke&K.Thudt:MANTechnologie,D
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ProceedingsofEuropeanConferenceonSpacecraftStructures,
Materials&MechanicalTesting.Noordwijk,NL2729March,1996
ESASP386,p11271135

[4656]

R.K.Bird,D.L.Dicus,J.N.Fridlyander,V.S.Sandler
AlLiAlloy1441forFuselageApplications
Proceedingsof7thInternationalConferenceonAluminiumAlloys,
Charlottesville,VA,April9142000,Pt2,p907912

[4657]

J.N.Fridlyander,V.V.Antipov,T.P.Federenko
ProductPropertiesofHighWorkability1441AlLiAlloy
Proceedingsof9thInternationalConferenceonAluminiumAlloys,
Brisbane,Australia,25August2004,p10511054

[4658]

W.M.Johnston,W.D.PollockandD.S.Dawicke
BiaxialTestingofAluminiumLithiumAlloy2195UsingCruciform
Specimens
NASACR2002211942(October2002).

[4659]

InternationalAlloyDesignationsandChemicalCompositionLimits
forWroughtAluminumandWroughtAluminumAlloys,Teal
SheetsandEnclosure09toAATealSheetsversion2004(April
2004)
TheAluminumAssociationInc.,Washington,DC20006,revisedApril
2004
Website:www.aluminum.org

119

ECSSEHB3220Part5A
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[4660]

ANSIH35.1AvailablefromTheAluminumAssociation,Washington
DC,ANSISecretariat
Website:www.aluminum.org

[4661]

StandardPracticeforNumberingMetalsandAlloys(UNS)
ASTME527.ASTMInternational,100BarrHarborDrive,POBox
C700,WestConshohocken,PA194282959,UnitedStates
Website:www.astm.org

[4662]

WebsitesforAlLialloysuppliers:
Alcan:www.alcan.comandwww.alcanaerospace.com
Alcoa:www.alcoa.comandwww.millproducts.alcoa.com
AMC:www.amcmmc.co.uk
DolgarrogAluminiumLtd.:www.dolgarrog.com
OttoFuchs:www.ottofuchs.com
VIAM:www.viam.ru

[4663]

E.A.StarkeJr.
NASAUVALightAerospaceAlloyandStructureTechnology
ProgramSupplement:AluminumBasedMaterialsforHighSpeed
Aircraft
NASACR97206248,December1997

[4664]

R.A.Edahletal.
EffectofThermalExposureontheTensilePropertiesofAluminum
AlloysforElevatedTemperatureService
NASA/TP2004212988,February2004

[4665]

M.S.Domacketal
EffectofThermalExposureontheStrengthToughnessBehaviorof
ElevatedTemperatureServiceAluminumAlloys
Proceedingsofthe6thInternationalConferenceonAluminumAlloys
Toyohashi,Japan(1998),pp.10811086

[4666]

RobertA.Hafley,JohnA.Wagner,andMarciaS.Domack
FatigueCrackGrowthRateTestResultsforAlLi2195Parent
Metal,VariablePolarityPlasmaArcWeldsandFrictionStirWelds
NASA/TM2000210098,May2000

[4667]

P.S.ChenandW.P.Stanton
ANewAgingTreatmentforImprovingCryogenicToughness
oftheMainStructuralAlloyoftheSuperLightweightTank
NASATM108524November1996

[4668]

SpaceShuttleSuperLightweightTank(SLWT)
IndependentAssessmentofRiskManagementActivities
NASAOfficeofSafetyandMissionAssurance
December12,1997
http://pbma.nasa.gov/docs/public/pbma/casestudies/SLWT_Independ
ent_Assessment_Report.pdf

120

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[4669]

V.C.Guillaumin:AirbusFrance
BenefitsfromtheUseofExtruded2196andC460AlLiAlloysin
A380FloorBeamApplications
AeroMat2004,Session3:TradeStudiesforAircraftStructures,June
10,2004,Seattle,USA

[4670]

AluminumlithiumalloysinAirbusairframes
Technologyupdate
AerospaceEngineering,May2005,p8.

[4671]

R.C.Riceetal.
MetallicMaterialsPropertiesDevelopmentandStandardization
(MMPDS)
DOT/FAA/ARMMPDS01,January2003
Website:http://www.mmpds.org/

[4672]

J.Jackson&R.Rice
PreliminaryMaterialPropertiesHandbook,Volume2:SIUnits
AFRLMLWPTR20014027,July,2000
Website:http://www.mmpds.org/

[4673]

AMCCalidus350xqDataSheet
Website:www.amcmmc.co.uk

[4674]

CompositeMaterialsHandbookVolume4,MetalMatrix
Composites,MILHDBK174A,17June2002,
ARL/WMRD
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http://assist1.daps.dla.mil/quicksearch/basic_profile.cfm?ident_numb
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[4675]

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121

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IsothermalFatigueTestingofParticulateMetalMatrixComposites,
MATC(MN)05,CentreforMaterialsMeasurementandTechnology
NationalPhysicalLaboratory,Teddington,UK
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Overviewoncontinuousfibrereinforcedlightmetals
MMCVIII,MetallicComposites&Foams,26/27.11.2001,
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SAMPEJournal,March/April2004
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[4683]

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DRMMCReinforcements
ASMHandbook,volume21,Composites,
ASMInternational,2001.ISBN:0871707039

[4684]

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AIAA19884444:AHS,andASEE,AircraftDesign,Systemsand
OperationsMeeting,Atlanta,GA,Sept.79,(1988)

122

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46.18.2 Sources
46.18.2.1 Al-Li alloy suppliers
Alcan
Alcoa

www.alcan.com
www.alcan-aerospace.com
www.alcoa.com
www.millproducts.alcoa.com

AMC

www.amc-mmc.co.uk

Dolgarrog Aluminium Ltd

www.dolgarrog.com

Otto Fuchs

www.otto-fuchs.com

VIAM

www.viam.ru

46.18.2.2 Discontinuously reinforced aluminium suppliers


AMT Aerospace Metal
http://www.amc-mmc.co.uk/
Composites (UK)
DWA

http://www.dwa-dra.com/

CPS - Ceramic Process Systems

http://www.alsic.com/

TTC Thermal Transfer


Products

http://www.thermaltc.com/index.html

M Cubed Technologies (USA)

http://www.mmmt.com/

MMCC-Metal Matrix Cast


Composites, (USA)

http://www.mmccinc.com/

Millennium Materials (USA)

http://www.millenmat.com/

Peak Werkstoff (D)

http://www.erbsloeh.de/deutsch/e_werkst
off/

46.18.2.3 Continuously reinforced aluminium suppliers


TRL Touchstone Research
http://www.trl.com/
Laboratory (USA)
MMCC-Metal Matrix Cast
http://www.mmccinc.com/
Composites, (USA)
3M MMC (USA)

http://www.3m.com/market/industrial/m
mc/

CMT Composite Metal


Technologies (UK)

http://www.cmt-plc.com/

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46.18.3 ECSS documents


[See:ECSSwebsite]

ECSSQ7071
ECSSQST7036

ECSSQST7037

Datafortheselectionofspacematerialsand
processes;previouslyESAPSS01701.
Materialselectionforcontrollingstress
corrosioncracking;previouslyESAPSS01
736.
Determinationofthesusceptibilityofmetals
tostresscorrosioncracking;previouslyESA
PSS01737.

46.18.4 ASTM standards


[See:ASTMwebsite]

ASTME527
ASTME1823
ASTMG34

ASTMG44

ASTMG47

StandardPracticeforNumberingMetalsand
Alloys(UNS)
StandardTerminologyrelatingtoFatigueand
FractureTesting:Annex2
<Titlenotstated>
<Titlenotstated>
<Titlenotstated>

46.18.5 Other standards

ANSIH35.1

AmericanNationalStandardAlloyandTemper
DesignationSystemsforAluminum(2004)

MILHDBK174A

CompositeMaterialsHandbookVolume4,Metal
MatrixComposites(June2002)

MMPDS

MetallicMaterialsPropertiesDevelopmentand
Standardization
DOT/FAA/ARMMPDS01(January2003)

NOTE

ReplacesMILHDBK5

PMP

PreliminaryMaterialPropertiesHandbook,
Volume2:SIunits
AFRLMLWPTR20014027(July2000)

NOTE

DestinedforinclusioninMMPDS

124

ECSSEHB3220Part5A
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47 Titanium alloys and their composites


47.1 Introduction
Themainfeaturesoftitaniumalloysusedinaerospacestructuresaredescribed.Theeffectsofalloying
andprocessingonthevariousgroupsofalloysarealsodiscussed.
Specificdesigndataonconventionaltitaniumalloysarenotgiveninthehandbook.
Superplasticity and the ability of titanium alloys to reabsorb oxide films at elevated temperatures
havemadethemofinterestforstructureswhichcanbesuperplasticallyformedanddiffusionbonded
inoneprocess(SPF/DB),[See:47.4;Chapter72].
Manufactureoftitaniummatrixcomposites(TialloyMMCs)hasprovedproblematical,owingtothe
reactivityofthealloywhenincontactwiththereinforcementphase.Asaresult:

Very few particulate reinforced composites have been produced with properties exceeding
thoseofthemorerecentplainalloys,[See:47.5].

Suitable continuous reinforcements are limited; all are monofilaments rather than fibres, [See:
47.6].

Processing methods are solidstate, rather than with a molten matrix phase, to limit
reinforcementdegradation.However,useatelevatedtemperaturesalsoresultsindegradation.

Typicalpropertiesaregivenforvariouscomposites,[See:47.7].
Use of titanium alloys in hydrogen environments needs very careful evaluation. They are prone to
hydrogenembrittlementatalltemperatures,exceptinthecryogenicrange,[See:47.8].
In oxygen atmospheres at temperature above 500C, oxidation occurs and, if scuffed or impacted,
ignitionandburningmayresult,[See:47.9].
Coatings are under development to reduce the effects of gaseous environments at operational
temperatures,[See:47.10].
SomepotentialapplicationsfortitaniumalloysandMMCsarediscussedin47.11.

47.2 Conventional alloys


47.2.1

Material selection factors

Theprimaryreasonsforusingtitaniumalloysstemfromthe:

goodcorrosionresistance.

usefulcombinationof:

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lowdensity(4500kg/cm3),

highstrength(0.2%yieldstressesupto1100MPa).

usefulpropertiesupto600C.

[See: ECSSQ7071: Data for the selection of space materials and processes, previously ESA PSS01
701]

47.2.2

Microstructure

47.2.2.1

Ductile-to-brittle transition

Sometitaniumalloys,notablylowinterstitialalpha(-) alloys, do not exhibit a ductile to brittle transition,


making them suitable for cryogenicapplications.

47.2.2.2

Allotropy

Animportantcharacteristicoftitaniumbasedmaterialsisthereversibletransformation(allotropy)of
thecrystalstructurefromanhexagonalclosepacked(hcp)statetoabodycentredcubic(bcc)state
aboveagiventemperature.
Theallotropictransformationdependsonthetypeandamountofalloycontents.Itenablescomplex
variations in microstructure and more diverse strengthening opportunities than those of other non
ferrousalloys,suchascopperoraluminium.

47.2.2.3

Thermo-mechanical processing

The diversity of microstructure and properties depends not only on alloy additions but also on
thermomechanicalprocessing.Byvaryingthermalormechanicalprocessing,orboth,abroadrange
ofpropertiescanbeproduced.

47.2.3

Effect of alloy elements

Theprincipaleffectofanalloyingelementisitsinfluenceonthetransformationtemperature.

Vanadiumisastabiliser,andiscombinedwithAluminiumtogivethe+alloyTi6Al4V.

Aluminiumincreasestensilestrength,creepresistanceandtheelasticmoduli.Limitedto6%,as
abovethislevelembrittlingaluminides(Ti3Al2)willform.

Tinhasextensivesolidsolubilityinbothand phasesandisoftenusedasasolidsolution
strengthenerinconjunctionwithaluminiumtoachievehigherstrengthswithoutembrittlement.

Zirconium forms a continuous solidsolution with titanium and increases strength at low and
intermediatetemperatures.

Molybdenum is an important stabiliser promoting hardenability and short time elevated


temperaturestrength.

Niobiumisanotherstabiliseraddedtoimproveoxidationresistanceathightemperatures.

Iron tends to lower creep strength. The reduced iron content in alloy Ti1100 is a means of
improvingcreepstrength.

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Carbon is an stabiliser that also widens the temperature difference between the and
transus. Typically, stabilisers cause a widening or flattening between the and transus
temperature.TheleancontentofthealloyIMI829givesanearalloywithasteeptransus
approachcurve.Incontrast,analloywithadditionalstabiliser,suchasTi6Al4Vresultsinan
alloy with a flattened approach curve. The use of carbon to flatten the approach curve
whilst stabilising the phase is the basis for the near alloy IMI 843. Alloy IMI 834 is heat
treatedhighintheregiontogiveabout7.5to15vol.%ofprimaryinafinegrain(0.1mm)
matrix of transformed . This combination of equiaxed and transformed provides a good
combinationofcreepandfatigueresistance.

Table47.2.1summarisestheeffectofalloyingelementsonmicrostructure.

Table47.21Titaniumalloys:Effectsofalloyingelementsonmicrostructure
Alloyingelement

Range
(approx.weight.%)

Aluminium (Al)
Tin (Sn)
Vanadium (V)
Molybdenum (Mo)
Chromium (Cr)

2 to 7
2 to 6
2 to 20
2 to 20
2 to 12

Copper (Cu)

2 to 6

Zirconium (Zr)
Silicon (Si)

2 to 8
0.05 to 1

47.2.4

Alloy classes

47.2.4.1

General

Effectonstructure

- stabiliser
- stabiliser
- stabiliser
- stabiliser
- stabiliser
- stabiliser
and strengthener
[See: 47.2]
Improves creep resistance

Titaniumalloysareclassifiedas:

Alpha,canincludenear

AlphaBeta,alsonear,superandlean

Beta.

Titanium alloys are specified by nationallybased, e.g. DIN, NF, etc. and internationallyaccepted
standards, e.g. ASTM, CEN. They are also commonly denoted by their proprietary product name,
e.g.IMIandTimetaldesignations.
AcomparisonofTialloyscoveredbyvariousstandardsandproductdesignationsisprovidedinRef.
[4726].

47.2.4.2

Near-a alloys

Table 47.2.2 shows how processing temperatures of near alloys can be influenced. This
demonstrates the options available for microstructural variations and their relationship to property
improvements.

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Table47.22Titaniumalloys:Influenceofprocessingtemperaturesonnear
alloys
Property

processed

processed

Tensile strength
Creep strength
Fatigue strength
Fracture toughness
Crack growth rate
Grain size

Moderate
Good
Moderate
Good
Good
Large

Good
Poor
Good
Poor
Moderate
Small

47.2.5

Alloys for aerospace use

47.2.5.1

General

Ofthetitaniumalloysappropriatetoaerospaceuse,Ti6Al4V()hasbeenthebaselinematerialfor
manyyears.Theprincipalproductformsofinterestare:

Wroughtformsforairframeuse,and

Forgingsforturbineenginecomponents.

Table47.23summarisesinformationonrelevanttitaniumalloys.

Table47.23Titaniumalloysforaerospaceuse:Characteristics
Alloygroupor
specification

Nominal
composition
(%)

Availableproduct
forms(Country)

Generaldescription

Typicalaerospace
applications

Excellent corrosion
resistance.
Good weldability

Readily fabricated
complex shapes
requiring
intermediate
strength.

Commerciallypure(CP),e.g.Timetal35Ato100A;Code12

All wrought forms


(UK)

Nearalloys

Timetal 6-2-4-2
[Ti-6242S]

Ti-6Al-2Sn4Zr-2Mo0.08Si
[Ti-6Al-4Zr2Mo-0.1Si]

Plate, sheet,
forgings, (UK &
USA)

Silicon imparts
additional creep
resistance

Timetal 685
[IMI 685]

Ti-6Al-5Zr0.5Mo-0.25Si

Rod, bar, billet,


extrusions, forgings
(UK)

Weldable medium
strength alloy.

Timetal 829
[IMI 829]

Ti-5.6Al3.5Sn-3Zr1Nb-0.25Mo0.3Si

Rod, bar, billet,


extrusions, forgings
& sheet (UK)

Timetal 834
[IMI 834]

Ti-5.8Al-4Sn3.5Zr-0.7Nb0.5Mo-0.3Si0.06C

As for IMI 829 (UK)

Weldable medium
strength alloy with good
thermal stability & high
creep resistance to 600C.
Weldable high
temperature alloy with
improved fatigue
performance over
Timetal 829 & 685.

Forgings and flatrolled products in


engines & airframes
needing high
strength &
toughness. Excellent
creep resistance &
stability to 450C
Alloy for elevated
temperature uses up
to ~520C. Weldable.
Elevated
temperature alloy for
service up to
540C. Weldable.
Maximum use
temperature up to
600C. Weldable.

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Alloygroupor
specification

Nominal
composition
(%)

Availableproduct
forms(Country)

Generaldescription

Typicalaerospace
applications

Timetal 1100
[Ti-1100]

Ti-6Al-2.7Sn4Zr-0.4Mo0.45Si

Billet, bar, sheet,


welding wire,
forgings, castings
(USA & Europe)

High combined strength,


creep, fatigue & fracture
toughness.

Maximum use
temperature up to
~600C.
Weldable.

alloys

Timetal 6-4
[IMI 318]

Ti-6Al-4V
Also: ELI
grade 0.1O2

All product forms


(Universal alloy)

Useful creep resistance


up to 300C & excellent
fatigue strength. Fair
weldability.

Aircraft gas turbine


disks & blades.
Airframe structural
components &
fastener stocks (heattreated to give
1100MPa tensile
strength).

Corona -5

Ti-4.5Al-5Mo1.5Cr

Researched for
plate, forgings &
SPF sheet (USA)

Improved fracture
toughness over
Ti-6Al-4V & easier to
work

Not taken up
replacement for Ti6Al-4V

Ti-4Al-4Mo2Sn-0.5Si

Rod, bar, billet,


extrusions, forgings
(UK)

High strength alloy with


Timetal 551 the highest
(4Sn). 550 weldable; 551
not weldable.

For high strength


applications
requiring useful
creep resistance to
400C.

Beta III

Ti-11.5Mo6Zr-4.5Sn

No longer produced
(USA)

Excellent forgeability &


cold workable. Very good
weldability.

Aircraft fasteners,
sheet metal parts.

Timetal 15-3
[Ti-15-3]

Ti-15V-3Al3Cr-3Sn

Sheet, strip, plate


(USA)

Cold formable alloy.


Heat treatable to
1310MPa tensile
strength. Weldable.

Timetal 17
[Ti-17]

Ti-5Al-2Sn2Zr-4Mo-4Cr

Forgings (USA)

Unlike other alloys,


offers good creep strength
up to 430C.

Timetal 21S
[Beta 21S]

Ti-15Mo-3Nb3Al

Sheet, strip, plate,


foil (USA)

High strength, cold


formable.

Timetal 550 & 551


[IMI 550 & 551]

alloys

High strength
aircraft & aerospace
components to 300C.
Matrix alloy for
composites.
Forgings for turbine
engine components
where hardenability,
strength, toughness
& fatigue are
important.
Honeycomb in engine
structures (228 to
593C), hydraulic
tubes. Matrix alloy
for composites.

47.2.5.2

Specifications

Within Europe, AECMA provide specifications for various aerospace titanium alloys and product
forms,Ref.[4726].
Forexample,CENspecification:

EN2517PR

TitaniumalloyTiP63alloy:annealedsheet,strip&plate,
a100mm

AECMAuseadifferentalloyreferencecomparedwithCEN,e.g.TiP63(CEN);TiP64001(AECMA)
fornominalcompositionalloyTi6Al4V.

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47.2.6

Heat treatment

Titaniumalloysareheattreatedwiththeaimsof:

Reducingresidualstressescausedbyfabrication(stressrelieving).

Optimisingcombinationsofductility,machinabilityanddimensionalstability(annealing).

Increasingstrength(solutiontreatingandageing)

Optimisingspecialpropertiessuchasfracturetoughness,fatiguestrengthandhightemperature
creepstrength.

The and near alloys can be stress relieved and annealed. High strength cannot be developed in
thesealloysbyanytypeofheattreatment.Thealloys,withmetastablearestrengthenedbyageing,
astheretaineddecomposes.Thealloyscanbeagehardened,asthestabilityoftheirphasegives
large section hardenability. For alloys, stress relieving and ageing treatments can be combined;
annealingandsolutiontreatmentmaybeidenticaloperations.
Thealloysexhibitheattreatmentcharacteristicsbetweenthatoftheandclasses.Theycanbe
age hardened by the decomposition of beta, but these alloys do not exhibit the same section
hardenabilityasthealloysowingtotheloweramountofretained.Nonetheless,thealloysare
themostversatileinthatcertainmicrostructurescanbeenhancedbyprocessingineithertheor
thephaseregion,asindicatedearlierfornearalloys.
Forcreepstrength,processingofnearalloysisuseful.Nearenablesworkingorheattreatment
in the phase field without loss of room temperature ductility (possible with other alloys). Near
alloyscanbeworkedhighintheforanintermediatemicrostructurewithamixtureofequiaxed
andacicular.

47.2.7

Mechanical properties

47.2.7.1

General

Table47.2.4presentsasummaryofproperties,whichshouldbeviewedinconjunctionwiththeheat
treatmentsapplied,Ref.[474].

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Table47.24Titaniumalloys:Indicativemechanicalproperties
Temp.

UTS

0.2%PS

El

RofA

(C)
RT
480

(MPa)
895
620

(MPa)
825
485

(%)
10
15

(%)
25
30

Forging
Stock
360mm

RT
520

950
610

880
480

6
9

15
20

IMI
829

Forging
Stock
300mm

RT
540

930
570

820
480

9
9

15
25

IMI
834

Forging
Stock
300mm

RT
600

1030
585

910
450

6
9

15
20

Sheet

RT

9601270

900

Plate
<10mm

RT

8951150

825

10

825

25

830

25

1100

940

15

785
10951335
11051240

773
9851245
10301170

22
6-12

Annealed.
Aged.

8-15

20-45

Solution treated &


aged.

Alloy

Form

Ti6242S

Forging
Stock

IMI
685

IMI
318
(Ti6Al4V)

IMI
550

Plate 10100mm
Bar
150mm
Wrought
product

RT
RT
RT

Ti15-3

Wrought
product

RT

Ti-17

Wrought
product

RT

Key:

8951150
9001160

Comments
Solution treated &
aged.
As manufactured,
surface cleaned &
etched. 1050C/
hr/OQ+550C/24hr
/AC.
As manufactured,
surface cleaned &
etched. 1050C/
hr/AC+625C/2hr/
AC.
As manufactured,
surface cleaned &
etched. Solution
Treated & aged.
Annealed.700C/20m
ins/AC. De-scaled.
Annealed.700C/20m
ins/AC. De-scaled &
pickled.
20% R of A for 25100mm plate.
Annealed.700C/hr/2
5mm section/AC.
Solution treated
900C/AC & aged.

Allvalues,exceptwherearangeisgiven,areminimumvaluesstatedbythesuppliers.
OQ:OilQuenched;AC:AirCooled.

47.2.7.2

Elevated temperature

The property data presented emphasises those alloys offering high temperature stability and their
improvementsoverTi6Al4V.ImprovementsinalloydevelopmentareshowninFigure47.2.1,Figure
47.2.2,Figure47.2.3andFigure47.2.4forUTS,creepandfatiguecurves.

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Figure47.21Titaniumalloys:Effectoftemperatureonstiffness

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Figure47.22Titaniumalloys:Effectoftemperatureonstrength

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Figure47.23Titaniumalloys:Creepproperties

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Figure47.24Titaniumalloys:Fatiguestrength
Inseekingtooperatetitaniumalloysclosetotheirmaximum,Dornierhavestudiedthepossibilityof
SPF/DBcomponentsforspaceplanestructuralconfigurations,Ref.[475],[See:47.4].
Figure47.2.5demonstratesthesuperiorityofIMI829andTi1100onstrengthretentionat600C,Ref.
[475]. This exercise established the viability of superplastic forming 0.8mm to 1.5mm sheet and
achieving diffusion bonding simultaneously. For Ti6Al4V, the forming temperature should not
exceed935C,whilstbothhightemperaturealloysneededthebondingtemperaturetobeintherange
950to980C.

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Ti-6Al-4V used as Reference

Figure47.25Titaniumalloys:UTSatelevatedtemperatureforIMI829andTi
1100
47.2.7.3

Fracture properties

[See:Table47.2.5]

47.2.8

Physical properties

[See:Table47.2.5]

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Table47.25Titaniumalloys:Physicalproperties
Alloy
Property

Ti6Al4V
(IMI318)

IMI685

IMI629

IMI634

6242S

Density (kg/m3)
- Transus
(C)
Thermal
Conductivity
(W m-1C-1)
CTE (10-6C-1) :
20 - 100C
20 - 200C
20 - 300C
20 - 400C
20 - 500C
20 - 600C
20 - 800C
20 - 1000C
Suitable Postweld
Treatments

4420

4450

4540

4550

4540

1020

1015

1045

995

6.7

4.2

8.6
9.0
9.2
9.4
9.5
9.7
-

9.8
9.3
9.5
9.8
10.1
10.1
-

9.45
9.77
9.98
10.34
10.39

10.6
10.9
11.0
11.2
11.3

9.9
-

550C/4-8hrs/
AC

625C/2hr/AC

625C/
1hr/AC

44-66
Equiaxed
with 910MPa
YS

68
For 910 MPa
0.2% PS

78
heat
treated
condition

37
Aged: 700C
/2hrs

65-79
- heat
treated &
aged

Fracture
Toughness
(MPa m )
Key:

TypicalRTValues;ACAirCooled

47.3 New alloys


47.3.1

Developments

Newalloydevelopmentshavecentredon:

alloymodificationstoassistfibrematrixcompatibility,and

processingtechniquestoenablecosteffectivefabrication.

47.3.2

Processing techniques

47.3.2.1

General

Fabricationtechniqueswhichhavepotentialcostreducingbenefitsare:

Superplasticforming(SPF),

Rapidsolidification(RS)technology.

Thesetechniquesarealsobeingusedfortitaniummetalmatrixcomposites.

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47.3.2.2

Superplastic forming

[See:47.4andChapter72]

47.3.2.3

Rapid solidification

Rapid solidification (RS) has demonstrated the ability to produce thin foils with fine grain sizes for
combination with reinforcement fibres. The consolidated composite had reduced reactions between
thefibreandmatrixwhichwasattributedtoasuperplasticformingmechanismoperatingduringthe
lowertemperatureconsolidation.
Powdermetallurgytitaniumalloysarealsobelievedtoofferadvantagesoverthefoilformofmatrix
forMMCs.Thishoweveristhesubjectofongoingdevelopment.

47.4 Superplastic forming and diffusion bonding


47.4.1

Superplasticity

Superplasticitycanbeachievedwithmostmetals.Thealloyisheatedtoaround50%ofmeltingand
deformedatlowstrainratesuptomanyhundredpercentstrain.AnessentialcharacteristicofanSPF
materialisafine,uniformgrainsizewithlimitedtexturing.Whilsttheprocessisslow,complex,thin
walled,shapeswithintegralstiffeningarefeasible,whicharenotachievablebyconventionalforming
processes.

47.4.2

Diffusion bonding

47.4.2.1

General

Twoormoremetalcomponentsareplacedintimatelyincontactandtemperature/pressureappliedto
achieveahomogeneousstructure.Theprocessresultsinajointwhichismetallurgicallyundetectable,
i.e.grainboundariesarenotconfinedtotheoriginaljointfaces.Bondstrengthsuptoparentmaterial
propertiesareachievable.

47.4.2.2

Characteristics of titanium alloys

The ability of titanium to absorb its oxide layer at high temperature in an inert atmosphere is a
phenomenon which makes this material readily bondable. These selfcleaning conditions are
obtained at the optimum SPF temperature for titanium alloys, so the SPF/DB process has become a
practicalpropositionfortitaniumcomponentmanufacture.

47.4.3

SPF/DB fabrication

47.4.3.1

General

Combiningsuperplasticforminganddiffusionbondingintoacombinedprocessingroute(SPF/DB)is
anelegantone,offeringasingleshotprocesstogivecomplexconfigurations,including:

Struts,

Cylinders,

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Accesspanels,and

Pressurevessels.

Combinedknowledgeandexpertiseisneededtounderstandthe:

Material,asitisstrained,

Jointing,

NetShapefabrication.

[See:Chapter72forSPF/DBtitaniumdesigns]

47.4.3.2

Cost factors

Cost saving in manufacture is the primary attraction of the SPF/DB process; especially for titanium
alloys,withtheirimportanceinspaceplanedevelopment.

47.4.4

Materials

47.4.4.1

Ti-6Al-4V alloy

Ti6Al4V is by far the most common titanium alloy to which SPF/DB is applied. However, if the
materialhasasuitablemicrostructure,mosttitaniumalloyscanbeprocessedinthisway.

47.4.4.2

IMI 829 and Ti-1100

WorkbyDornier,Ref.[475],hasdemonstratedthatthealloysIMI829andTi1100canbeformedand
bonded, given close control of strain rate in relation to the forming temperature. Figure 47.4.1
providesthemvalues(StrainRateSensitivity)forthreealloys.
WithIMI829andTi1100materials,atemperatureof980Cisneededtoensuretruesuperplasticity,
whilst at 935C plastic deformation and undesirable necking characteristics predominate. Ti6Al4V
showsthismvalueat935C.Aminimummvalueof0.5issoughttodemonstratesuperplasticity.

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IMI 834 has replaced IMI 829, [See: 72.4]

Figure47.41SPF/DBfabrication:Titaniumalloymvaluesasafunctionofstrain
rate

47.5 Discontinuously reinforced Ti-alloys


47.5.1

Difficulties

Initialstudiesofdiscontinuouslyreinforcedtitaniumalloysprovedlargelyunsuccessfulowingtothe
reactivity of the matrix with the reinforcement. For whisker and particulate reinforcement, little
remainedaftertheconsolidationandhencenobenefitinmechanicalperformancewasachieved.

47.5.2

Particulate reinforcements

47.5.2.1

General

Certainparticlescanbeusedasreinforcements,including:

boroncarbide,

titaniumdiboride,

titaniumcarbide.

Theuseoftitaniumcompoundsenablescompatibilitywithtitaniumalloys.Evidenceofgoodmatrix
toparticleadhesionisseenwith10vol.%titaniumcarbideadditionstoTi6Al4V,Ref.[4710].

47.5.2.2

Particulate content

Work with allparticulate MMC materials suggests that reinforcement contents need to be kept
modest(lessthan20vol.%)toavoidlossofductilityandtoughness.

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47.5.3

Processing

Particulate reinforced composites have been made by a powder route, with hot pressing for
consolidation.

47.5.4

Properties

Lowparticulatecontentsareneededtoavoidseriouslossofductility.
Inthecaseof10vol.%TiMMCpmaterial,asmallincreaseinmoduluswouldbeexperiencedwitha
4%reductionindensity.Thisisonlyamarginalimprovementinperformanceconsideringtheprocess
difficulties.
TheadditionofTiCparticlesmayimprovethehightemperaturestabilityandcreepresistanceofTi
6Al4V. However, alloys such as IMI 834 and Beta 21S, with better inherent thermal performance,
renderparticleadditionstoTi6Al4Vunnecessary.

47.5.5

Further development

ParticulateTiMMCmaterialscanbeworthwhileifbasedonthemoreadvancedalloycompositions,
includingtitaniumaluminides,[Seealso:Chapter49IntermetallicMaterials].
Atpresent,nosignificantcommercialdevelopmentsofthistypecanbedescribed.

47.6 Continuous fibre reinforced Ti-alloy MMC


47.6.1

Composite development

47.6.1.1

General

Continuousfibrereinforcementoftitaniumalloysaimstoachieve:

Increasedstiffnessandstrength

Reducedmaterialdensity

Improvedcreepresistance,and

Improvedfatiguelife.

Development of these materials has been driven by the need for efficient titanium composites in
aircraft gas turbine engines and hypersonic spaceplanes, e.g. NASP. The commercial availability of
someTiMMCsisgiveninRef.[4726].

47.6.1.2

Fibres

Initial development work on titanium composites concentrated on development of fibres having


acceptablecompatibilitywiththetitaniummatrix.Thehighreactivityoftitaniumcausesseverefibre
degradation during processing. This led to the introduction of selected fibre coating systems and
reducedtemperatureprocessingtechniques.

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Thehighreactivityoftitaniumexcludestheuseofsmallerdiameter(5mto15m)reinforcingfibres,
suchascarbonorsiliconcarbide.Effortshavethereforebeenconcentratedonmonofilaments.
In work going back twenty years, those studied have been the large diameter filaments (100m to
200m),including:

SiliconCarbide(SiC)

BoronCarbidecoatedBoron(B4C/B)

Borsic(B/SiC)

47.6.1.3

Matrix alloys

EarlyworkconcentratedontheuseofTi6Al4Valloyasthematrixmaterial,presumablybecauseit
was a well understood alloy and readily available. Ti6Al4V proved adequate for studying and
refiningprocesstechniquesbutthecompositehasonlymodestthermalperformance.
Laterworkmovedtonearandalloysasameansofextendingthermalcapabilitiestowards600to
700C.
Thealloyscanalsobecoldrolledtoproducethinfoilswhichareusedtopreparecompositesbyhot
pressing.Developmenthasprogressedfromthesealloystotitaniumaluminidematrices,[See:Chapter
49].

47.6.2

Monofilament reinforcements

47.6.2.1

Availability

With the rationalisation in commercial fibres, there are now only two monofilament options for
titaniummatrixcomposites(TMC):

Textronsiliconcarbide:SCS6(140mdiameter).

BPSIGMA:uncoatedbasefibreSM1040(100mdiameter).

47.6.2.2

Filament Manufacture

Both are made by chemical vapour deposition (CVD) of silicon carbide on to a precursor wire. The
wireistungstenforSIGMAandcarbonforSCS6.

47.6.2.3

Filament coatings

The CVD process has been taken a step further to modify the outer filament surface to a chemical
composition which is more compatible with titanium matrices. These coatings form the interface
between fibre and matrix and ultimately define the level of mechanical properties attainable by the
composite.
Thecoatingsappliedtocommercialfibresare:

SCS6:Thecoatingis3mthickandiscarbonrich.Thesiliconcontentexhibitsamaximumat
theoutersurfaceandat1.5mfromtheoutersurface.

SIGMA:Twovariants,withcoatingsappliedtothebasefibreSM1040:

SM1140+:hasa4.5mcarboncoating.Forusewithaggressivealloys.

SM1240:hasaduplexcoatingof1moverlayedwith1mtitaniumdiboride(TiB2).

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47.6.2.4

Characteristics

Bothfibresexhibitreasonabletensilestrengths,inexcessof3000MPa,butthereisadegreeofscatter.
The manufacturers have improved the consistency of their respective processes to improve the
claimedstandarddeviationfrom500MPato200MPa.Thelargemonofilamentdiametersinfluence
theselectionofcompositeprocesstechniques.

47.6.3

Matrix selection

47.6.3.1

Thermal stability

Toimprovethethermalperformanceoftitaniummatrixcomposites(TMCs),Ti6Al4Vmatriceshave
beenreplacedbynear,e.g.Timetal834(IMI834)andTimetal1100(Ti1100),andsystems.

[Seealso:47.2forconventionalalloys]

IntheUSA,theprogressionseeninalloyshasbeen:
BetaIIITi153Timetal21S(Beta21S)

47.6.3.2

Availability

Matrixselectionisalsoinfluencedbymorepracticalconsiderations,suchastheavailabilityofthinfoil
for stacking and consolidation. The inability to obtain certain alloys in foil form, e.g. Ti6242S, has
excludedtheiruseinTMCmaterialsmadebythisroute.Theselectionofalloyshasbeendrivenby
theirabilitytobereadilycoldworkedintothinfoils,whilstofferinggoodintermediatetemperature
capabilities.Thenearalloyshavehighertemperaturecapabilitiesandareavailableinpowderform;
farlessasfoils.
Theuseofsputtering,Ref.[4715],orpowderroutesforTMCpreparationenablesotheralloymatrices
tobeconsidered.

47.6.3.3

Oxidation

Wherehighoperatingtemperaturesareenvisagedforprolongedperiods,oxidationresistanceshould
beconsidered.
Inthisrespect,Beta21SisbetterthanTi153.However,forprolongeduse>450C,allTMCmaterials
requireanadditionalcoatingsystemtoprovideanoxygenbarrier.

47.6.4

Composite process technologies

The handling characteristics of monofilaments are such that they are processed individually rather
thanasbundlesortows,aswithtraditionalfibres.
Each monofilament is encapsulated with matrix and the overall composite consolidated. The matrix
cannotbeworkedintheliquidstateasitistooreactive.
Consolidation is therefore in the solid state, relying on diffusion bonding under pressure at
temperaturesbelow900C.Theacceptedprocessesare:

ConsolidationoffilamentsseparatedbymetalfoillayersusinghotpressingorHIPtechniques.

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Consolidationofpowdercoatedfilamentprepregsbyhotpressing.

Fusion of individually matrixcoated filaments which have been stacked or wound in the
desiredconfiguration,thematrixcoatingnormallybeingappliedbysputtering.

These processes lead to very wide variations in fibre volume fractions from 17% to 80%, with the
range35%to45%beingthemostcommon.Keyprocessingrequirementsaretoobtainanevenfibre
distributionandavoidfibrestouchingeachother.

47.7 Continuous fibre reinforced Ti-alloy MMC: properties


47.7.1

Composite optimisation

Owingtothehighreactivityoftitaniumanditsalloys,detailedoptimisationofthecompositesystem
isalwaysrequiredtogivehightemperaturecapabilitiesintherange450Cto650Candgoodthermo
mechanicalfatigue(TMF)life.
Poor transverse strength in 90 plies and deleterious fibrematrix interactions are the constraining
factors.

47.7.2

Tensile strength and stiffness

47.7.2.1

General

Themajorityofpublisheddataprovidessimpleunidirectionaltensilestiffnessandstrengthvaluesfor
variousfibrematrixcombinations,asshowninTable47.7.1andTable47.7.2,Ref.[4711].

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Table47.71Titaniummatrixcomposites:Typicalroomtemperaturetensileproperties
Matrix Alloy
[See: Notes]

Fibre Type

Fibre Volume
%

Ti-6Al-4V
CP-Ti

None
Borsic
Borsic
Boron

Nil
28
32
28
35-40
Not stated
Not stated

Ti-6Al-4V
Ti-6Al-4V
Ti-6Al-4V
Ti-6Al-4V
Ti-6Al-4V

Ultimate Tensile Strength


Transverse
Longitudinal (MPa)
(MPa)
890
890
860
276
620
324
1000
340
(1630)
(286)
970
>345
895
365
813
324
827
289

Modulus (GPa)

Notes

120
193
204
(201)
190
205
207
200

Commercial Purity
( ) predicted values

Ti-6Al-4V

Borsic
Borsic
Borsic
Borsic
B4C/B

32

1450

>345

Ti-6Al-4V

B4C/B

Not stated

978-1054

303-310

Ti-6Al-4V

B4C/B

38

1550

>345

221

Ti-6Al-4V

B4C/B

Not stated

985-1033

324-351

199-207

Ti-6Al-4V

B4C/B

35-40

1055

310

205

Ti-6Al-4V

B4C/B

Not stated

875-1047

310

203-218

Ti-6Al-4V

B4C/B

Not stated

882-1068

317-344

215-229

214
Range of properties
are from materials
made by different
companies.
(DWA and AVCO in U.S.A.)

Ti-6Al-4V
SiC
35-40
820
380
225
Ti-6Al-4V
SiC
Not stated
779
289
189
Ti-6Al-4V
SiC
Not stated
771
379
196
Ti-6Al-4V
SCS-6
Not stated
1040
338
240
Ti-6Al-4V
SCS-6
35-40
1455
340
240
Ti-6Al-4V
SCS-6
Not stated
909
303
233
Ti-6Al-4V
SCS-6
Not stated
833
365
213
Beta III
Borsic
Not stated
854
Ti-11.5Mo-6Zr-4.5Sn
Ti-10Mo
Borsic
Not stated
730
331
Beta III
Borsic
Not stated
854
Ti-11.5Mo-6Zr-4.5Sn
Ti-10Mo
Borsic
Not stated
730
331
Key: : Borsic, boron and B4C fibres are no longer appropriate for use in titanium composites; : Mill annealed 732C/2 hours/Air cooled; : After fabrication & low temperature
595C/512 hours exposure; : After fabrication and 760C/64 hours exposure; : After fabrication and 900C/5 hours exposure

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Table47.72Titaniummatrixcomposites:TypicalstrengthsofUDSIGMASiC
reinforcedalloys
Alloy

Ti-6Al-4V
Ti-15-3-3-3
Beta 21S
Aluminium 6061

Filament

UTS

Modulus

(Vol.%)

(MPa)

(GPa)

35 - 38
30 - 35
27 - 30
30 - 35

1755
1450
1470
1200

235
230
185
180

Therearewidevariationsinthedata,butsignificantimprovementsinambienttemperaturestrength
arefeasible,althoughtherearetemperaturelimitationsonpropertyretention.
Thetransversestrengthsofunidirectionalmaterialsarelowerthanthebasematrixmaterial.

47.7.2.2

Loading

Unidirectional TMC materials are attractive for applications with a single load direction, e.g. hoop
stress. Multiple loads require more complex layups with correspondingly reduced maximum
strengthcapabilities.

47.7.3

Fatigue

Table47.7.3givesfatiguepropertiesforvariouscomposites,Ref.[4712].
Dataareincludedforcompositesafterahightemperaturetreatment.

[Seealso:Thermomechanicalfatigue(TMF)]

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Table47.73Titaniummatrixcomposites:Fatigueproperties
Fibre
type

Matrixtype
[See:Notes]
Ti-6Al-4V
Ti-6Al-4V
Ti-6Al-4V
Ti-6Al-4V
Ti-6Al-4V
Ti-6Al-4V
Ti-6Al-4V
Ti-6Al-4V
Ti-6Al-4V
Beta III
(Ti-11.5Mo-6Zr4.5Sn)
Ti CP
Ti-10Mo

Fibre
vol.%

Cyclesto
failure

UTS
(MPa)

None
None
Borsic
Borsic
SiC
SCS-6
SCS-6
B4C/B
B4C/B

Nil
Nil
35 to 40
Not stated
35-40
35-40
Not stated
35-40
Not stated

(x104)
6
4 to 6
6
~1
2 to 200*
20
~1
1000
3 to 10

Borsic

Not stated

3 to 6

Borsic
Borsic

Not stated
Not stated

1 to 3
1 to 2

890
895
820
1455
1055
-

Key:

:Millannealed732C/2hours/AC;:Afterfabrication955C/8hour
exposure;:Borsic,boronandB4Cfibresarenolongerappropriate
foruseinTicomposites;*:Poorconsolidationofcomposite.

Testconditions:

Asfabricated4plyunidirectionalspecimens.R=+0.1,max.=515MPa,Room
Temperature.AxialFatigue

47.7.4

Fracture toughness

ThefracturetoughnessofTMCmaterialsisdifficulttoassessbecauseofthedirectionality.Thelevelof
matrixtofibrebondingalsostronglyinfluencesthecrackpropagationcharacteristics.

47.7.5

Elevated temperatures

In preparing TMC materials every attempt is made to minimise deleterious chemical interactions
between matrix and reinforcement, usually by using the lowest effective temperature for
consolidation. Whilst this controls the problem at the processing stage, cumulative degradation can
stilloccurinserviceathightemperatures.

47.7.6

Thermo-mechanical fatigue

47.7.6.1

General

Combinedthermalcyclingandstresscyclingiscalledthermomechanicalfatigue(TMF).Anexample
ofitseffectsisgiveninRef.[4720],[Seealso:Chapter83].

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47.7.6.2

Composite type

AsymmetricalcrossplylaminateofSCS6/Ti153wasprepared,[0/90]2S,consistingof8plieswitha
fibrevolumefractionof38%andanoverallthicknessof1.69mm.ThealloyTi15V3Al3Sn3Crwas
afavouredmatrixmaterialintheUSA.
Simple tensile tests on the laminate indicated that firstply failure (FPF) in the transverse 90 plies
occurred at the applied stress of 450MPa at 427C. Maximum failure strain for the composite were
around0.8%.

47.7.6.3

Test regimes

TwoTMFtestregimeswereused:

Inphase,wherepeakstresscoincidedwithpeaktemperature.

180OutofPhase.

Thethermalcycleoperatedbetween149Cand427Coveraperiodof48seconds.Appliedmaximum
stresslevelsvariedbetween244MPaand612MPa.

47.7.6.4

Effect of thermo-mechanical fatigue

Figure47.7.1showsagraphicalpresentationoftheresultsfromeightspecimens.Althoughviewedas
indicativeonly,itdoesdemonstrateanumberoffeatures,including:

Athighstresses(i.e.abovetheFPFstresslevel),thefatiguelifeforinphaseTMFwaslessthan
foroutofphaseTMFconditions.

BelowtheFPFstress,thelinescrossandthefatiguelifeforinphaseTMFconditionsshowsa
progressiveimprovementovertheoutofphaseconditions.

This is not surprising as the residual stresses within a TMC are highest near ambient temperature
reflecting the accumulated stress in cooling from the consolidation temperature. The FPF stress is
significantlyloweratRTcomparedtothe427Cvalueof450MPa.

47.7.6.5

Damage mechanisms

Theprimaryfatiguedamagemechanismistransversecrackingoriginatingatthefibrematrixinterface
of90fibres.However,thefinaldamagemodesaredependentonthestresslevelandtestconditions.
FortestsaboveFPFlevel(427C),thetransversecracksin90pliespropagatingtowards0fibreswere
deflectedinthelongitudinaldirection,owingtoeitherhighstressesoraweakerinterface.Thiscaused
thetransversecracksinthe90plyofthespecimentobedeflectedandcoalesceonvariouslevelsin
the specimen at failure. It also causeda localised necking or channelling effect of matrix materialat
pointsbetweenfailed0fibresgeneratinglocalstressconcentrationsandlimitedductilefailureinthe
matrixmaterials.

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Ti-6Al-4V used as Reference

Figure47.71Titaniummatrixcomposites:Fatiguelifefrominphaseandoutof
phasethermalmechanicalfatiguetests

47.8 Titanium alloys: Effect of hydrogen


47.8.1

Material degradation mechanisms

Theeffectsofhydrogenontitaniumalloyscanbesummarisedas:

Mostcommercialalloysarehighlysusceptibletodegradation.

Microstructurestronglyinfluencesmechanismsdueto:

variationsinhydrogensolubility.

hydrogentransportmechanisms.

Alloyshavingmainlyphasedegradebyrepeatedhydrideformationandfractureatornear
thegasmetalinterface.

Continuous phase (in + alloys) provides a path for hydrogen to penetrate material and
formhydridesinneighbouringphaseoratinterfaces.

AdvancedTialloysforuseathightemperaturesconsistprimarilyofintermetalliccompounds.
The effect of hydrogen on intermetallics is largely unquantified. Transport and hydride
formationoccursviatheandphasespresent.

[Seealso:Chapter85]

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Table 47.8.1 describes the mechanism of hydrogen embrittlement, and the effects at various
temperaturesandconditions,Ref.[4724],[4725].

Table47.81Titaniumalloys:Effectofhydrogen
Conditions
Hydrogen embrittlement
(HE) mechanism
Cryogenic Temperatures

Ambient to ~400C

>450C

Surface contamination

Characteristics
Absorption of hydrogen at ~90
to 150ppm causes hydride
precipitation.
Resistance to liquid hydrogen.
Erratic behaviour, not easily
predicted. Factors include:
Oxide-free surface
Stress
Acicular microstructure
Increasing temperature
Increasing pressure
Intact oxide films (without
other active factors) reduce
hydrogen penetration below
~450C.
Sensitive to hydrogen
Fe & Fe-Ni surface
contamination prohibits
formation of Ti oxide film.
These are sites for rapid
hydrogen penetration &
embrittlement of the alloy.

Comments
For Ti-10V-2Fe: Linked to phase stabilisation inhibiting
martensite transformation.
Insufficient heat to promote
dissociation at 20K
Turbine blades operating at
350C found to chip in
stressed regions (leading
edge) owing to high hydrogen
contents.
Reduce hydrogen content by
vacuum heat-treatment (700
C for 7 hours, typically).

Ti structures fabricated with


Fe-based tooling require:
Surface pickling to
remove contamination.
Use of Ti brushes for
scratch-brushing
operations.

47.9 Titanium alloys: Effect of oxygen


47.9.1

Oxidation

47.9.1.1

General

Titanium is a reactive material and oxidises, although the reaction is minimised by the oxide film
passivatingthesurface.

47.9.1.2

Elevated temperatures

At high temperatures the passivation is ultimately overcome and excessive oxidation occurs. This
limits titanium alloys to around 500C for continuous operation in air unless advanced alloys or
protectionsystemsareused.

[SeealsoChapter85]

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47.9.2

Ignition and burning

Under certain conditions of oxygen temperature and pressure, if scuffed or impacted then titanium
alloyscanigniteandsustainburning;asshown,forstaticanddynamicoxygenenvironments,inTable
47.9.1,Ref.[4725].

Table47.91Titaniumalloys:Ignitionandburncharacteristics
Conditions

Static

Dynamic

Characteristic

Freshly exposed Ti surface in contact with oxygen causes


ignition.
Reaction is dependent on oxygen content and pressure, the
lower the O2 content, the higher the pressure needed.
Pure O2 static conditions pressure of ~2.5MPa required.
Affected by purity of O2 atmosphere.
At O2 concentrations <~47%, ignition does not occur.
Ignition limits are not influenced by surface to volume ratio or
by temperatures up to ~300C.
Increased possibility of ignition
Limited to oxygen concentration < 35%.
Ignition will not occur in air.
Ignition is not self sustaining in water or aqueous solution.
Ignition may occur in vapour space above solution, if
conditions are favourable.

47.10 Coatings and protection systems


47.10.1 Requirements
Theuseofcurrentlycommerciallyavailablealloysislimitedtoaround500Cduetotheirmechanical
propertydegradationinoxygenandhydrogenenvironments,[Seealso:Chapter85].
However,demandstooptimisetheweightoffuturespacepropulsionsystemscouldresultintitanium
alloysbeingusedinregionsnotexperiencingexcessivetemperatures,primarilyrotationalparts.This
canbeachievedbyeither:

Alloydevelopmentcombinedwithnovelprocessingtechniques.

Withtheaidofcoatings.

47.10.2 Potential coatings


Table47.10.1summarisesongoingstudiesofcoatingsystemsfortitaniumalloys,Ref.[4724],[4725].

[Seealso:74.6]

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Table47.101Titaniumalloys:Potentialcoatingsystems
Coating

Application

composition

method

Ti-6Al-4V

NiCr

Sputtering

TiCP

SiC

(99.5%)

Si3N4
Al

IMI829

Ti-8.5Si

Substrate

Key:

Sputtering

Comments

Coating thickness 1 to 8 m
Natural oxide stripped before
coating
SiC cracked therefore not effective
Thermal shock:
SiC spalled
NiCr & Al did not spall
No metallurgical changes found with
Si3N4 coatings
Coating thickness 50 to 80m
typically
Coating polluted by Al
No significant diffusion between
coating/substrate at 700C
Structural change in coating to Sirich phases
Coating reduced oxygen penetration
from 35 atomic% to 10 atomic%
uniformly

:ActualcompositionTi8.6Si0.48Al.

47.11 Ti-alloys and MMCs: Potential applications


47.11.1 Current use
Titanium alloys have traditionally filled applications operating in the temperature range 200C to
600C, i.e. above aluminium and below superalloys. This has placed titanium in and around power
plants(engines)andforsurfacesexperiencingaerodynamicheating.Thehighermodulusoftitanium
sometimespromotesitsuseinsteadofaluminium.
Alloys such as Timetal 834 and Timetal 1100 assist in progressively increasing the temperature
capabilityoftitanium.
[See:Table47.2.3foraerospacealloys]

47.11.2 Developments
There are two significant developments in titanium technology which influence its use beyond its
currentrole.Theseare:

Superplastic Forming/Diffusion Bonding (SPF/DB): A production technique which allows


complexbutweightefficientconstructionstobemadewiththedesiredtitaniumalloyand,for
certaincomponents,atalowermanufacturingcost.

[Seealso:Chapter72SPF/DBtitaniumdesigns]

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Titanium Matrix Composites (TMCs): The addition of continuous reinforcements, notably


silicon carbide filaments, increases specific strength and thermal capabilities. This can prove
attractive for applications experiencing loading in a single, predominant direction (UD
composite).

[See:Table47.7.1forTMCdevelopment]

The evolution of titanium matrix composites is dependent on controlling the reactive nature of
titanium by material composition and processing. The poor transverse properties severely limit the
useofbidirectionalcomposites.

47.11.3 Aerospace applications


47.11.3.1 General
AreviewofpotentialapplicationsfortitaniumbasedmaterialsingiveninRef.[4727].Thisconcluded
that:

Idealapplicationsarethosesubjectedtohighlydirectionalloadingsathightemperatures.

Successful fibre coating techniques are a prerequisite for optimising TMC characteristics. A
magnetronsputteringtechniqueprovedsuccessful.

Use of orthorhombic titanium aluminides or oxidation resistance coatings enables the service
temperaturestoexceed500C.[See:49.5TitaniumAluminides].

ONERAhaveseveraldevelopmentsprogrammesfortitaniumbasedmaterials.

47.11.3.2 Propulsion systems


Work on TMCs within Europe and the USA has considered improvements in the performance for
turbineenginepropulsionsystems,particularlyforhighlyloadedcomponents.Thisledsubsequently
tothepossibleapplicationofTMCsinpropulsionsystemsforreusablespacevehicles.

47.11.3.3 Hypersonic vehicles


IntheUSA,TMCsarebeingevaluatedforvariousstructuralandpowerplantelementsunderNASP
andsubsequentlyXprogramvehicles.
Detailedinformationonthematerialsevaluatedandtheirintendedapplicationsisrestrictedoutside
theUS,Ref.[4731].
Within Europe, FESTIP considered titaniumbased materials for hot skin applications (mainly
titaniumaluminidesandcompositesthereof),Ref.[4729].
[Seealso:49.5Titaniumaluminides]

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47.12 References
47.12.1 General
[471]

M.J.DonachieJnr.(Editor)
TitaniumandTitaniumAlloySourceBook
AmericanSocietyforMetals,1982,ISBN:0871701405

[472]

J.Wilson&D.P.Bashford:FulmerResearchLtd.,UK
ReviewofEmergingHighTemperatureAdvancedMaterialsfor
SpaceApplications.FulmerResearchLtd.ReportNo.R1176/1/April
1988.ESAContract7090/87/NL/PH

[473]

MILHDBK5F:MetallicMaterialsandElementsforAerospace
VehicleStructures.November1990
NOTE

ReplacedbyMMPDS01,Ref.[4732]

[474]

MetalsHandbook,Volume2,10thEdition
PropertiesandSelection:NonferrousAlloysandSpecialPurpose
Materials
ASMInternational,ISBN0871703785(V.2),1990

[475]

AdvancedMaterialsforSpaceTransportation
DornierGmbHBattelleEuropeFinalReport,June1992ESTEC
Contract8807/90/NL/PP(SC)

[476]

A.K.Green:FulmerResearchLaboratories,UK
GuidelinesfortheUseofSuperplasticFormingofMetalsin
SpacecraftConstruction.
FulmerResearchLaboratories(FRL)
ReportR878/3A/January
1982andsupplementFRLReport
R878/19/July1985.ESAContract5497/83/NL/PB(SC)

[477]

C.R.Parkinson:BAeFilton,UK
ApplicationofSPF/DBtoSpacecraftStructures
BAeFiltonReport,July1985.ESAContractNo.5588/83/NL/PB(SC)

[478]

G.Brodin
SPF/DBAManufacturingTechniqueforLightweightStructures
ESASP336:AdvancedMaterialsforLightweightStructures(October
1992),p149154

[479]

M.H.Mansbridge
TheIntroductionofTitaniumSuperplasticallyFormedandDiffusion
BondedComponentsintoServiceonAirbusAircraft.22nd
InternationalSAMPETechnicalConference,November691990,
p224236

[4710]

D.G.Konitzer&M.H.Loretto
MicrostructuralAssessmentofTi6Al4V/TiCMetalMatrix
Composite.Acto.Metall.Vol.37.No.2,1989,p397406

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[4711]

P.R.Smith&F.H.Froes
DevelopmentsinTitaniumMetalMatrixComposites
JournalofMetals,March1984,p1926

[4712]

P.R.Smithetal
CorrelationofFractureCharacteristicsandMechanicalPropertiesfor
TitaniumMatrixComposites
ProceedingsofMechanicalBehaviourofMetalMatrixComposites
111thAIMEAnnualMeeting,Dallas,Texas
February16181982,p143168

[4713]

W.Wei
HighTemperatureLowCycleFatigueofaSiC/TiMatrixComposite.
ECCM4.September1990,p319324.ElsevierSciencePublishing
ISBN1851665625

[4714]

HJDudeketal
SiCFibreReinforcedTitaniumAlloys:Processing,Interfacesand
MechanicalProperties.ECCM4.September1990,p339344.Elsevier
SciencePublishing
ISBN1851665625

[4715]

C.M.WardClose&P.G.Partridge
ProductionandPropertiesofContinuouslyReinforcedTitanium
AlloyMMC.MetalMatrixComposites:PropertyOptimisationand
Applications89November1989,TheInstituteofMetals,London

[4716]

A.Vasseletal
Structural&MechanicalCharacterisationofAVCOSCS6/Ti64
Composite.BRITETiMMCProgramme,ONERAReport5/3684M.
August1988

[4717]

A.Vasseletal
ASinglefibreTestTechniqueforTitaniumMMCs.IOPShort
MeetingSeriesNo.28onTestTechniquesforMetalMatrix
Composites,November1990,p5564.ISBN0854985301

[4718]

N.A.James
SmallCouponTensileTestsforRankingMonofilamentreinforced
TitaniumMMCs.IOPShortMeetingSeriesNo.28onTestTechniques
forMetalMatrixComposites,November1990,p4054.ISBN085498
5301

[4719]

P.Bowenetal
FatigueCrackGrowthinContinuousFibreReinforcedMetalMatrix
Composites.IOPShortMeetingSeriesNo.28onTestTechniquesfor
MetalMatrixComposites,November1990,p4054.ISBN085498530
1

[4720]

J.J.Schubbe&S.Mall
DamageMechanismsinaCrossplyMetalMatrixCompositeunder
ThermalmechanicalCycling.ICCM8,1519July1991,Paper20,
p20B120B9

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[4721]

T.P.Gableetal
IsothermalandNonisothermalFatigueBehaviourofaMetalMatrix
Composite.JournalofCompositeMaterials,vol.24,June1990,p667
686

[4722]

M.Mnchen:MTVMotoren&TurbinenUnion,Mnchen,D
HydrogenAbsorptionofTitaniumAlloysDuringDescalingProcess.
DeutscheGesellschaftfrMetalkunde,Adenaurallee21,1985p1275
1281

[4723]

IMITitanium,Birmingham,UK
CorrosionResistanceofTitanium

[4724]

M.Meyer&R.Suchentruck:MBB,D
HighTemperatureOxidationBarriersonTitaniumTheOxidation
BehaviourofThinSputteredNiCrSiCSi3N4andAllayers.
Proceedingsof1stConferenceonIonandPlasmaAssisted
Techniques,IPAT7thGeneva,CH.May31June2,1989,p293298

[4725]

C.Indrigoetal:ONERA,F
HighTemperatureOxidationResistanceofSputterDeposited
TiSiCoatings.ONERATPNo.198454,ProceedingsofIPAT
Meeting,Geneva,CH.May31June21989,p335339

[4726]

B.Hussey&J.Wilson:RJTechnicalConsultants,UK
LightAlloysDirectory&Databook
Chapman&Hall(1998).ISBN0412804107

[4727]

J.Kumpfertetal:DLR,D
AdvancedTMCsforHighlyloadedComponents
ProceedingsofEuropeanConferenceonSpacecraftStructures,
Materials&MechanicalTesting.Braunschweig,Germany46
November,1998.ESASP428,p315320

[4728]

J.Sorensen
TitaniumMatrixCompositesNASPMaterials&Structures
AugmentationProgram.AIAA905207,10.90.ExtractfromTimet
website(April2003)

[4729]

H.Kringsetal:MANTechnologie,D
FESTIPTechnologyDevelopmentinMaterials
ProceedingsofEuropeanConferenceonSpacecraftStructures,
Materials&MechanicalTesting.Noordwijk,NL2729March,1996.
ESASP386,p10851096

[4730]

T.OConnell:Timet,USA
Timetal1100
ExtractfromASMTitaniumAlloysandMetalPropertiesHandbook,
suppliedbyTimet,USA(April2003)

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[4731]

PrivatecommunicationwithTimet(April2003)

[4732]

R.C.Riceetal.
MetallicMaterialsPropertiesDevelopmentandStandardization
(MMPDS)
DOT/FAA/ARMMPDS01,January2003
Website:http://www.mmpds.org/

47.12.2 ECSS documents


[See:ECSSwebsite].

ECSSQ7071

Datafortheselectionofspacematerialsand
processes;previouslyESAPSS01701.

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48 Superalloys and their composites


48.1 Introduction
48.1.1

General

The superalloys are established aerospace materials for engines and turbine components;
demonstratingmanyyearsofservice,[See:48.2;48.15forapplicationsforsuperalloys].

[Seealso:ECSSQ7071:Datafortheselectionofspacematerials]

48.1.2

Alloy development

Demands for improved engine performance have led to requirements for higher operating
temperaturesandlongerservicelives.
Toincreasetheirhighthermalstabilityfurther,superalloycompositionsandprocessingmethodshave
developedjointly,suchas:

DirectionalSolidification(DS).

SingleCrystal(SC).

PowderMetallurgy;includingOxideDispersionStrengthening(ODS)alloys.

[See:48.3forthecharacteristicsofthesealloys]

Innovativecomponentdesignshavedeveloped,wherebyalloyanisotropy(likecompositeanisotropy)
isusedtosustaindirectionalloads.

48.1.3

Composites

Developmentofsuperalloymatrixcompositesisrestrictedbytheavailabilityofareinforcementphase
whichcansurvivethehightemperatureprocessingrequiredformoltensuperalloys.

[See:48.4and48.5]

Work has concentrated on tungstenbased continuous reinforcement. These are large diameter
filaments(>100m,typically).

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Compatibilitywiththematrixremainsaproblem,andoftenadiffusionbarriercoatingisneededon
the fibre to prevent excessive damage during prolonged high temperature use. Developments in
Tungsten Fibre Reinforced Superalloys (TFRS) are described, along with mechanical property data,
[See:48.6].Thequantityofdataislimitedforanyparticularcomposite.

48.1.4

Service environment

Superalloyapplicationsgenerallyinvolvehightemperatures,incombustionenvironments.
In aeroengines, oxidation and the possibility of scuffing resulting in ignition should be considered,
[See:48.8].
For space vehicles, both in engines and active cooling systems, hydrogeninduced material
degradationshouldbeconsidered;especiallyforreusable,longlifestructures.Theeffectsofhydrogen
onsuperalloysarediscussed;alongwithdataonthepossiblepropertylosses,[See:48.7].

[Seealso:Chapter85]

48.1.5

Coating systems

Operationinhotandhostileenvironmentsmeansthatsuperalloycomponentsoftenrequireacoating
topreventexcessiveoxidation,corrosionorotherthermallyinduceddamage,[See:74.7].
Coating systems are commercially available, but are being developed further as operational
temperaturesincrease.
The various types of coating system are described along with the factors to be considered for the
designofthecoatedcomponent,[See:48.9,48.10,48.11,48.12,48.13and48.14].

48.2 Conventional alloys


48.2.1

General

This Topic provides an introduction to the superalloy class of materials, in terms of their role and
requirementsforaerospaceapplications.Itdoesnotprovideextensivepropertydata,butservesasa
basisfortheTopicswhichdescribethemorerecentmaterialdevelopments.
DesigndataisavailableinMILHDBK5;replacedbyMMPDS,Ref.[4849]

48.2.2

Alloy groups

48.2.2.1

General

Superalloysaregenerallygroupedbytheirmainalloyconstituent:

Nickelbased.

Ironbased.

Cobaltbased.

Withineachgroupthereisawidevarietyofalloyswhichdifferbothincompositionandassociated
mechanicalandphysicalproperties.

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48.2.2.2

Requirements

Each family of materials has steadily evolved since the 1940s to meet applications which demand
increasinglygoodmechanicalperformanceathighertemperaturescoupledwithgoodoxidationand
corrosionresistance.
Figure 48.2.1 shows a development curve for superalloys with respect to processing improvements,
Ref.[485].

48.2.2.3

Applications

Theapplicationshavetendedtoberelatedtoturbinecomponents,bothforaircraftenginesandland
basedpowergeneratorunits.

Figure48.21Superalloys:DevelopmentCurve

48.2.3

Aircraft engine applications

48.2.3.1

Requirements

The superalloy material development has attempted to keep pace with demands from aeroengine
manufacturerswithexactingrequirementsformaterialstohelpachieveimprovedengineperformance
intermsof,Ref.[482]:

thrusttoweightratio,

fuelconsumption,

increasedservicelife(periodbetweenoverhauls),and

lowercostofownership.

Table 48.2.1 lists the property requirements for aeroengine components met by Conventional
Superalloydesigns,Ref.[482],[484],[486].
Modernaeroenginestypicallycompriseofapproximately30%byweightsuperalloy,Ref.[483].

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Table48.21Superalloys:Propertyrequirementsforenginecomponents
Application

Turbine discs

Turbine blades

Gas turbine engines

Nozzle guide vanes


and combustion
hardware
Key:

Propertyrequirements

Operating temperatures 200 to 700C typ.


Cyclic stress up to 1100 MPa typ.
Oxidising atmosphere
Hot corrosion resistance (1)
Centrifugal loading
Rim temperature 677C typ.
Temperature gradients
High yield stress
Tensile strength to 700C typ.
Creep and creep fatigue resistance
Low and high cycle fatigue resistance (LCF, HCF)
Crack growth resistance
Oxidisation resistance
Hot corrosion resistance
Centrifugal stresses 150 to 200 MPa, typ.
Gas entry temperature 1377C, typ
Gas temperature at incipient melting point (2)
Thermal gradients: Blade tip to root.
Blade temperatures 1047C, typ.
Static and cyclic loading
High temperature creep strength (at 0.8 Tm.) (3)
Fatigue resistance
Density
Thermal conductivity
Thermal emissivity
Thermal expansion
Melting point
Stiffness
Tensile strength
Creep strength
Fatigue strength
Fracture resistance
Impact resistance
Toughness
High temperature properties similar to blades even
though they are static components.
Sheet form: High tensile and creep resistance.

(1)Bysaltsinmarineenvironments&lowgradefuelcontaminants.
(2)Cooledbladeswithinternalchannels.
(3)TmisthemeltingtemperatureinC

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48.2.3.2

Materials

Ofthethreegenericclasses,Nickelbasedmaterialsaremostwidelyusedbecausetheypossesscertain
beneficialmetallurgicalstabilitycharacteristicsathightemperaturesoverIronbasedalloys,Ref.[48
3].
Cobalt superalloys have also been replaced by nickelbased alloys, partly because of an inability to
provide further strengthening through conventional mechanisms, but primarily due to the world
wideshortageofCobaltinthelate1970s.Thisledtoaprogrammeofworktoreassessthelevelsof
cobalt additions in other superalloy families, and reduced them without detriment to the alloy
performance,Ref.[484].
Table48.2.2listssomeofthealloysusedforaeroenginecomponents,Ref.[484],[485],[486],[487].
Thelistisnotexhaustive.

48.2.3.3

Mechanical properties

Table48.2.3providestypicalmechanicalpropertiesofsomeofthebetterknownsuperalloysatvarious
temperatures,Ref.[489].

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Table48.22Superalloys:Foraeroenginecomponentapplications
Alloydesignation[Manufacturer]

Application

Notes

Nimonic 901 [INCO]


Inconel 718 [INCO]
Rene 41 [TELEDYNE]
Waspalloy [UN.TECH]
Astroloy [-]
Rene 95 [TELEDYNE]

disc
disc
disc
disc + blade
disc
disc

IN 100 [-]

disc + blade

Denoted as Ni-Fe
Denoted as Ni-Fe
Powder Met. Variant
Powder Met. Variant
Powder Met. Variant
also MERL 76 for HIP

Udimet 700 [SPEC. MTLS]


Udimet 710, 720 [-]
PA101 [-]
AF115 [-]
AF2-1DA [-]
MAR-M200 [MARTIN MAR]
MAR-M002
MAR-M247
Nimonic 80A [INCO]
Nimonic 90
Nimonic 105
Nimonic 115

disc + blade
disc
disc
disc
disc

Powder Met. Alloy


Powder Met. Alloy
Powder Met. Alloy

disc
disc
disc
disc
disc
disc

Principle Fe-based
alloys used in USA

Nickelbased:

Ironbased:

Discaloy [WEST. ELEC]


Tinadur
M308
A286
V57
FV537
Cobaltbased:

FSX-414
MAR-M 322
MAR-M 302
IN 102
Key:

Nozzle
diaphragm
casting

INCO:TheInternationalNickelCo.Inc.;
TELEDYNE:TeledyneAllvac;

Weldability

UNTECH:UnitedTechnologiesCorp.;

SPEC.MTLS:SpecialMetalsCorp.;

MARTINMAR:MartinMariettaCorp.;

WESTELEC:WestinghouseElectricalCorp.

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Table48.23Superalloys:Typicalmechanicalproperties
Alloy

Form

sheet

bar

Inconel 600

bar

Inconel 625

bar

Temp.

TS

YS

El

R of A

Notch
TS

DEWSIM

Melting
Range

(C)

(MPa)

(MPa)

(%)

(%)

(GPa)

(MPa)

100h

1000h

(gcm-3)

(C)

-253

1210

910

22

8.42

1354-1415

24

910

885

-257

1280

1210

20

56

220

1530(a)

-253

1250

1100

30

58

-196

1160

1030

26

62

-78

985

910

20

56

24

940

890

15

56

170

1230(a)

21

620

250

47

540

580

195

47

650

450

180

39

760

185

115

46

815

55

39

870

105

62

80

37

24

21

855

490

50

540

745

405

50

650

710

420

35

440(b)

370(b)

760

505

420

42

815

130(b)

93(b)

870

285

475

125

72(b)

48(b)

Stress Rupture

Comments

Hard, cold rolled,


long dir.

Cold drawn, long


dir.
(a) Kt = Not stated

Not stated

8.44

1290-1350

(b) Solution Treated


(ST):1150C

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Alloy

Form

sheet

sheet

Inconel 718

sheet

bar

Inconel 718

bar

Temp.

TS

YS

El

R of A

Notch
TS

Stress Rupture

DEWSIM

Melting
Range
(C)

Comments

(C)

(MPa)

(MPa)

(%)

(%)

(GPa)

(MPa)

100h

1000h

(g/cm3)

-253

1740

1340

16

1550(c)

-196

1730

1310

21

1560

-78

1490

1190

17

1470

24

1330

1090

18

1330

-253

1770

1370

16

1500(c)

+720C/8hr/FC to

-196

1700

1300

21

1500

620C/10hr/AC

-78

1480

1210

12

1450

24

1320

1100

18

1300

21

1280

1050

22

540

1140

945

26

650

1030

870

15

760

675

625

-269

1810

1410

21

20

Longitudinal dir:

-196

1650

1340

21

20

Aged:980C/45
min/AC

24

1410

1170

15

18

+720C/8hr/FC to
620C/10hr/AC

21

1430

1190

21

540

1280

1060

18

951(d)

595

860(d)

760(d)

650

1230

1020

19

690(d)

585(d)

760

950

740

25

870

340

330

88

Longitudinal dir.
Aged:955C/1hr/AC

(c) Kt = 10
transverse dir:
Condition - as
above:
(c) Kt = 10

(d) 730C/2hr.

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Alloy

Form

bar

Inconel X750

Temp.

TS

YS

El

R of A

Notch
TS

Stress Rupture

DEWSIM

Melting
Range
(C)
393-1425

(C)

(MPa)

(MPa)

(%)

(%)

(GPa)

(MPa)

100h

1000h

(g/cm3)

-257

1720

1080

33

46

8.25

-253

1700

1090

33

42

-196

1570

1050

32

45

24

1340

985

25

49

21

1120

635

24

540

965

580

22

827(e)

650

825

565

Longitudinal dir.
Annealed Aged:
700C/20hr/AC

(e) 1150C +
840C/24hr/? +
705C/20hr/?

bar

Rene 41

bar

760

485

455

870

235

165

47

83(e)

45(e)

925

58(e)

21(e)

21

1420

1060

14

540

1400

1010

14

650

1340

1000

14

760

1100

940

11

870

620

550

19

Comments

8.25

1232-1371

Not stated

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Alloy

Waspalloy

MAR-M-246

Form

bar

DS

DEWSIM

Melting
Range

1000h

(g/cm3)

(C)

8.20

1339-1355

35

131

183

Transverse

760

103

Longitudinal

760

149

Transverse

Temp.

TS

YS

El

R of A

Notch
TS

(C)

(MPa)

(MPa)

(%)

(%)

(GPa)

(MPa)

100h

21

1280

795

25

540

1170

725

23

650

1120

690

34

760

795

675

28

870

525

515

21

21

Stress Rupture

Comments

Not stated

Longitudinal

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48.2.3.4

Design

It is widely believed that aeroengine requirements have exceeded the capability of conventional
superalloys and little can be gained by further alloy development alone. That said, there are
innovative component designsin service which cope with over temperature of gasesimpinging on
superalloy blades and discs by incorporation of cooling channel systems. Blades are by their nature
very complex components, as shown in Figure 48.2.2, and there is a possibility of further
improvementswithdesign,Ref.[486].

Figure48.22Superalloys:Cooledturbineblade

48.2.4

Spacecraft engine applications

48.2.4.1

Operational conditions

The operating conditions for some turbines in advanced rocket engines are, in some respects, more
severethantheirairbreathingaeroenginecounterparts.
Table48.2.4comparestheoperatingconditionsofrocketengineandaircraftengineturbines,Ref.[48
8].

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Table48.24Superalloys:Comparisonofrocketengineandaircraftengine
turbineoperation
Servicecondition

Rocketengine

Aircraftengine

Fuel
Oxidiser
Pressure (MPa)
Speed (rpm)
Tip speed (m/s)
Horsepower/blade
Inlet temperature (C)
Heat transfer coeff.
(kW/m2/C)
Thermal transients (C/sec)
Starts
Life (hours)

Hydrogen/Methane
Oxygen
38
36000 to110000
564
630
880 to 1 215

Petroleum distillate
Air
2.8
15000
564
200 to 500
1435

306.6

2.84

17770
55 to 700
7.5 to 100

55
2400
8000

Key:

:SpaceShuttlemainengine(SSME).Highpressureturbopumpturbine

Mostnoticeablearethedifferencescausedbythecombustionofhighpressurehydrogenfuelbetween:

heat transfer coefficients, and

thermal transients.

48.2.4.2

Requirements

For rocket engine turbines, Figure 48.2.3 compares the Space Shuttle and Aero turbine engine
operatingregimes,Ref.[488].

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Figure48.23OperatingregimesforSpaceShuttleandaeroengineturbines

Thecombinationoffatiguebothatlowandhighcycleandhydrogenenvironmenthavemeantthatthe
designaimof7.5hr(55launches)wasnotbeenachievedwithconventionalsuperalloys.

48.2.4.3

Material development

Table48.2.5liststhematerialsystemsunderevaluationforrocketengineapplication,Ref.[488].

Table48.25Superalloys:Potentialbladematerialsunderevaluationforrocket
engineturbinecomponents
Typeofmaterial

Notes

Directionally solidified alloys (DS)


Single crystal superalloys (SC)
Rapid solidification (RS)
Fibre reinforced superalloys
(TFRS)
Monolithic ceramics

MAR-M246 + Hf eutectic alloys


[See: Table 48.2.6]
[See: 48.6]
[See: Chapter 43]

Of these materials Single crystal superalloys (SC) and certain alloys within that group, as shown in
Table48.2.6,areconsideredtohavepotentialforturbinepropulsionsystemsinSpaceShuttle,Ref.[48
8].

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Table48.26Singlecrystalsuperalloys:Potentialuseinrocketengineturbines
Alloy

AF56
N5
PWA 1480
RR 2000
N4
CMSX-4C
SC180
SRR 99
MAR-M246
CMSX 2 0
CMSX 2 CM

Ranking

Best

Worst
Key:

Rankedonhydrogenstrengthratioroomtemperature
notchtensioninhighpressurehydrogen.

48.3 New alloys


48.3.1

Developments

48.3.1.1

Combined alloying and processing

Thedevelopmentswithsuperalloyshaveconcentratedonenhancingpropertiesbyacombinationof
alloymodificationandspecialistprocessingtechniques,suchas:

Directional solidification (DS)

Single crystal (SC)

Powder metallurgy (PM), e.g. directional recrystallisation of extruded powder, Hot isostatic pressing
(HIP)

Oxide dispersion strengthened (ODS)

48.3.1.2

Characteristics

Theprocessingofthefirstthreegroupsleadstomaterialswithdirectionalpropertiesusefulinturbine
blades.TheDSgroupareknownasInsituorNaturalcomposites,wherethestrengtheningphaseis
usuallyinchemicalequilibriumwiththematrix.

Oxide dispersion strengthened (ODS) alloys are not considered to be composites, as the dispersions
areextremelyfine(submicron)andinteractwiththehostalloyatamicroscopiclevelinthesameway
astheprecipitatesformedbyalloying.

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48.3.2

Directional solidification (DS)

48.3.2.1

Composition

InDSalloys,thecompositionisadjustedtoproduceaeutecticuponsolidification.
Table48.3.1listssomeoftheeutecticsystemsunderevaluation,Ref.[4810],[4811].

Table48.31Reinforcingphasesindirectionallysolidified(DS)eutectic
superalloys
Composition

Typeofreinforcement

Co-TaC
Ni-TaC
Ni3Al-Ni3Nb
/

Fibrous. 5 to 12 vol.%, typ.


Fibrous. 5 to 12 vol.%, typ.
Lamella. 30 to 40 vol.%, typ.
-

Key:

:Typicalcontents.

48.3.2.2

Application

The fibrous types of DS alloy are of interest for turbine blade applications, where the fibres can be
alignedalongtheaxisoftheblade.Table48.3.2listssomeDSalloys,Ref.[4813].

Table48.32Directionallysolidified(DS)superalloys
Alloy

Composition(BalanceNickel)

MAR-M
200+Hf

2.2Ti - 4.9Al - 9.5Co - 1Nb - 12W - 1.7Hf - 9.5Cr - 0.14C - 0.015B

Rene 80 H
441
MAR-M 247

4.7Ti - 3.1Al - 9.3Co - 4Mo - 3.8W - 0.72Hf - 13.9Cr - 0.15C 0.015B


5.9Al - 11.7Co - 1.1Mo - 7.1Ta - 5.5W - 1.4Hf - 6.6Cr - 3.1Re 0.06C - 0.02B
10Co - 8.4Cr - 0.6Mo - 10W - 3.3Ta - 5.5Al - 1Ti - 1.4Hf - 0.15C 0.015B - 0.05Zr

48.3.3

Single crystal (SC)

ThesetypesofmaterialsofferbettercreepandfatiguelifethantheDSfamilyandareofinterestfor
turbine blade applications. Their properties are highly anisotropic and are dependent on the
crystallographicorientation.
Table48.3.3listssomeoftheSingleCrystal(SC)alloys.

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Table48.33Singlecrystal(SC)superalloys
Alloy

Composition

NASAIR 100
"Alloy 3''
CMSX-3
PWA 1480
SRR-99
AF 56
RR 2000
N4
CMSX-4C
CMSX 2 0
CMSX 2 CM

BalNi-0Cr-1Mo-10.5W-3.3Ta-5.8Al-1Ti
BalNi-5.1Co-8.7Cr-8Mo-10W-3.2Ta-5.4Al-1.1Ti-0.6Hf
BalNi-4Co-7.5Cr-.5Mo-7.5W-6Ta-5.5Al-.0Ti-.1Hf
BalNi-5Co-10Cr-4W-12Ta-5Al-1.5Ti
BalNi-5Co-8.5Cr-9.5W-2.8Ta-5.5Al-2.2Ti

Other SC alloys investigated for use in N5 Space


Shuttle Main Engine (SSME) Turbine

48.3.4

Powder metallurgy (PM)

Production of superalloy materials by powder techniques became of interest when deficiencies in


conventional processing methods were observed for highly alloyed variants. Compared with
conventionallyproducedsuperalloys,PMsuperalloysarerecognisedasproviding,Ref.[4848]:

improvedstrength,

improvedcreepresistance,

improvedcreepfatigue,

betterlowcyclefatigueproperties.

Thesecharacteristicshavebeenachievedbytwomainprocessrelateddevelopments,Ref.[4848]:

gatorising (Pratt and Whitney) or isothermal forging: to reduce the fracture initiation and
growth of those defects present. this process improves LCF properties compared with as
HIPpedcomponents.Wherecreepstrengthisthesoledesigncriterion,asHIPpedcomponents
areused,butmostengineapplicationsuseisothermalforging.

finerpowder(<106m,often44mmax.):toreducethesizeofnonmetallicdefects.

heattreatment:supersolvustoincreasedgrainsizeanddamagetolerance.ForNibasedalloys,
producingagammaprimephase(upto64%,dependingontheparticularalloycomposition).

PMsuperalloydevelopmentwasaccompaniedbysometechnicalproblems,assummarisedinTable
48.3.4,Ref.[484],[485],[488].
Thesehavelargelybeenovercomeby,Ref.[4848]:

processcontrol:whenstrictlycontrolled,thiscansuccessfullylimitnonmetallicdefectsduring
processingandafteratomisation.

contamination:significantlyreducedbyuseofcleanroomenvironments,oftenwithvacuumor
inertgasscreeningandloading.

fracture mechanics (defect size and crack growth rate): a major design criterion for PM
application.Definingandlimitingdefects(inherentinPMproducts)isessential.

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Table48.34Powdermetallurgyofsuperalloys
Process

Problem

Powder
production

High oxygen levels

Powder forging

Extruded
powder billet

Limited deformation &


recrystallisation

Hot isostatic
pressing (HIP)

Key:

Comments

Process in vacuum & inert


gas. Acceptable levels now
100 ppm.
Improved mechanical
properties.
Fine grain size &
superplasticity.
Alloy modified to fine tune C
content and carbide
stabilisers (Nb, Ta, Hf) for
HIP alloys.

Prior particle boundaries


not eliminated
Exogenous defects
Porosity in SC alloys act as
initiators for fatigue cracks.

Improved if HIPped
-

Potentialcostreductionof35to40%forturbineblades.

Asaresult,afamilyofpowdermetallurgy(PM)superalloysarecommerciallyavailable.Someofthese
arelistedinTable48.3.5,Ref.[484],[4848].

Table48.35Powdermetallurgynickelbasedsuperalloys:Composition
Alloy
AF115
AF2-1DA
Astroloy
IN100
MERL76
N 18
PA101
Rene 88T
Rene 95
Key:

Composition
BalNi-10.5Cr-15Co-2.8Mo-5.9W-1.8Nb-3.8Al-3.9Ti-0.05Zr-0.8Hf0.02B-0.05C
BalNi-12Cr-10Co-3Mo-6W-1.5Ta-4.6Al-3Ti-0.35C
BalNi-15Cr-17Co-5Mo-4Al-3.5Ti-0.25B-0.03C (1)
BalNi-12.4Cr-18.4Co-3.2Mo-5Al-4.3Ti-.8V-0.06Zr-0.02B-0.07C
BalNi-12.4Cr-18.5Co-3.2Mo-1.4Nb-5Al-4.3Ti-0.06Zr-0.4Hf-0.02B0.025C (2)
BalNi-11.5Cr-15.7Co-6.5Mo-4.35Ti-4.35Al-0.02B-0.03Zr-0.02C-0.5Hf
BalNi-12.5Cr-9Co-2Mo-4W-4Ta-3.4Al-4.1Ti-.11Zr-1Hf-0.015B-0.016C
BalNi-16Cr-13Co-4.0Mo-4.0W-3.7Ti-2.0Al-0.015B-0.03Zr-0.03C-0.7Nb
BalNi-13Cr-8Co-3.5Mo-3.6W-3.5Nb-3.5Al-2.5Ti-0.05Zr-0.01B-0.06C

(1)SimilartoUDIMET700,APK1,MTS1024.
(2Powdermetallurgy(PM)modificationofIN100atomisedfordirectHot
IsostaticPressed(HIP)components.

PM processing techniques are also appropriate to the ODS class of superalloys, i.e. materials
strengthenedbyoxidedispersionsorbyothersimilarlyhardparticles.

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48.3.5

Oxide dispersion strengthened (ODS) alloys

Table48.3.6listssomecompositionsofcommercialODSsuperalloys.Yttria(Y2O3)isastableoxideat
hightemperatures.Additionsaremadeduringpowderproduction,Ref.[4813],[4846],[4847].
The resultant materials offer significant mechanical properties up to approximately 0.9 of their
meltingtemperature,Ref.[4813].

Table48.36Oxidedispersionstrengthened(ODS)superalloys:Composition
Alloy

Composition

MA 753
MA 754
MA 758
MA 760
MA 956

BalNi-20Cr-1.5Al-2.5Ti-0.05C-0.007B-0.07Zr-1.3Y2O3
BalNi-1Fe-20Cr-0.3Al-0.5Ti-0.05C-0.6 Y203
BalNi-30Cr-0.3Al-0.5W-0.3Al-0.05C-0.37O (total) + Y2O3
BalNi-19.5Cr-6Al-3.4W-1.2Fe-0.6C-0.3N-0.6O (total) + Y2O3
BalFe-20Cr-4.5Al-0.5Ti-0.05C-0.5Y2O3
BalNi-15Cr-4.5Al-2.5Ti-0.05C-4W-2Mo-2Ta-0.01B-0.15Zr1.1Y2O3
BalNi-9.5Cr-8.5Al-0.05C-6.6W-3.4Mo-0.01B-0.15Zr-1.1Y2O3
BalNi-9.5Cr-7Al-0.05C-8W-2Mo-1Ta-0.15B-1.1Y2O3
BalNi-20Cr-3.0Fe-0.5Ti-0.3Al-0.6Y2O3

MA 6000
Alloy 51
Alloy 69
PM 1000

Certainthermomechanicalandrecrystallisationproceduresenablefurtherpropertyimprovementsin
ODSalloysathightemperatures,Ref.[4813],[4814].
Figure 48.3.1 compares tensile properties of some ODS alloys and two cast alloys at elevated
temperatures,Ref.[4813].

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0.2% Offset.
MAR-M Martin Marietta Corp.

Figure48.31ODSsuperalloys:Comparisonofyieldstrengthwithcasting
superalloys
AcomparisonbetweenthetensileelongationforsomeODSalloysandcastalloysisshowninFigure
48.3.2,Ref.[4813].
AlthoughthemajorityofefforthasbeenplacedonY2O3ODSmaterials,thisstrengtheningmechanism
isappropriateforotherdispersoidshavinghightemperaturestability,e.g.nitrides,Ref.[485].

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MAR-M Martin Marietta Corp.

Figure48.32ODSsuperalloys:Comparisonoftensileelongationwithcasting
superalloys

48.4 Discontinuously reinforced composites


Therearenodiscontinuouslyreinforcedcompositeswithdeliberateadditionsofeither:

Particulates,or

Whiskers.

Thereinforcingmediacannotsurviveprocessingwithmoltensuperalloys,giventheirmeltingranges.
The nearest materials are the directionally solidified (DS) and oxide dispersion strengthened (ODS)
variants,[See:48.3].

[See:Table48.5.1forexamplesofdiscontinuousreinforcementsexaminedforsuperalloys]

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48.5 Continuously reinforced composites


48.5.1

Composite development

48.5.1.1

General

Continuous reinforcing fibres and filaments which survive processing in molten superalloys are
extremelylimited.

48.5.1.2

Reinforcements

Interesthasfocusedoncombiningrefractorymetalreinforcementphaseswithsuperalloystoincrease
strengthathightemperatures.
Table48.5.1 lists the reinforcement phases considered forsuperalloysand notes on their success. Of
thoselisted,Tungstenandthoriatedtungsten(ThO2)Wwireshavereceivedmostattention.
The typical range of diameters for continuous reinforcements is 100 to 500m. They are
monofilamentsbutarealsodescribedaswiresinsomepublications,fibresorfilamentsinothers.

Table48.51Superalloycomposites:Reinforcementphases
Type

Particulate

Whisker

Continuous
wires

Key:

Material

Comments

HfO
ZrO
SiC
Si3N4
Sapphire
Alumina
Mo
Nb
(ThO2)W
W-Hf-C
W-Hf-ReC

Severe degradation during fabrication or


subsequent thermal soak.
[See: 48.4]
Attacked by Ni during fabrication.
Less affected by matrix.
Newer materials. Higher strengths.

Typicaldiameterrange:100mto500m.

48.5.1.3

Matrix alloys

Table 48.5.2 summarises a number of superalloys that have been considered as the matrix phase
primarilywithtungstenbasedwires.

[Seealso:48.6forTFRSTungstenfibrereinforcedsuperalloys]

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Table48.52Superalloys:Typicalmechanicalpropertiesofmatrixmaterialsfor
composites
Alloyclassification

Units

IN102

MAR-M 322
(c)

MAR-M 302
(c)

Discaloy (d)

FeCrAlY

Density
Thermal
Conductivit
y
Thermal
Expansion

g/cm3

8.22

8.19

8.19

8.55

8.91

9.21

7.95

Wm/
K

9.7

11.2

11.2

10-6
/K

13.8

12.7

13.0

14.0

RT
760
870
RT
760
870
RT
760

358-380
262
179
787
435
255
195
-

621-740
504
262
1235
758
400
-

1056
628
1276
676
200
155

504
386
200
959
441
214
-

RT
760
870

43
37
50
Sheet
Wrough
t

24
20
34
Bar
Wrough
t

22
8
Sheet
Wrough
t

47
110
110
Bar
Wrough
t

690
386
310
932
704
448
227
160
150
nom.
2
8
11
-

730
428
173
1000
483
195
-

870

628
379
345
828
628
552
227
160
150
nom.
3.2
6.5
12
-

Cast

Cast

40
32
33
Wrough
t

0.2% Proof
Stress

MPa

Tensile
Strength

MPa

Young's
Modulus

GPa

Elongation

(C)

Material
Form

Key:

(b)

Property

Inconel 718 (b)

Ironbase

Nimonic 80A
(b)

Cobaltbase

Hastelloy X (a)

Nickelbase
Temp

(a)CabotCorp.(b)TheInternationalNickelCo.Inc.;(c)MartinMariettaCorp.(d)
WestinghouseElectricCorp.
:At20C;:Between20Cand95C;:FeCrAlYalloysareonlyconsideredassuperalloyswith
OxideDispersionStrengthening.

48.6 Tungsten fibre reinforced superalloy (TFRS)


composites
48.6.1

Development

Studiesoftungstenbasedreinforcementsinvarioussuperalloymatriceshaveconsidered:

Refractorywiresandtheirfabrication

Optimisationofthematrixalloycomposition

Fabricationprocesses

Fibrematrixinteraction

Diffusionbarriertechnology

Mechanicalpropertydetermination

Owing to the large number of materialcombinations, data tends to be incomplete onany particular
compositesystem.

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48.6.2

Matrix alloys

48.6.2.1

General

Of the three prime superalloy classes, ironbased superalloys are more compatible with tungsten
based reinforcements, as shown in Table 48.6.1, of which FeCrAlY offers considerable promise, Ref.
[4815].

Table48.61Tungstenfibrereinforcedcomposites:Reinforcementandsuperalloy
matrix
Recrystallisation temperature of W reduced by: Ni, Al & Mn.
Reinforcement
Reaction of W with matrix.
Formation of intermetallic and/or carbide compounds in
Matrix
proximity of fibre, reducing composite integrity.
Lower solubility of W in Fe, compared with Ni.
Iron-based
Less active in promoting W recrystallisation.
superalloys
Fe-W intermetallics are more stable at high temperatures
than W-Ni compounds.
High oxidation resistance
FeCrAlY
High melting point
Compatible with W

48.6.2.2

Diffusion Barrier Coatings

For other TFRS systems, effort has concentrated on developing diffusion barrier coatings to deter
matrixfibreinteraction,Ref.[4815].Thevarioustypesofcoating,orcombinations,beingconsidered
are:

Hafnium compounds: HfN, HfO.

Titanium compounds: TiC, TiN.

Zirconium compounds: ZrC, ZrO2.

Thisisarecognisedmethodofreducinginterdiffusion,butanoptimisedsystemshouldbeusedfor
eachspecificmatrix.

48.6.3

Mechanical properties

48.6.3.1

General

Dataonmechanicalpropertiesarelargelydrawnfromresearchpublicationsinwhichthenumberof
materialcombinationsarediverse.Datasetstendtobeincompleteonanyparticularmatrixandfibre
combination.

48.6.3.2

Tensile

ThepropertiesshowninTable48.6.2,Table48.6.3andTable48.6.4areanindicationofwhatcanbe
achievedfromthevariousmaterialsystems,Ref.[4815].

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Table48.62Tungstenfibrereinforced,nickelbasedsuperalloys:Tensilepropertiesofdevelopmentcomposites
Filament

Matrix

Ni

W-2%Th02

MAR M 200

MAR M 200
only

HSTW wire
only

Key:

Fibre vol
(%)
40-44
''
''
''
''
''
50-55
''
''
''
''
''
''
''
''
-

Diffusion
barrier
coating
TiC
TiC
TiN
TiN
-

CompositesHIPped1120C,138MPafor2hrs.

Fibre
angle
()
0
0
0
0
0
0
0
0
10
45
90
0
10
45
90
-

Test
temp
(C)
650
930
650
930
650
930
870
980
980
980
980
1090
1090
1090
1090
870
980
1090
870
980
1090

0.2% YS
(MPa)

UTS
(MPa)

E
(GPa)

Elong.
(%)

R of A
(%)

193
70
121
60
-

270
127
232
117
201
99
1157
839
638
440
449
595
430
147
119
840
523
213
1371
1212
1109

1.67
8.6
2.6
>12.4
9.0
24.5
24.8
29.7
29.4
-

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Table48.63Tungstenfibrereinforced,cobaltbasedsuperalloys:Tensilepropertiesofdevelopmentcomposites
Filament

W-2%Th02

W-2%Th02 only

Matrix
MAR M 332C
''
MAR M 322D
''
''
''
MAR M 322E
''
''
MAR M 332C
only
MAR M 322E
only
-

Fibre vol
(%)
33
35
43
44
40
44
40
38
40
-

Diffusion
barrier coating
-

Fibre
angle ()
0
0
0
0
0
0
0
0
0
-

Test temp
(C)
RT
900
980
1093
1150
1315
980
1093
1150
RT
1093
RT
900
980
RT
650
870
1093

0.2% YS
(MPa)
537
488
392
96
537
419
392
710
214
303
276
110
-

UTS
(MPa)
345
590
545
520
420
103
545
434
448
214
448
386
117
2170
1791
1780
1309

E
Elong.
(GPa)
(%)
0.2
4.9
4.7
3.2
4.0
0.5
3.6
9.0
18
-

R of A
(%)
6
30
28
25

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Table48.64Tungstenfibrereinforced,ironbasedsuperalloys:Tensilepropertiesofdevelopmentcomposites
Filament

Matrix

W-1%Th02

AISI 1095

W-2%Th02

304 SS

W-2%Th02

Kovar

W-1%Th02

FeCrAlY

Fibre vol
(%)
20
20
20
20
20
25
25
25
25
35
35
35
35
35
35
25
25
35
35
35
35
35
35

Diffusion
barrier coating
-

Fibre angle
()
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
15
45
90
15
45

Test temp
(C)
RT
RT
RT
380
600
700
980
RT
200
360
500
RT
200
360
500
700
980
RT
600
RT
648
648
648
760
760

0.2% YS
(MPa)
-

UTS
(MPa)
400
938
650
566
470
470
300
540
700
625
560
660
840
710
760
600
470
620
500
620
746
551
185
552
169

E
Elong.
(GPa)
(%)
297
293
179
19
29
3.4
13
24

R of A
(%)
-

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Filament

Matrix

W-1%Th02

FeCrAlY

W-Hf-C

FeCrAlY

Key:

Fibre vol
(%)
35
35
35
35
30
30
50
<38
42
44

Diffusion
barrier coating
-

Fibre angle
()
90
90
0
0
0
0
0
0
0
0

Test temp
(C)
760
RT
648
648
982
1093
982
982
1093
1093

0.2% YS
(MPa)
615
665
428
540

UTS
(MPa)
111
654
737
768
460
381
684
724
>548
607

E
Elong.
(GPa)
(%)
6.5
179
3
2.9
0.6
0.3
152
3.2
151
2.4
265
>1.6
3

R of A
(%)
-

After heat treating


Composites HIPped 1050 to 1200C & 150 to 250 MPa
Composites hot pressed
As fabricated, after creep testing at: 1037C for 1077 hrs. 1093C for 99 hrs.
Composites hot pressed

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48.6.3.3

Long-term elevated temperature use

WithregardtotheintendeduseofTFRSatelevatedservicetemperatures,limiteddataareavailable
on:

fatigue,

creep,

impact,and

oxidationresistance.

Generally the data have been produced for comparative purposes during studies on fibrematrix
interactionsorprocessingtechnology.Thereforeitisspecifictothematerialandtestconditions.

48.6.3.4

Thermal cycling

Table 48.6.5 provides an indication of thermal cycling resistance for a tungstenreinforced FeCrAlY
composite, Ref. [4816]. The loss of RT tensile strength was attributed to matrix damage due to
different fibre and matrix thermal expansion characteristics and improved fibrematrix bonding
permittingcrackpropagationacrossthebondintothefibres.Nodamagetothefibreswasnoted.

Table48.65Tungstenfibrereinforcedsuperalloy:Roomtemperaturetensile
strengthofthermallycycledcomposite
Maximumcyclictemperature

RTtensilestrength

(C)

(MPa)

Control
850
1000
1090

772
785
655
489

Key:

Replicates

3
3
2
2

Material4ply218CSTungstenfibreinFe22Cr5.5Almatrix.Unidirectional.37%fibre
volume.

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48.6.4

Characteristics

Table48.66providessomegeneralcommentsonTFRSsystems,theiradvantages,andareasrequiring
furtherevaluation,Ref.[4815].

Table48.66Summaryoftungstenfibrereinforcedsuperalloy(TFRS)systems
Advantages

Disadvantages

Futuredevelopment

Perceived operating
temperature 1100C +

RT Tensile properties less


than matrix alone.
W ductile-to-brittle
transition temperature 150
to 370C; flaw sensitivity
in brittle state.

At elevated
temperatures TFRS
have superior
properties:
1.7x at 1090C
WTh02/Ni
3.2x at 980C
WTh02/Co

Development centred on
air-breathing aero engine
requirements.

Effect of rocket
engine environment
with H-based fuels
required.

Improved stress
rupture characteristics.

Some systems susceptible


to thermal fatigue.
FeCrAlY superior to other
systems.

FeCrAlY good
corrosion/oxidation
resistance.

High density.

Considerable
experience in applying
conventional
superalloys to high
temperature
environments.

Offer ~100C improvement


over the conventional and
new superalloys.

Full evaluation
programme for most
appropriate
combination.
Need to establish
long-term
environmental
stability.

48.7 Effect of hydrogen


48.7.1

Degradation mechanisms

Hydrogenisknowntobedetrimentaltotheperformanceofawiderangeofmaterialsbychanging:

ductility(embrittlement)

crackbehaviour

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48.7.2

Hydrogen embrittlement (HE)

Theeffectsofhydrogenembrittlement(HE),dependupon,Ref.[4817]:

magnitudeandextentofhydrogeninteractionwiththematerial,

easeofhydrogentransportfromtheenvironmenttothematerial.

Table48.7.1summarisesseveralphenomenathathavebeendetermined,Ref.[4817].
Theeffectofhydrogenonsuperalloyscanbesummarisedas:

Effectscanbeextensive.

Influencesdeformationbehaviourbyinteractionwithdislocations.

Reducesductilitybydecreasingflowstressandenhancingplanarslip.

Affectslatticebondinteractionsateithergrainboundariesorthroughgrains.

Leadstobrittlehydrideformation,causinglatticeexpansion,stableatandbelowRT

Effectsareactivetotemperatureofapproximately600C

Table48.71Establishedmechanismsofhydrogendegradationinmaterials
Phenomenon

Characteristics

Occurs at high temperature.


Formation of a reaction product between hydrogen &
alloying element, e.g. H2 + C methane, in steels.
Hydrogen attack Both reactants diffuse to an internal interface to combine
& form a cavity.
Continued reaction produces high pressure gas pockets
inside material.
Occurs at RT, or below, plus high temperatures.
Diffusion of protonic hydrogen through material to
interface.
Internal hydrogen
Depends on a supersaturation level.
pressure
Reacts to form high pressure molecular H2 gas pockets
inside material.
Molecular hydrogen is largely immobile.
Wide temperature range.
Dislocation
Does not require super saturation of protonic H.
interaction
Strongly influences plastic behaviour.
Protonic hydrogen levels above saturation.
Reacts to form a brittle metal hydride.
Hydride formation
Hydrides precipitate at selected planes and local regions
of high strain.

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48.7.3

Hydrogen environment embrittlement (HEE)

Inspacepropulsionunits,wherehydrogen(asafuelorcoolant)isindirectcontactwiththematerials,
additionalfactorshavebeenidentified.ThesearedescribedasHydrogenEnvironmentEmbrittlement
(HEE)andoccurwithoutaholdtime;i.e.withoutallowinghydrogenchargingofthematerial,and
areinadditiontothoseeffectsdenotedasHE.
CharacteristiceffectsofHEEareshowninTable48.7.2,Ref.[4818].
For materials under prolonged high temperatures, factors associated with HEE and HE become
important,andcanactinsynergy.

Table48.72Characteristicsofhydrogenenvironmentembrittlement(HEE)
Condition

Characteristics

Occurs without H charging of material.


Environment Degradation of properties compared with
air or inert environment, i.e. He.
Effects thin surface layer which then cracks
Material
when deformed (strain-to-crack initiation).
Relevant to all materials.
Lower tensile ductility.
Tensile plastic deformation causes surface
cracking.
Mechanical
Sub-critical crack growth.
properties
Faster crack growth rates, both under cyclic
and sustained loads.
Reduced notched tensile strength.
Occurs between cryogenic up to ~1144K,
Temperature typically.
Most severe at approx. RT.
Increases with increasing Hydrogen
Pressure and
pressure.
purity
Sensitive to gas purity.

Comments

Elastic
properties and
tensile yield
strength
largely
unchanged

Pure hydrogen
most severe.

48.7.4

Material sensitivity

48.7.4.1

General

Table48.7.3summarisesthesensitivityofcertainalloyswithregardtotheirtensilepropertyretention
ratioinhydrogenandaninertatmosphere,i.e.helium,Ref.[4818].

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Table48.73Sensitivityofsuperalloystohydrogen
AlloySpec.

Waspalloy
IN 625
IN 903
A 286
Haynes 188
Rene 41
Hastalloy X
MAR M 246

MAR M 246
MAR M 246
PWA 1480
CM-SX2 Std
CM-SX2-CM
CM-SX4-C
RR2000
IN 713 LC
IN 718
IN 718

AF 56
N-5
N4
SC180
SR99
Rene N4
Key:

Hydrogen
Pressure
(MPa)
3.45
48.3
48.3
34.5
48.3
34.5
48.3
34.5
34.5
41.4
3.45
3.45
48.3
34.5
51.3
34.5
42.7
48.3
34.5
34.5
48.3
34.5
34.0
34.5
34.5
34.0
34.5
34.5
34.0
34.5
34.0
34.5
34.0
48.3
48.3
34.5
34.5
34.5
34.5
34.5
34.5
34.5
34.5
34.5
34.0
34.0
34.0
34.0
34.0
34.5
34.5

RatioH2:He
Notched
UTS
0.64(a)
0.77(b)
0.98(c)
0.78(b)
1.01(c)
0.98(c)
1.00(c)
0.88(c)
0.98(c)
0.87(c)
0.88(c)
0.33(b)
0.24(b)
0.60(b)
0.18
0.84(b)
0.49(c)
0.49
0.29(b)
0.29(b)
0.17
0.35(c)
0.36
0.54(b)
0.47
0.83(b)
0.54
0.59
0.86
0.7
0.57
0.86
0.71
0.76
0.77
0.84
0.84
0.46
0.30
0.25
0.44(b)
0.46(c)

RatioH2:HeUnnotched
RofA
0.45
0.74
0.48
0.37
0.98
1.15
0.93
0.99
0.60
0.17
1.00
0.55
0.61
0.80
0.40
0.40
0.30
0.69
0.74
0.52
0.17
0.17
0.81
0.38
0.76
0.31
0.37
0.67
0.62
0.54
0.78
0.34
0.39
0.62
0.49
0.48

Comments

Wrought
Wrought
Wrought
Wrought
Wrought
Wrought

Conventionally Cast
Directionally
Solidified
Single Crystal
Cast
Cast
Single Crystal
Cast
Single Crystal
Cast
Single Crystal
Cast
Single Crystal
Conventionally Cast
Cast
Wrought RB
F
P
RB
F
P
RB
F
P
Single Crystal
Single Crystal
Single Crystal
Single Crystal
Single Crystal
Cast

(a)Kt=8.4;(b)Kt=6.3;(c)Kt=8.0.;
SA2:NASAHeatTreatment;[ST:940C+A:718Cto621C];
STA2:NASAHeatTreatment;[ST:940C+A:816Cto649C];
R.B:Rolledbar;F:Forging;P:Plate;
STA1:NASAHeatTreatment;[ST:1052C+A:760Cto649C]usedforSpaceShuttleMainEngine.

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48.7.4.2

Directionally solidified (DS) alloys

Table 48.7.4 compares the effect of hydrogen on directionally solidified MARM246 (DS) with its
conventionallycast(CC)equivalent,forvarioustestandsurfaceconditions,Ref.[4818].

Table48.74EffectofhydrogenonMARM246superalloys

(C)

RatioH2:He

RatioH2:He

Temp

Unnotched

Unnotched
UTS

NotchedUTS

RofA

Comments

ConventionallyCast
RT

0.75

0.89

After 870C/8 hr at 34.5 MPa H2 or


He. Tested in air.

0.71

After 870C/8 hr at 34.5 MPa H2 or


He. Tested in air.

DirectionalSolidification
RT

0.97

-73

0.83 [0.68]

24

0.28 [0.37]

149

0.45 [0.71]

RT
RT

0.76
0.65

[0.47]
0.28
[0.29]
0
[0.17]
0.57
0.20

RT

0.86

0.62

Key:

After 538C/12hr at 34.5 MPa


H2 Tested in H2 (or He).

As ground 32 rms
32 rms + 871C/8h stress relief.
Oxidised stress relief + glass bead
hone.
Tested in 34.5 MPa H2.

ValuesinbracketsarefornoH2precharging,butsametestenvironment.

48.7.4.3

Single crystal (SC) alloys

Table 48.7.5 shows that the performance of single crystal (SC) alloys in hydrogen is influenced by
crystalorientation,Ref.[4819].

Table48.75EffectofcrystalanisotropyonRThydrogenperformanceofPWA
1480singlecrystalalloy
Crystalorientation

<001>
<013>
<012>
<123>
<223>
<110>
<111>

RatioH2:He
NotchedUTS

0.57
0.65
0.73
0.74
0.76
0.79
0.88

Hydrogenpressure34.5MPa.Kt=8.0

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48.7.4.4

DSE and ODS alloys

LimiteddataonDSE,ODSandFRSmaterialsaresummarisedinTable48.7.6,Ref.[4818].

Table48.76Effectofhydrogenondirectionallysolidifiedeutectic(DSE)and
oxidedispersionstrengthened(ODS)superalloys
AlloyComposition
or
Specification

RatioH2:He

RatioH2:He

NotchedUTS

UnnotchedRofA

DirectionallySolidifiedEutectic(DSE)Alloy
Ni-45.5W
0.63
Ni-19.7Nb-6Cr-2.5Al
0.60

0.42
0.08

Ni-21.75Nb-2.5Al

0.05

0.64

OxideDispersionStrengthened(ODS)Alloys
MA957: T
0.34
L
0.58
MA6000:
T
0.92
L
0.86
MA754: T
0.94
L
0.96
Key: T : Transverse. L: Longitudinal

0.13
0
0.5
4
0.27
0.19

Comments

RT in 34.5 MPa H2 or He.


Experience severe degradation.
Extreme levels of secondary
surface cracking plus fibre/matrix
interfaces.
RT in 34.5 MPa H2 or He.
Combined effects of ODS &
precipitation strengthening
reduce HEE susceptibility; but no
significant benefits over current
materials.

48.7.4.5

Composites

Ashortstudyofasuperalloycomposite,Ref.[4818],hasshownthat:

Notched tensile values are largely unaffected at medium H2 pressures and lower notch factors (less
severe).

Matrix shields fibres from H2 degradation.

Fibres act as 'barriers' to transverse, planar crack propagation in matrix.

48.7.5

Creep in hydrogen environments

48.7.5.1

General

To date, available data on creep performance in hydrogen are limited because the relatively short
design lives of current rocket engines largely avoid creep phenomena. Creep characteristics are of
importanceforlonglife,reusablevehicleconcepts.
Preliminarystudiesindicatethat:

Lifereductionsinhighpressurehydrogenaregenerallynotsevere.

Creepductilitycanbeslightlyaffected,butarewithinthescatterbandsforinertenvironment
testing.

Increasedcreepstrainrateresultsinareductioninthetimetorupture.

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48.7.5.2

Creep-rupture

Theeffectofhydrogenonthecreeprupture(LarsonMillertypecurve)behaviourofvariousalloysare
summarisedin,Ref.[4818]:

Figure 48.7.1 and Figure 48.7.2 shows the effect of heat treatment on Inconel 718. STA are
standardheattreatmentsforSpaceShuttleengineparts.

Figure48.7.3forInconel625.

Figure48.7.4forWaspalloy.

TheeffectsofprocessingonMARM246alloyoncreeprupturearesummarisedin,Ref.[4818]:

Figure48.7.5forconventionallycast.

Figure48.7.6fordirectionallysolidified.

Figure48.7.7forsinglecrystal.

Hydrogen pressure: 34.5 MPa.

Figure48.71EffectofhydrogenoncreepruptureofInconel718STA2

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Hydrogen pressure: 34.5 MPa.

Figure48.72EffectofhydrogenoncreepruptureofInconel718STA1

Hydrogen pressure: 34.5 MPa.

Figure48.73EffectofhydrogenoncreepruptureofInconel625

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Hydrogen pressure: 34.5 MPa.

Figure48.74EffectofhydrogenoncreepruptureofWaspalloy

Hydrogen pressure: 34.5 MPa.

Figure48.75EffectofhydrogenoncreepruptureofMARM246conventionally
cast

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Hydrogen pressure: 34.5 MPa.

Figure48.76EffectofhydrogenoncreepruptureofMARM246directionally
solidified

Hydrogen pressure: 34.5 MPa.

Figure48.77EffectofhydrogenoncreepruptureofMARM246singlecrystal

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48.7.6

Fatigue in hydrogen environments

48.7.6.1

Low cycle fatigue (LCF)

Ingeneral,alloysexhibitinglowsensitivitytohighpressurehydrogenintensiletestingshowsimilar
levelsofreductiontoLCFinHEE.
Figure48.7.8showsthemaximumlifereductionoccursat~RTforIN718,Ref.[4818].
Table48.7.7summarisesLCFstudiesonotheralloys,Ref.[4818].

Hydrogen pressure: 34.5 MPa. 2% strain rate.

Figure48.78Lowcyclefatigue(LCF)lifeofInconel718againsttemperature

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Table48.77Lowcyclefatigue(LCF)lifedegradationofsuperalloysinhydrogen
environments
Alloy

Condition

Inconel 718

STA2

Inconel 718
Inconel 625
Hastelloy X
Waspalloy
IN 100
Haynes 188

STA 1
-

A286

DSMAR M
200
DSMAR M
246

CCMAR 246

Testtemperature,(C)
25
677
-162
677
25
25
677
677
677
25
677
677

Strainrange,(%)
2
2
2
1
2
2
1.8
1
1.5
2
2
1

LCFlifeloss,(%)
67
20
-75
5
88
-100
50
69
33
0
0
-400

760
871
750
871(a)

2
2
0.5
0.5

8
-87
14
62

Key:

(a);loadcontrol;H2Pressure34.5(MPa).

STA1&2:NASAHeattreatmentsusedforSpaceShuttleMainEngineparts.

48.7.6.2

High cycle fatigue (HCF)

Todate,studiesonHCFhavebeeninconclusive.Indicationsarethat:

Crack propagation is affected if hydrogen penetrates to the crack tip.

High mean stress fatigueismoststronglyaffected.

48.7.7

Fracture characteristics

Hydrogenenvironmentinfluencesthefracturecharacteristics,including:

Threshold stress intensity.

Crack propagation rate.

Figure48.7.9showstheeffectofstressintensityoncrackgrowthratesofIN718invarioushydrogen
environments,Ref.[4818].
In Figure 48.7.10 the crack growth rates of IN718 are related to cycle rates in various hydrogen
environments,Ref.[4818].

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Conditions
Helium
Hydrogen

Pressure (MPa)
34.5
0.69
34.5
68.9

Temperature
RT

Figure48.79Superalloys:CrackgrowthrateofIN718undervariousstress
intensitiesandhydrogenenvironments

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Conditions
Stress Intensity
Hydrogen
Temperature

54.7 (MPa)
68.9 (MPa)
RT

Figure48.710Superalloys:CrackgrowthrateofIN718asafunctionofcyclic
ratesandhydrogenenvironments

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48.8 Effect of oxygen


48.8.1

Material selection factors

Factorsassociatedwithmaterialselectioninclude:

oxidationresistance,

effectofoxygendiffusionintothematerial,

ignitionandburnresistance.

[Seealso:Chapter85]

48.8.2

Oxidation

Theprimeconcernsofoxidationarethatit:

reducesthecomponentloadbearingcrosssectionalarea,and

introducessourcesofstressconcentrations,detrimentaltofatigueresistance.

Themechanismsinvolvedare:

surfacescaling

internaloxidation

oxidespalling

oxidevaporisation

Oxidationresistanceislargelydictatedby:

materialcomposition,and

the ability to form an adherent, stable, oxide layer throughout its range of operating
temperaturesandenvironments,e.g.oxidative,reducing.

48.8.3

Oxidation resistance

48.8.3.1

Conventional alloys

TheoxidationresistanceisprovidedbytheCrandAlpresent,plusTaforNiandCobasedalloys,at
temperaturesupto~900C,bytheformationofadenseCr2O3layer.
At temperatures above 1000C, the oxide morphology changes to the more volatile CrO3 with an
accompanyinglossofprotection,andalsocausingpreferentialoxidationatcarbidelines.
For high temperatures, the formation of Al2O3 gives added resistance, but this has poor adherence
unlessY,HforZrispresentinthebasealloycomposition,Ref.[489].

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48.8.3.2

High temperature alloys

Forthosealloysparticularlydevelopedtoenhancemechanicalperformance(creepresistance)atvery
hightemperatures,i.e.to~1200C,thelevelsofCrandAlpresentincompositionsaregenerallytoo
low to provide sufficient oxidation resistance alone. Under these conditions the use of a protective
coatingisadvisable.

[See:48.9;Chapter74]

48.8.4

Ignition and burn

48.8.4.1

General

Undercertainconditionsofoxygentemperatureandpressure,mostmaterialsifimpactedorscuffed
can ignite and sustain burning. This characteristic is most important in applications involving
rotationalmachineryinwarmgaseousO2environments,oftenatveryhighO2pressures,e.g.oxygen
turbopumps.

48.8.4.2

Ignition hazards

Ignitionhazardscanbeclassifiedas,Ref.[4820]:

Mechanical rubbing (e.g. turbine tips, bearings), caused by:

Thermalexpansionandcreep

Enginestartupandshutdowntransients

Tribologyofdifferentmaterials

Debris impact of foreign materials

48.8.4.3

Material sensitivity

Nickel and copper offer the best impact and burn resistance, as shown in Table 48.8.1, which ranks
materials on their calculated Burn Factor. This ranking has been confirmed by experiment under
highpressureoxygen,Ref.[4820].

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Table48.81Ignitionandburncharacteristicsofmaterialsinoxygen
environments
Material

Ranking

Zirconium Copper
Nickel 200
Silicon Carbide
Monel 400
K Monel 500
Inconel 600
316 Stainless Steel
Invar 36
Hastelloy X

Best

Worst

Key: Calculated Burn Factor, BF:


where:
0

BF H f

heat of oxidation
thermal diffusivity

48.9 Coatings and protection systems


48.9.1

Requirements

Oftenhighmechanicalperformancecannotbeachievedathightemperatures,becausesuperalloysdo
not have sufficient levels of Al or Cr in their chemical compositions to form and maintain a stable
oxidescale,[See:48.8].
For applications such as firststage blades and vanes in gas turbine engines, a coating is normally
appliedtoimprovetheiroxidationandcorrosionresistance,Ref.[4824].
Theobjectiveofsuchcoatingsistoprovideabarrierbetweentheenvironmentandthecomponent,in
termsof:

longterm stability with respect to the oxidation and corrosion environment, but also against
interdiffusionwiththesubstratealloy.

resistancetothermalcyclingandthermalshock.

loadbearingcapability.

[Seealso:Chapter74]

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48.9.2

Types of coatings

Numerous types of coatings have been developed to combat aggressive environments. The work
continues as demands for improved engine efficiency through higher operating temperatures, and
higherthrustaremade.Ingeneralcoatingscanbedescribedaseither:

Metallic: alloys capable of forming and maintaining stable oxide scales (usually Al2O3) under
serviceconditions

Ceramics:oxidesormixturesofstableoxides.

Themethodsofapplyingcoatingsalsodescribespecificcoatingtypesandaregroupedaseither:

Diffusion,wherealloysurfacecompositionsareenrichedinAl,CrorSiorwherenativeoxides
aremanipulatedthroughthermodynamicprinciplestoformmorestabletypes;[See:48.10].

Overlay, where either a metallic or ceramic layer is deposited onto the component surfaces,
[See:48.11].

In regions where components experience high heat fluxes or intense gas wash, the application of a
ceramiclayer(havinglowthermalconductivityandhighmeltingpoint)canpreventoverheatingand
erosion.ThesearecalledThermalbarriercoatings(TBCs),andareessentiallythickerceramicoverlay
coatings,[See:48.12].

48.9.3

Coating systems

Variouscoatingsystemshavebeendevelopedtocombatoxidationandcorrosionorhighheatfluxes.
Manyarecommercialproductsandhavedemonstratedtheirperformanceinaircraftengines.

48.9.4

Coated components

Acoatedcomponentbecomesacomplexmaterialsystem:

Coating+Interface+Substrate

It requires knowledge of mechanical performance and chemical effects (such as diffusion kinetics)
whenexposedtothermalcyclingforextendedperiods.
If a component is to be coated, the design has to fully consider the effect the coating has on the
substratematerialproperties;inboththelongandshortterm,[See:48.13].

48.9.5

Hydrogen fuel

Forspaceenginesusinghydrogenfuel,itisgenerallyperceivedthatcoatingswhichpreventhydrogen
transport into the material are of benefit in reducing (or avoiding) the effects of hydrogen
embrittlement.Suchcoatingsareeither:

Barrier,topreventhydrogentransport,or

Catalytic,todiscouragedissociationandencourageassociation.

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However,owingtothekineticsofhydrogendiffusion,bothtypesofcoatingsneedtobecontinuousat
all times. With one imperfection, hydrogen can enter the material substrate and then is prevented
fromdiffusingoutbyregionsofintactcoating.Consequentlymoredamagecanresultbytheuseofa
coating,especiallyascoatingintegrityisdifficulttoinspect,Ref.[4817].

48.10 Diffusion coatings


48.10.1 Types of coatings
Somedifferenttypesofdiffusioncoatingscanbeobtainedby:

Chromising

Aluminising

PlatinumAluminide

SelectiveOxidation

Silicide

ModifiedNativeOxides

Theirselectiondependson:

substratealloys,and

serviceconditions

Table48.10.1summarisesthevarioustypesofdiffusioncoatingsalongwiththeirusesandlimitations,
Ref. [4825], [4826], [4827]. All have been developed to enhance the oxidation and corrosion
resistanceofsuperalloys(notablyNibased)forgasturbineapplications.
CommerciallyavailabletypesaregiveninTable48.10.2,Ref.[4825].

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Table48.101Diffusioncoatingsforsuperalloys:Varioustypesanduse
Coating
Chromising
Diffusion of Cr into substrate
forming chromium oxide on
exposure.

Application
Low alloy steels in
industrial & marine gas
turbines.

Selective oxidation
Controlled oxidation of
substrate to form more stable
oxides.

Limitations

Comments

Resistance to low
temperature sulphidation
corrosion.
Temperature range 973 to
1023K.

Chromia scales worse than


alumina scales at >1123K in high
velocity gas-streams.

Owing to volatility of
chromium oxide.

Inexpensive.
Easy to apply and strip
during overhaul.
Proprietary coating media
'Packs' available.
Ability to form & replenish
Al203 scale.

Used where metal


temperatures/environment not
severe.
Brittle.
In exacting conditions, coating
may crack due to rapid thermal
cycling & allow substrate
corrosion.
Poor thermal fatigue.

Extensively used
satisfying ~90% of
applications.
High DuctileBrittle
transition temperature.
Coating thickness 50m
typ.

As above.

Proprietary coating media


'Packs' available.
Extensive aero-engine
service.
Good high temperature hot
corrosion (Type I) resistance.

Susceptible to low temperature hot


corrosion. (Type II)

Platinum deposited prior


to aluminising.

Superalloys with
sufficient levels of Cr &
Al.

Controlled oxidation of
substrate.
No second phase added to
surface.

Modest oxidation-corrosion
resistance.
Poor Adhesion.
Seldom solely Al2O3 formed (due
to substrate).

Not appropriate for high


temperature applications
(oxide stability).

Aluminising : Low and high activity pack


Diffusion of Al into substrate
Ni-based & Co-based
forming NiAl coat (Ni-based
super-alloys in aerosubstrate) or CoAl coat (Coengines (industrial/
based substrate). Forming
marine gas turbines).
Al2O3 on exposure.

Platinum aluminide
Diffusion as above of Pt into
coating & substrate.
Exact coat composition depends
on proprietary process.

Benefits

Silicide

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Coating
Diffusion of Si into substrate
forming Al-Si, Ni-Cr-Si, Ni-CrAl-Si compounds forming SiO2
on exposure.
Amorphous SiO2 layer (<10
m).
Modified native oxides
See: Selective oxidation

Application

Benefits

Limitations

Comments

Industrial & Marine Gas


Turbine blades.
Ni- & Co-based
superalloys.
Ni-based superalloy.

Resistant to vanadiumcontaining fuels.


Decay to Al2O3 stable oxide.

Brittle.
Low melting point.
Low thermal shock resistance.
Rapid diffusion between coat &
substrate.
Experimental study (in static air).

Not appropriate for high


temperature
applications.
Need further study for
in-service environment.

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Table48.102Diffusioncoatings:Commerciallyavailabletypes
Coatingtype

Aluminide

PlatinumAluminide

Key:

Designation

Supplier

Codep B
RPS320
PWA273
LDC-2

Rolls Royce plc


Pratt & Witney Aircraft Co
Deutch Edelstahlwerke
Akteingesellschaft
Chromalloy
Howmet Thermatech Div.
Johnson Matthey

RT22
LDC-2E
JML1
USAsource.

48.11 Overlay coatings


48.11.1 Development
48.11.1.1 General
Metalliccoatingsystemsweredevelopedtoimproveoxidationandcorrosionresistanceofsuperalloys
at high temperatures to generally overcome the brittleness of diffusion type coatings. Their
developmentisstronglylinkedtomethodsenablingeffectivedepositionofalloys.

48.11.1.2 Metallic coatings


ThemetalliccoatingsarebasedontheMCrAlYformulation,where:

M = Nickel and/or Cobalt and/or Fe.

Chromium: >20 wt% typ. for corrosion resistance.

Aluminium: >6 wt% typ. high temp oxidation resistance.

Yttrium: <1 wt% typ. to promoteoxideadherence.

Ironbasedcoatingsarenotappropriateforgasturbineuse.

48.11.1.3 Coating formulation


Theprecisecoatingformulationcanbeadjustedwithrespectto:

Substratealloycomposition.

Operatingthermalregimes.

Operatingcorrosivespecies.

As a consequence, a wide variety of formulations have been developed and are commercially
available,asshowninTable48.11.1,Ref.[4828].

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Table48.111CommerciallyavailableMCrAlYoverlaycoatings
CoatingComposition
(wt.%)

Co-18Cr-8Al-0.5Y
Co-18Cr-11Al-O.3Y
Co-19Cr-10Al-0.5Y
Co-23Cr-12Al-0.3Y
Co-23Cr-13Al-0.6Y
Co-30Cr-5Al-0.5Y
Co-32Ni-21Cr-7.5Al-0.5Y
Co-32Ni-21Cr-8Al-o.5Y
Co-23Ni-30Cr-3Al-0.5Y
Co-10Ni-25Cr-7Al-0.6Y-5Ta
Ni-17Cr-6Al-0.5Y
Ni-22Cr-10Al-1.0Y
Ni-25Cr-12Al-0.3Y
Ni-25Cr-5Al-0.4Y
Ni-38Cr-11Al-0.3Y
Ni-22Co-18Cr-12Al-0.3Y
Ni-20Co-42Cr-5Al-0.3Y
Ni-22Co-21Cr-7.5Al-0.5Y
Ni-23Co-20Cr-8.5Al-0.6Y-4Ta
Ni-0.5Co-20Cr-11Al-0.5Y0.5Mo
Fe-24Cr-8Al-0.4Y
Fe-24Cr-11Al-0.6Y

Designation

Company

Application
Method

LCO29
ATD5
LOC5
ATD2
LCO7
ATD14
LCO22
Amdry 995
LCO37
Amdry 996
Amdry 961
Amdry 962
ATD16
Amdry 963
ATD1
ATD7
ATD9
LN21
Amdry 997
LN34

Union Carbide
Airco Temescal
Union Carbide
Airco Temescal
Union Carbide
Airco Temescal
Union Carbide
Alloy Metal
Union Carbide
Alloy Metals
Alloy Metals
Alloy Metals
Airco Temescal
Alloy Metals
Airco Temescal
Airco Temescal
Airco Temescal
Union Carbide
Alloy Metals
Union Carbide

PS(argon)
EB-PVD
PS(argon)
EB-PVD
PS(argon)
EB-PVD
PS(argon)
LPPS
PS(argon)
LPPS
LPPS
LPPS
EB-PVD
LPPS
EB-PVD
EB-PVD
EB-PVD
PS(argon)
LPPS
PS(argon)

Amdry 970
ATD8

Alloy Metals
Airco Temescal

LPPS
EB-PVD

Key:

PS(argon)PlasmaSpray,underargon.

EBPVDElectronBeamPhysicalVapourDeposition.

LPPSLowPressurePlasmaSpray.

Later work has concentrated on additions of Tantalum and Hafnium to further enhance coating
performanceonsuperalloys;asshowninTable48.11.2alongwithcoatingrecipeandsubstratealloy.

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Table48.112Overlaycoatings:LaterstudieswithMCrAlYtypecoatingsand
superalloyssubstrates
CoatingComposition(wt.%)
Ni-l7Cr-12Al-O.4Y
Ni-23Co-18Cr-13Al-0.6Y
CoCrAlY + 4.5 or 3Ta
NiCoCrAlYTa
NiCoCrAlTa

U700
IN 100
MAR M 002
CMSX2

Application
Method
PVD
LPPS
LPPS
PS
LPPS

Ref. [48-31]

MA 6000

LPPS

Ref. [48-31]

CMSX2

LPPS

Ref. [48-32]
Ref. [48-32]
Bond coat for TBC, Ref.

Substrate
B1900 + Hf

Ni-23Co-20Cr-8.5Al-4Ta-0.6Y
Co-10Ni-25Cr-7Al-5Ta-0.6Y

IN 100

LPPS

Hastelloy X

ED

NiCoCrAlYTa

CMSX2
Cotac 784

LPPS
PS(Vac)

NiCrAlY

IN713LC

PS(p.p)

X40

PS(p.p)

NiCoCrAlY
(PWA276)

PWA 1480

LPPS

PWA286

Alloy 185

NiCrAlHf

Rene 80

Laser(RS)

NiCrAlYTa

NiCoCrAlYTa

Comments
Ref. [48-29]
Ref. [48-30]

[48-33]
Ref. [48-34]
Ref. [48-35]
Ref. [48-36]
Ref. [48-36]

Pratt & Whitney


Aircraft Co.
designations
Ref. [48-37]
Increased Hf content in
solid solution. Ref.

[48-38]

Key:

PVD:PhysicalVapourDeposition

PS(vac):PlasmaSpray,undervacuum

LPPS:LowPressurePlasmaSpray

PS(p.p.):PlasmaSpray,partialpressure

PS:PlasmaSpray

Laser(RS):Laser(RapidSolidification)

ED:ElectrophoreticDeposition

TBC:ThermalBarrierCoating

48.12 Thermal barrier coatings (TBC)


48.12.1 Function
The objective of thermal barrier coatings (TBCs) is to provide protection to selected regions of
componentsexperiencinghighheatfluxesorintensegaswash,suchas:

combustionchambers

nozzleguidevanes

rotorblades.

Allovercoatingsarepronetocrackingandspalling.

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48.12.2 Coating construction


TBCsnormallycompriseofthreelayers,asshowninFigure48.12.1.

Ceramic
Bond coat

~0.4 mm thick, typically


usually MCrAlY-type metallic Overlay coating

Substrate superalloy

Figure48.121Thermalbarriercoating:Typicalconstructionmaterials

Table48.12.1summarisesthetypesofmaterialsystems,includingtheirattributesandproblems,Ref.
[4825],[4839].
The development is ongoing, so Table 48.12.2 presents a summary of later work which is aimed at
optimisingtheirperformance.

Table48.121Thermalbarriercoatings:Materialsystems
Ceramiclayer

Zirconia, commonly with Magnesia


and Yttria additions to partially
stabilise,
Zirconia has a high melting point and
low thermal conductivity.
Porous, hence permeable to oxygen
and corrosive species,
As-deposited coatings have uneven
stress state. Annealing heat
treatment,
Key:

Bondcoatlayer

To accommodate thermal strains


between substrate and ceramic
layer,
Act as mechanical key for ceramic
layer,
Act as impermeable layer between
porous ceramic and substrate.
Oxidation corrosion of bond coat
due to permeable ceramic layer.

FullystabilisedZirconiahaspoorthermalshockperformance.

Averyroughceramic/bondcoatinterfacemaycauseahigherstressstateintheceramic
leadingtoprematurefailurebycrackingadjacenttotheinterface.
AnnealingmaycauseaslightincreaseinThermalConductivity,dependingonceramic
composition.
DifferencesinCTEbetweenthebondcoatandceramictendtocausecrackingadjacenttotheir
interface.
Crackingallowsaccommodationofthermalfatiguestresses.

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Table48.122Thermalbarriercoatingtechnology:Laterstudies
Ceramiclayer
composition

Bondcoat
composition

[Application
method]

[Application
method]

Substrate
alloy

ZrO2+8Y2O3
[PS]

NiCrAlYTa
[EP + Aluminising]

Hastalloy
X

ZrO2+CaO,
MgO,Y2O3
additions
[PS]

NiCrAl
[PS]

IN 100

ZrO2-6Y2O3
[-]

NiCrAl
[-]

Superalloy

NiCrAlYb
ZrO2-6Y2O3
[PS]

CoCrAlYb
CoCrAlY
FeCrAlYb
FeCrAlY
[PS]

MAR M
200+Hf
MAR M
509
Fe-22Cr5.8Al0.5Co

Comments
Bond coat is cellular.
Improved thermal shock.
Cells act as crack stoppers.
Carbide layer at Bond Coat/ Substrate
interface due to C-content of Hastelloy.
Bond coat: 200m.
Ceramic: 300m, Ref. [48-33].
Bond coat: 0.1mm.
Ceramic: 0.4mm.
ZrO2+7Y2O3 gave best thermal cycling
resistance, Ref. [48-39].
Finite Element Modelling of coating
mechanical performance.
Stress State Model, Ref. [48-40].
Effect of Yb additions on diffusion
mechanisms on bond coat.
Morphology of oxide(s) on bond coat.
Thermal cycling resistance, Ref. [4841].

Key:PSPlasmaspraying;EPElectrophoreticdeposition

48.13 Coating influence on design


48.13.1 Factors
48.13.1.1 General
Inrecommendingtheuseofacoating,thereareasignificantnumberoffactorstobeevaluatedwith
respect to the particular material system, i.e. coating(s) and substrate alloy, for a given service
environment.
Many coatingsubstrate alloy systems have been the subject of intense metallurgical examination.
Althoughfundamentaltotheunderstandingofhowvarioussystemsinteract,detailedinformationis
notgivenhere.

48.13.1.2 Technical
Table48.13.1summarisesthefactorsassociatedforcoatingsystemsofferingoxidationandcorrosion
resistance,Ref.[4834].
Table48.13.2comparestechnicalaspectsofdiffusionandoverlaycoatings.

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Table48.131Coatingdesign:Factorsassociatedwithcoatingsystemsfor
oxidationandcorrosionresistance
Coating
property

Location
Requirements

Operating environment is known:


- temperature(s)
- corrosive species
- erosive species
- design life
Oxidation/ Low rates of scale formation
Corrosion Uniform surface attack
resistance Stable surface oxide
(thermodynamically)
Ductile surface scales
Adherent surface scales
High concentration of scale forming
elements in coating (self-repairing)
Low rate of diffusion across
interface at service temperatures
Interface
Limited compositional changes
stability
across interface
Avoidance of brittle phase
formation in service
Matched coating to substrate
properties to reduce stresses at
interface
Good
Optimised surface condition prior to
adhesion
coating
Minimise stress during coating
process
Coatings should withstand service
loading:
- creep
- fatigue
- impact
Mechanical - thermally induced
Well matched coefficient of thermal
strength
expansion
Coating does not adversely affect
component performance
Coating heat treatments does not
affect component heat-treatments
Key:

Coating
surface

Coating
bulk

C:S
Interface

X
X
X
X
X
X
X

X
X

X
X
X

X
X
X
X
X

X
X
X

CCoating;SSubstrate.

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Table48.132Coatingdesign:Comparisonoftechnicalfactorsfordiffusionand
overlaycoatings
Diffusioncoatings
Environmentalresistance
Chromising:
Forming Cr oxide surface. Corrosion
resistance to sulphates at temperatures
<1123K (high velocity gas streams).
Aluminising:
Formation of NiAl or CoAl in Ni-base & Cobase superalloy respectively. Forming
Al2O3 surface scales. Temperatures
<1100C; not too corrosive. Prone to
thermal fatigue cracking.

Modified aluminides:
>1100C. Improved thermal fatigue.

Overlaycoatings(MCrAlYTypes)
Contain ~7wt% Al to form Al2O3.
Increase Cr content to combat hot corrosion
(sulphate contamination).
Too high Cr or Si content (used to combat
Type II hot corrosion) may affect diffusional
stability of C:S interface at high
temperatures.
Cr oxide provides oxidation resistance up to
~900C.
Al oxide provides oxidation resistance up to
~1200C.
Al oxide-scales are not adherent when
thermally cycled. add Y.
Presence of Cr to combat acid or basic fluxing
mechanisms (Type I & Type II hot corrosion).

Chemicalcompatibility(Interfacestability/Adhesion)
Interdiffusion effects between coating/
Interdiffusion across interface Al
substrate lowers oxidation resistance of
Substrate; Ni Coating, depending on
coating, notably Ti.
alloy composition.
Diffusionally stable systems are: NiCrAlY on
Ni-base or Fe-base substrates, CoCrAY on Febase.
Unstable systems are: CoCrAlY on Ni-base,
FeCrAlY on Ni-base or Fe-base.
Mechanical strength
Aluminide CTE < substrate at high temps
Ductile Brittle transition temperature >
600C typical.
Complex structure, difficult to determine
intrinsic properties.

Carbide interface forming for MCrAlY on Cobase (less for CoCrAlY) (preferential oxidation
path &/or spalling of coating).
CTE difference should not exceed 2 x 10-4 /K.
DuctileBrittle transition temp increases
with increasing Al content (100 to 600C).
Some compositions exhibit superplasticity.

48.13.1.3 Economic
Inadditiontotechnicalfactors,theeconomicfactorstobeconsideredinclude:

availabilityandcostofcoatingmaterials.

availability and cost of coating equipment, including temperaturetime (energy) demands per
batchsize.

subsequentheattreatments:

densificationofcoating,

recoveryofsubstratealloymechanicalproperties.

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48.13.2 Effect of coatings on mechanical properties


The combination of a coating and a substrate alloy becomes a complex material with each part
optimisedforaparticularfunction:

Coating:environmentalresistance,

Interface:maintaincoatingadherenceandminimiseinterdiffusioneffects,

Substrate:hightemperaturemechanicalperformance.

Consequentlyeachpartpossessesdifferent:

chemicalcompositions,

metallurgicalstructures,

bulkproperties,suchas:

stiffness

strength

creepresistance

fatigueresistance

thermalproperties,e.g.CTE,thermalconductivity.

The mismatch in properties causes coatingsubstrate interactions which can influence the overall
properties of the component. Operation at high temperatures causes compositional changes
(diffusion)whichinturncausestheinitialpropertiestochangethroughouttheservicelife.Coatings
andsubstratealloysshouldbeevaluatedtogether,notasindependentquantities.
Theoverallmechanicalperformanceofthecoatedmaterialsystemisaffectedby:

environmentalconditionsexperienced(duringtestingorinservice)and,

coatingapplicationmethod.

48.13.3 Chemical interaction


48.13.3.1 Oxidation
Oxidation reduces the Al content of coatings due to the formation of Al2O3 surface scales. This can
increasetheductilityofthecoatingwithincreasingtimeinservice.

48.13.3.2 Diffusion
Higher chromium and aluminium contents (in hot corrosion resistant coatings) than the substrate
alloy results in increasing Al and Cr in the interdiffusion zone, causing the formation of brittle
phases. Diffusion can also lead to Kirkendall voids, giving porosity near the coatingtosubstrate
interface.Theseporescanactascrackinitiationsitesandgiverisetodebondingofthecoating.
In uncooled components, the interdiffusion zone can be small compared with the overall material
thickness.Increasingtemperatureincreasestheinterdiffusionzone.

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Inacooledcomponent,thethinwallsofsubstratealloycanbecometheentireinterdiffusionzone,i.e.
thewholematerialcompositionischanged,hencemechanicalpropertiesarealtered.
Temperature gradients reduce diffusion penetration depths. This effect is summarised in Figure
48.13.1,Ref.[4844].
Atgrainboundariesdiffusionofcoatingelementscanbesignificantlyenhanced;penetrationisgreater
thanexpectedfrombulkdiffusioncalculations.

Diffusion of Al in a Ni-based alloy.


Surface temperature: 1400K
D0 = 1.0 cm 2/s
Diffusion time: 30 000 hours
E = 250 kJ/mol

Figure48.131Coatingdesign:Effectoftemperaturegradientsondiffusion

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48.13.4 Residual strains


48.13.4.1 Property mismatch
Mismatch of physical or mechanical properties between coating and substrate causes residual or
additional strains which promote premature cracking and spalling of the coating; causing a loss of
protection.
Coatingcracksalsoactasinitiationandpropagationsitesforsubstratecracksduringfatigueorcreep
loading.Therelevantpropertiesare,Ref.[4844]:

Modulus(E)

Coefficientofthermalexpansion(CTE)

Thermalconductivity

Yieldstress

Fracturestrainandtoughness

Creepandrelaxationbehaviour.

TheinitialstressstatecanbeapproximatedbyEandCTEdifferencesincoatingandsubstrateduring
processing,basedontheprocessingtemperature.Ahypotheticaltemperaturecanbedeterminedfora
stressfreestate.
Itisassumedthat:

Diffusion or Annealing
Heat Treatment Temperature

<

Deposition
Temperature

<

Service
Temperature

Residualstrainsandstressescanbecalculatedby:

Erc T

[48.131]

rc

Ec XT
1

[48.132]

48.13.4.2 Thermal expansion


Residual strain is at a maximum near the coatingsubstrate interface. If differences in CTE are too
large,coatingscancrackduringcoolingafterdeposition.Theseeffectscanbereducedbyminimising
CTEdifferencesto~2x106/K.
Where CTE (coat) < CTE(substrate), such as TBC ceramics, the coating has residual compressive
stressesandstrains.
PartiallystabilisingZrO2(usingMgO,CaO,Y2O3)reduces:

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volumetricphasetransformations,and

minimisesresidualstresses.

Theprocessingtemperatureischosentobeaslowaspossible.
Internalstressescanreachfrom200MPato450MPaowingtoCTEmismatch,causingdebondingof
coatingswhichinturnarelocalhotspots.

48.13.4.3 Processing
Nonisothermal(spray)processesincreaseresidualstressesby:

Contractionofdropletsonsurfaces

Phasetransformations

Tocounteracttheseeffects,adjustthecoatingcoolingprocessesorpreheatthesubstrate.
Themoduluscanbeanisotropicduetoprocessparameters.Forbrittlecoatings,ductilityisdependent
oncoatingthickness.
Compressivestressescanbegeneratedasaresultoflateralgrowthofthecoating.

48.13.4.4 Ductile Brittle transition temperature


The strains need considering with respect to the ductile brittle transition temperatures (DBTT) of
coatings.Ifacoatingexperiencestoohigherstrainwhilstitisbrittle,cracksresultwhereasstrainscan
beaccommodatedwithoutfracturewhencoatingsareabovetheirDBTT.

48.13.5 Tensile behaviour


48.13.5.1 General
Coated components can be treated like composite materials; using the Rule of Mixtures, an
approximation of modulus and strength of the material system (coat and substrate) can be made.
Becausecoatingthicknessesareusuallysmallcomparedwiththatofthesubstrate,e.g.0.1to0.3mm
coatingcomparedwith1to5mmblade;thecoatingsdonothavemuchinfluence,otherthanreducing
theoverallcrosssectionalareaofthesubstratealloy,Ref.[4844].
Loadistransferredfromthesubstratealloytothecoatingbyshearstressesattheinterface:

Shearstressexceedsbondstrength:Thecoatingdetaches.

Bond strength exceeds shear stress: The coating follows the extension of the substrate alloy
until:

HighE,brittlecoating:CrackingoccursbeforetheUTSof thesubstrate.

LowE,ductilecoating:deformsuptoUTSofthesubstrate.

48.13.5.2 Residual stress


Residual stresses or strains affect this behaviour and are added (if tensile) or subtracted (if
compressive).Tensionresultsinprematurecrackformation,theconverseistrueforcompression.

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Table48.13.3providestypicaltensilepropertiesofcoatedCMSX2(SC)andCotac784(DS)alloys,Ref.
[4834].

Table48.133Coatingdesign:Tensilepropertiesofcoatedmaterialsystems
Materialssystem
Coating
[Thickness,m]

None
[-]

Aluminide
(High Activity)
[75m]

Ni-23Co-20Cr8.5Al-4Ta-0.6Y (3)
[100m]

[None]

Ni-23Co-20Cr8.5Al-4Ta-0.6Y
[100m]

Substrat
e(1)

CMSX-2
(SC)

CMSX-2
(SC)

Test
Thermal
history(2)

temp.
(C)

ST:1315C/30
Mins/ACA:10
50C/
16h/AC+
850C/24h/AC
ST + A.
Coat:
700C/7h/?+
diffusion HT
(as for alloy)

CMSX-2
(SC)

ST + A Coat:
PS(vacuum)+
diffusion HT
(1st alloy
ageing
treatment)

Cotac 784
(DS)

ST:1250C/90
min
1180C/AC
A:1050C/16h
r/AC+
850C/24h/AC

Cotac 784
(DS)

ST + A Coat:
PS(vacuum)+
diffusion HT
(lst alloy
ageing
treatment)

RT
850
1050
RT
850
1050

RT
850
1050

Mechanicalproperties
UTS

YS

(MPa)

(MPa)

Elon
g

Comments

(%)
1157
1019
483

1021
860
415

13
-

1049
1044
492

1043
953
417

0.8
25
30

1071
1068
474

1061
967
396

13
26
29

844
366

707
342

8.7
7.7

1228
823
344

786
690
324

9.8
9
10

RT: Coat
fractured at 0.5%
and failed at c:s
interface. At high
temps., no cracks
seen prior to
rupture of test
piece.
-

900
1100

RT
900
1100

RT: Coat
fractured at 0.5%
and failed at c:s
interface. At high
temps., no crack
seen prior to
rupture of test
piece.

Key:(1) SC:Singlecrystal;DSDirectionallysolidified.[001]direction.
(2) ST:Solutiontreatment;A:Ageing;AC:Aircool;PS(vacuum):Plasmasprayundervacuum.
(3) Coatingcomposition+applicationmethodproducessuperplasticity>800C.

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48.13.6 Fatigue resistance


48.13.6.1 General
Forcrackedcoatings,fracturemechanicsdeterminewhetherthecrackdepthissignificanttostimulate
brittlefractureorsubcriticalcrackgrowthduetofatigueorcreepconditions,asshownby:

K1 > K1c instability


K1 >K1.th fatigue
Given certain conditions, the reaction of a substrate alloy to crack depth (coating thickness) can be
determinedfromfailurediagrams;anexampleisshowninFigure48.13.2,Ref.[4844].

Boundaryconditions:850Cfor~200hrandRT.

Figure48.132Coatingdesign:ExampleoffailurediagramforIN738LC

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Table48.13.4showstypicalfatiguepropertiesofcoatedRene80andCMSX2(SC)alloys,Ref.[4835],
[4845].

Table48.134Coatingdesign:Fatiguepropertiesofcoatedmaterialsystems
Materialsystem
Coating

Substrate

Thermalhistory

Test
temp.

Fatiguelife,Nf
Comments

(x103cycles)

(C)
900

286 103

ST + A: not stated
1068C/6h/?
(simulated coat
H.T.)
ST:1315C/30
mins/AC
A:1050C/16hr/AC
+
850/24 hr/AC
Coat: 700C/7 hr/?

900

764 261

870

ST + A as above
Coat: PS
(vacuum) +
diffusion (1st
alloy ageing
temp)

870

Significantly
lowers HCF
resistance. At 107
cycles stress
reduced by 100
MPa. Similar
effect as for
aluminide/CMSX2 combination.
Cracks initiate at
coating-tosubstrate
interface. Cracks
also observed on
surface of
coating. Change
in mechanism
from uncoated,
where cracks
initiate from
internal
micropores of
alloy.

Codep B
(Low
activity
aluminide)

Rene 80

ST + A: not stated
Coat: 1068C/6h/?

Fatigue Test:
90 Hz; R = 0.1
Coating HT
changes microstructure of
substrate
alloy; crack
initiates in
coating,
change in c.s.a.

Rene 80

Aluminide
(high
activity)
[75m]

CMSX-2
(SC)

Ni-23Co20Cr8.5Al-4Ta0.6Y
[100m]

CMSX-2
(SC)

Key:

HT:Heattreatment;c.s.a:Crosssectionalarea;ST:Solutiontreatment;A:Aged;SC:Single
crystal;PS(Vacuum):Plasmasprayinvacuum.

Fatigue Test:
70 Hz;
Load ratio R =
0.95

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48.13.6.2 High cycle fatigue


HCFbehaviourisstronglyinfluencedbycrackinitiationconditions.Factorsinclude,Ref.[4844]:

Fatiguelimitofcoating,

Modulus,

Particlesizewithincoating,

Coatingresidualstress/strains,

Surfaceroughness.

Fatigueinitiationsitesinclude:

Cracks,

Internalporesinsubstrate(notablycastalloys),

Interfacedefects(porosity,brittleprecipitates).

Figure48.13.3showstheeffectofHCFonCoatedCMSX2alloy,Ref.[4834].

Temperature: 870C.

Figure48.133Coatingdesign:HighcyclefatiguecharacteristicsofcoatedCMSX2

48.13.6.3 Low cycle fatigue


LCF behaviour is largely unaffected by coatings, and tends to be similar to the thermal fatigue
response.

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48.13.6.4 Thermal fatigue


Thermalfatigueperformanceislargelydependentupon:

Coating thickness

Ductile Brittletransitiontemperature

CTE mismatch

CoatingswithoptimumthicknessandCTEmismatchabovetheDBTTdonotsignificantlyinfluence
thermalfatiguecharacteristics.

48.13.7 Creep and relaxation


Creepbehaviourofacoatedsystemiscomparedwiththatofthesubstratealloyandseparatecoating
materialinFigure48.13.4andFigure48.13.5,Ref.[4844].

Figure48.134Coatingdesign:Schematiccreepcurvesforsubstratemetaland
coating

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Figure48.135Coatingdesign:Schematiccreepcurvesforcoatedsystem

CoatingswithhighDBTTaremorecreepresistantwithlowercreepductility.However,whensteady
statecreepconditionsareachieved(afterinitialloadattemperature)themorecreepresistantpartis
forcedtocreepfasterthannormal,provokingahigherdamagerate.
Coatingswithfinegrainedstructuresareoftenlesscreepresistantthanthesubstratealloy.Hencethe
alloy creep behaviour predominates. Failure is dictated by the creep ductility of each part of the
materialsystem.
Inpractice,creepbehaviourissensitiveto:

coatingprocess,

heattreatmentduetocoatingprocess,

residualstresses,

crackinitiation(surfaceofcoatsubstrateinterface),

diffusionofcoatintosubstrateespeciallyatgrainboundaries,

reducingeffectivecrosssectionalareaofsubstrate.

differentcreepbehavioursofsubstrateandcoat,especiallyatlowstrains.

Creep rupture characteristics for CMSX2 alloys with various coatings are shown in Figure 48.13.6,
Ref.[4834].
TheeffectofcoatingsonCotac784alloyisshowninFigure48.13.7,Ref.[4834].

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Figure48.136Coatingdesign:Effectofcoatingsonstressrupturepropertiesof
CSMX2alloy

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Figure48.137Coatingdesign:Effectofplasmasprayedcoatingonstressrupture
propertiesofCotac784alloy

Table48.13.5showstypicalcreeppropertiesofRene80,CMSX2(SC)andCotac784(DS)alloys,Ref.
[4835],[4845].

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Table48.135Coatingdesign:Creeppropertiesofcoatedmaterialsystems
Materialsystem
Coating
Codep (low
activity
aluminide)
None

Substrate
Rene 80

Ni-23Co20Cr-8.5Al4Ta + 0.6Y
[100m]

CMSX-2
(SC)

Ni-23Co20Cr-8.5Al4Ta + 0.6Y
[100m]

Cotac 784
(DS)

Rene 80

Thermalhistory

Testtemp.
(C)

Creeprupture
life

Mincreeprate,
(h1)

ST+A: not stated


Coat: 1068C/6hr

900

38.6
6.5

99
14

ST+A: not stated +


1068C/6hr
(simulated coating HT)
ST:1315C/30 mins/
AC
A:1050C/16hr/AC +
850C/24hr/AC +
Coat:PS (vacuum) +
Diffusion (Ist alloy
ageing temperature)
ST: 1250C/90 mins
1180C/AC
A: 1050C/16hrs/AC +
850C/24 hr/AC
Coat: PS (Vacuum) +
Diffusion (as for alloy)

900

43.2
4.5

119
43

850

Negligible effect on rupture stress.


Creep deformation is dictated by
the alloy metallurgical structure.
Coating procedures matched to
alloy heat treatment. Limited
interdiffusion between coat &
substrate.
Coating lowers creep strength. Life
reduced by 20 to 30% at 900C &
50% at 1100C. Large deformations.
Interdiffusion disrupted the
metallurgical structure responsible
for inferring creep resistance to the
alloy.

1050

900
1100

Key:

Coating:heattreatmentchangesmicrostructureofalloy:changeinc.s.a;cracksinitiateincoating.

HT:Heattreatment;SC:Singlecrystal;A:Aged;ST:Solutiontreatment;c.s.a:Crosssectionalarea;
PS(Vacuum):Plasmasprayinvacuum

48.13.8 Creep fatigue


For a temperature gradient, cyclic temperature changes and loading all act together and each cycle
requiresanalysis;asthefatiguecycledictatestheloadonthenextcreepperiod,andviceversa.
Figure48.13.8showsatypicalstresstimeresponseforacooledgasturbineblade,Ref.[4844].

Factorsinfluencingcreepfatigueinclude:

Coatingapplicationmethod,

Thermalhistory,i.e.heattreatments,

Testmethod,

Environment,and

Temperature(s).

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Figure48.138Coatingdesign:Typicalcreepfatigueeffectsforcooledgasturbine
blades

48.14 Coatings: Future developments


48.14.1 Materials
Theworkislikelytoconcentrateonoptimising:

coatingsystemsforsinglecrystal(SC),directionallysolidified(DS)andotherhighperformance
alloys,

bondcoatformulationsforTBCsystems(bothforceramicandsubstrate),

ceramiclayercompositionswithrespecttobondcoat.

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The modification of substrate alloys is not viewed as an available option. Changes in alloy
compositionsresultinchangedpropertiesandprocessingparameters.

48.14.2 Service temperature


Allthefactorsrequireoptimisationforeveryincreaseinoperatingtemperature;whichimposesmore
severethermalcycling,andthermomechanicalstrainregimesforincreasingservicetimes.

48.14.3 Hydrogen environments


Hydrogen fuel environments impose higher thermal transients and heat flux effects than those of
carbonbasedfuels.TheintentiontousehydrogeninactivecoolingsystemsofThermalManagement
SystemsinSingleStagetoOrbit(SSTO)vehiclesleadstothedevelopmentofcoatingstocombatthe
knowndetrimentaleffectsofhydrogenonmaterials,[See:48.7].Twophilosophiesexisttocombatthis
problem:

Designcomponentsonthebasisofknownandprovenmaterialperformancedatainhydrogen
environments.

Developprotectivecoatings.

Withregardtocoatingdevelopment,Ref.[4817]:

Barriercoatingsaredeemedunreliableastheirbenefitisnegatedbythesmallestdefectwhich
enableshydrogentoenterthematerialandthentrapsitbeneaththeregionsofintactcoating.

Catalyticcoatingscouldprovemoreeffectiveprovidedthattheircompositionsareoptimisedto
belightweight,effective,easytoapplyandcanbeguaranteedtogivecompletecoverage.

48.15 Superalloys: Potential applications


48.15.1 Conventional alloys
48.15.1.1 Resum
Themainfeaturesofconventionalsuperalloyscanbesummarisedas:

Superalloysareusedforhightemperatureapplicationsusuallyintherange700Cto1200C.

Forspaceuse,theirhighdensityisasignificantdrawback.

The huge pool of knowledge relating to gasturbine engine and their use in other high
temperature, aggressive industrial environments, means that superalloys can be used in the
foreseeablefuturefor:

Engines: PM alloys are used by European and US manufacturers, e.g. 1.4kg cooling
plates;640kgcompressordisk,Ref.[4848].

Propulsionunits.

Thermalprotectionsystemsforspacecraft.

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ECSSEHB3220Part5A
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Proven materials, e.g: superalloys, have considerable attractions over newer systems, such as
ceramicmatrixcomposites.

Othermaterials,whenproven,arelikelytoerodetheiruseratherthansuperalloyconsumption
increasing,e.g.titaniumaluminidesinenginecomponents.[See:Chapter49].

48.15.1.2 Applications
Otherthanwithinenginesandpowerplants,reusablespaceplaneconceptshaveprovidedtheimpetus
forfurthersuperalloydevelopments.HoneycombpanelsfortheexternalhotstructuresoftheVenture
StarspaceplanehavebeenproducedfromfoilsofPM1000(NibasedODS)withPM2000(Febased
ODS)superalloy,Ref.[4846].Thecharacteristicsofthesematerialswhichmakethemsuitableforthis
applicationsinclude,Ref.[4846]:

NibasedPM1000:

excellentcreepstrengthathightemperatures,

hotgascorrosionresistantupto1100C,

superiorlowcyclefatiguepropertiesupto1300C,

optimisedemissivitypropertiesforspaceapplicationsupto1300C.

FebasedPM2000:

extraordinarycreepresistanceupto1300C,

highhotstrength,

excellentoxidationresistance,

highstabilityagainsthighspeedgasflowsattemperaturesupto1100C.

Thehoneycombpanels,showninFigure48.15.1,areassembledbybrazing,Ref.[4846].

Brazed PM 1000 (Ni-based) / PM 2000 (Fe-based) honeycomb panels

Figure48.151Superalloys:SpaceapplicationsHotstructure
Theadvantagesprovidedbythesemetallicexternalpanelsonspaceplanesinclude,Ref.[4846]:

costefficientmaintenance,

easyoperability,

selfhealingoxidelayerwithhighemmissivity.

229

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48.16 References
48.16.1 General
[481]
NOTE

MILHDBK5F:MetallicMaterialsandElementsforAerospace
VehicleStructures.November1990
ReplacedbyMMPDS01,Ref.[4849]

[482]

M.J.Weaver
MechanicalPropertyRequirementsforAeroGasTurbineMaterials
MaterialScience&Technology.Vol3.September1987p695700

[483]

J.E.King
FatigueCrackPropagationinNibasedSuperalloyseffectof
Microstructure,LoadRatioandTemperature
MaterialScience&Technology.Vol3.September1987,p750764

[484]

F.Sczerzenie&G.E.Maurer
DevelopmentsinDiscMaterials
MaterialScience&Technology.Vol3.September1987,p733742

[485]

G.S.Hoppin&W.P.Danesi
FutureofSuperalloys
Chapter20ofSuperalloysII.JohnWileypublication1986

[486]

G.A.Webster
HighTemperatureFatigueCrackGrowthinSuperalloyblade
Materials
MaterialsScience&Technology.Vol3.September1987,p716725

[487]

A.Grellieretal
FabricationetpropritsdelalliageUDIMET720destinaudomaine
desmoteursaronautiques
MatriauxetTechniques

[488]

R.L.Dresfieldetal
ApplicationofSingleCrystalSuperalloysforEarthtoOrbit
PropulsionSystems
AIAAPaper871976.JointPropulsionConference,1987

[489]

E.F.Bradley(Ed)
SuperalloysTechnicalGuide
ASMInternational,ISBN087170327

[4810]

A.K.Green&D.P.Bashford:FulmerResearchLtd,(UK)
AGuidetoMetalMatrixCompositeTechnologyanditsPotentialfor
SpacecraftConstruction
FulmerResearchLtd.ReportNo.R878/6A/January1983
ESAContract4389/80/NL/AK(SC)

230

ECSSEHB3220Part5A
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[4811]

J.Wilson&D.P.Bashford:FulmerResearchLtd(UK)
ReviewofEmergingHighTemperatureAdvancedMaterialsfor
SpaceApplications
FulmerResearchLtd.ReportNoR1176/1/April1988
ESAContract7090/87/NL/PH

[4812]

HIPDiffusionBondingofPMAlloysforCompositeLandBasedGas
TurbineBuckets
MetalPowdersReport.October1986.p729738

[4813]

R.C.Benn
MicrostructureandPropertyRelationshipsinOxideDispersion
StrengthenedAlloys

[4814]

K.Mino&K.Asakawa
AnOxideDispersionStrengthened(ODS)NickelbaseSuperalloy
withExcellentHighTemperatureStrength
Trans.IronSteelInst.Japan.October

[4815]

M.V.Islametal.
ArtificialCompositesforHighTemperatureApplications:AReview.
NationalResearchCouncil,Canada.
DME007,NRCNo27323,1987/01

[4816]

R.C.Wetherhold,L.J.Westfall
ThermalCyclingofTFRSComposites
JournalofMaterialsScience23(1988),p713717

[4817]

H.G.Nelson:NASAAmesResearchCenter,(USA)
HydrogenandAdvancedAerospaceMaterials
SAMPEQuarterly,October1988,p2023

[4818]

L.G.Fritzemeier&W.T.Chandler:RockwellInt.,(USA)
HydrogenEmbrittlementRocketEngineApplication
Superalloys,SuperCompositesandSuperceramics
ISBNO12690845,AcademicPress,1989p491524

[4819]

R.L.Dreshfield&R.A.Parr
NASALewisResearchCenterNASA

[4820]

L.Schoenman:AerojetTechSystemsCo.(USA)
SelectionofBurnResistantMaterialsforOxygenDrivenTurbo
Pumps
AerojetTechnology,Vol.3.,pt.1,1986p1524

[4821]

J.Wilson&D.P.Bashford:FulmerResearchLtd.,(UK)
HighTemperatureMetalsandMetalMatrixComposites
ReportNo.R1176/D6/December1989(Draft)forESTEC.

[4822]

W.Betteridge&S.W.K.Shaw:InternationalNickelLtd./Inco
EngineeredProductsLtd.,(UK)
DevelopmentofSuperalloys

231

ECSSEHB3220Part5A
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MaterialsScience&Technology,Sept.1987,Vol.3.p682694
[4823]

JMdeMonicault:SEP,Vernon,(F)
Besoin,CoordinationdesActionsOrganisationMiseenPlace
Actes1erColloqueMateriauxVULCAIN,12fevrier1990,
VernonFrance

[4824]

C.Duretetal
ONERA/SNECMA/UniversitedeNancy,(F)
UsersGuidetoMaterialsforGasTurbineCorrosionResistance
HighTemperatureAlloysforGasTurbine&OtherApplications
Comm.Eur.Communities,1986.EUR10567,p405410

[4825]

J.E.Restall:RoyalAerospaceEstablishment,(UK)
CoatingsforProtectingHighTemperatureComponentsinMarine
GasTurbines
RAETechnicalMemoP1137,19May1988,HMSOLondon1988

[4826]

S.R.J.Saunders&J.R.Nicholls:NPL/CranfieldInstituteof
Technology,(UK)
CoatingsandSurfaceTreatmentsforHighTemperatureOxidation
Resistance
MaterialsScience&Technology,August1989,Vol5.p780798

[4827]

M.J.Bennetetal:HarwellLaboratory,(UK)
OxidationProtectionofAlloyIN738LCbyPlasmaassistedvapour
depositedsilicacoating
MaterialsScience&Technology,August1989,Vol.5,p841852

[4828]

R.Merveletal:ONERA/SNECMA,(F)
MCrAlYCoatings
ONERATPNo.198913;Proc.oflstInt.CongressonHigh
TechMaterialsandFinishing,Berlin1214March1989

[4829]

R.R.Biedermanetal:WorcesterPolytechnicInstitute,(USA)
CharacterizationofHighTemperatureOxidationResistantCoatings
onSuperalloys
MicrostructuralScience.Vol.16,p363378

[4830]

P.Fox&G.J.Tatlock:UniversityofLiverpool,(UK)
EffectofTaAdditionsonOxidationofOverlayCoatedSuperalloys
MaterialsScience&Technology,August1989,Vol..5,p816827

[4831]

M.Francesetal:UniversitedeNancy,(F)
HotCorrosionofNiCoCrAlYTaCoatings
Paper6.49.Proc.of10thICMC,Madras,India,Nov.1987
KeyEng.Mater.2028(2),p14191427,1988

[4832]

A.M.Huntzetal:UniversitedeParisSud,(F)
ImprovementoftheOxidationResistanceofSuperalloysbyLPPS
MCrAlYTaCoatings
OxidationofMetals,Vol.30,Nos.3/4,1988p141183

232

ECSSEHB3220Part5A
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[4833]

D.Fayeulleetal:EcoleNational&SuperieuredesMines/SNECMA;
(F)
ThermalBarrierBondcoatObtainedbyElectrophoreticDepositionof
MCrAlYPowdersonNibasedSuperalloys
Paper39.1;PMAerospaceMaterials87,Lucerne
Switzerland.Nov.1987

[4834]

J.MVerus:ONERA,(F)
InfluenceofProtectiveCoatingsontheMechanicalPropertiesof
Cotac784
MaterialsScience&Engineering88(1987)p253260

[4835]

J.M.Veysetal:ONERA,(F)
InfluenceofProtectiveCoatingsontheMechanicalPropertiesof
Cotac784andCMSX2
ONERATPNo.198673,Proc.ofColloqueInternationalesurla
corrosionHauteTemperature,Marseille,711juillet1986

[4836]

P.Mazarsetal:Ste.Heurechrome,(F)
DegradationofMCrAlYCoatingsbyInterdiffusion
Paper87GT58,ASME,Proc.of32ndInt.GasTurbineConf.&Exhib.
Anaheim,U.S.A.May31June41987

[4837]

.G.Meyeretal:Pratt&WhitneyDiv.,(USA)
HighTemperatureConstitutive&CrackInitiationModellingof
CoatedSingleCrystalSuperalloys
NASALewisResearchCenterTurbineEngineHotSection
Technology,1987,p401412

[4838]

C.Ribandoetal:UniversityofIllinois,(USA)
LaserCladNi70,Al20,Cr9,Hf3AlloyswithExtendedSolidSolution
ofHfPartII:OxidationBehaviour
MetallurgicalTransactionsA,Vol.20A,Nov.1989,p24892497

[4839]

G.Johneretal:MTU.MotorenundTurbinenUnionMnchen
GmbH,(D)
ThermalBarrierCoatingsforJetEngineImprovement
ThinSolidFilms119(1984)p301315

[4840]

G.C.Changetal:ClevelandStateUniversity/NASALewisResearch
Center,(USA)
AStudyonThermalBarrierCoatingsincludingThermalExpansion
Mismatch&BondCoatOxidation
N8912919;NASAESUCooperativeResearchAgreement
No.NCC327p415434

[4841]

S.Stecura:NASALewisResearchCenter,(USA)
AdvancedThermalBarrierSystemBondCoatingsforUseonNi,Co
&FeBasedAlloySubstrates
NASATech.Memo87062,July1985

233

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[4842]

L.Peichletal:MTUMotorenundTurbinenUnionMnchenGmbH,
(D)
HighTemperatureBehaviourofDifferentCoatingsin
HighPerformanceGasTurbinesandinLaboratoryTests
JournalofVacuumScienceTechnologyA4(6)
Nov/Dec1986p25832592

[4843]

R.Merveletal:ONERA/STPA,MinisteredelaDefense,(F)
EffectofProtectiveCoatingsonMechanicalPropertiesofSuperalloys
Paper9,NATO/AGARD68thMeetingOttowa,Canada
April23281989

[4844]

H.W.Grnlingetal:BrownBoverindCieAG.,(D)
MechanicalPropertiesofCoatedSystems
MaterialsScience&Engineering,88(1987)p177189

[4845]

H.J.Kolkman:NationalAerospaceLaboratory,(NL)
Creep,Fatigue&theirInteractioninCoated&UncoatedRene80
MaterialsScience&Engineering89(1987)p8191

[4846]

ExtractfromPlanseeGmbHwebsite:www.plansee.com
(April2003)

[4847]

H.K.D.H.Bhadeshia:CambridgeUniversity,(UK)
DirectionalRecrystallisation&itsExploitationinMechanically
AlloyedMetals
Proceedingsof21stRisoInternationalSymposiumonMaterials
Science,Denmark(2000),p1528

[4848]

Dr.WilliamEisenetal:
PowderMetallurgySuperalloys
MaterialsWorld,Vol.4,(1996),p2224

[4849]

R.C.Riceetal.
MetallicMaterialsPropertiesDevelopmentandStandardization
(MMPDS)
DOT/FAA/ARMMPDS01,January2003
Website:http://www.mmpds.org/

48.16.2 ECSS documents


[See:ECSSwebsite]

ECSSQ7071

Datafortheselectionofspacematerialsand
processes;previouslyESAPSS01701

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49 Intermetallic materials
49.1 Introduction
49.1.1

Types of intermetallic compounds

An intermetallic compound is a chemical compound havinga fixed (stoichiometric) composition. In


alloys,intermetalliccompoundsformfromthealloyconstituentsinthesolidsolution.Theyareoften
usedasstrengtheningmechanisms.
Interesthasfocusedoncertainofthealuminiumcontainingcompounds[See:49.2],including:

Nickel,[See:49.3].

Titanium,[See:49.5].

Ironbased,[See:49.7].

AllthesearewidelypublicisedasAluminides.Aluminideisageneralterm.Eachofthecompounds
hascertaincharacteristicswhichcanbeviewedaseitheradvantagesordisadvantagesdependingon
theintendedapplication.

49.2 Aluminide development


49.2.1

Features

Table 49.02.1 summarises features of various aluminides, Ref. [493]. Their high aluminium content
meansthat,ingeneral,aluminidesoffergoodhightemperatureoxidationresistance.

Table49.21Intermetalliccompounds:Comparisonofaluminidegroups
Type

Titanium
Aluminide
[See: 49.5]
Nickel Aluminide
[See: 49.3]
Iron Aluminide
[See: 49.7]

Chemicalcompound

Meltingpoint(C)

Density(kg/m3)

Ti3Al
TiAl

1600
1460

4200
3900

Ni3Al
NiAl
Fe3Al
FeAl

1390
1640
1540
1330

7500
5900
6700
5600

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Effort has been put into developing the aluminide intermetallic compounds as they offer certain
inherentstrengthandstiffnessbenefitsasaresultoftheir:

crystallography,combinedwith

lowerdensitiesthanthesuperalloyfamily,but

similarmeltingpoints.

Therearetwosignificantdeficiencieswhichhaltedinitialstudiesintothesematerials:

Brittlenessatambienttemperatures.

Lackofadequatecreepresistanceathightemperatures.

Renewedinterestresultedfromimprovementsinductilityandcreepresistance(achievedbydoping
ormicroalloying),andadvancesinanalyticalandmaterialsprocessingtechniques.

49.2.2

Applications

49.2.2.1

Aeroengines

Theaimofdevelopingthealuminidematerialsisto,Ref.[491],[4920],[4922]:

replacecertainaeroenginepartstoenableoperationathighergasorcomponenttemperatures
toimprovetheirefficiencyandsavefuel.

decrease engine weight and operating stresses, primarily for rotating or moving parts, to
improveservicelifeofdiscs,shaftsandassociatedbearingmechanisms.

Demonstrator parts for certain engine components (blades and compressor rotors) have been
fabricatedandevaluated,Ref.[491],[492],[4920];mainlytitaniumaluminides,[See:49.5].

49.2.2.2

Space

TheEuropeanFESTIPprogrammeinvestigatedintermetallicmaterialsforseveralspaceapplications.
Withinthefamilyofintermetallics,titaniumaluminideswereconsideredmoreadvancedthantheNi
andFebasedmaterialsorrefractorymetalsilicides(MoSi2,NbSi2),Ref.[4923].
Potentialapplicationsincluded:

structuralhotskinsandinthermalprotectionsystems(TPS)forspaceplanes,Ref.[4921],[49
23].

matrixphasesforintermetallicmatrixcomposites(IMC),Ref.[4919],[4923].

protective coatings for conventional Tialloys, Tibased composites (TMC) and Tialuminides,
Ref.[4919].

Titaniumaluminideintermetallicmatrixcomposites(IMC)arealsodescribedinliteratureastitanium
matrixcomposites(TMC),Ref.[4919].
[See:49.5Titaniumaluminides]

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49.2.3

Property data

Data presented for materials under development are limited and largely taken from laboratory
research publications. For the commercially more advanced intermetallics, data are mainly single
sourceorproprietary.

Somealuminidesystems,notablytitaniumbased,[See:49.5]areundergoingafullmethodical
mechanicalandenvironmentalevaluationfor:

aeroenginecomponents,Ref.[4919],[4920].

spaceapplications,Ref.[4921].

Materialsprocessingtechniquesareoptimisedforcertainapplicationsandadvancedforothers,
[See:49.8].

Joiningtechniquesareunderdevelopment,[See:49.8].

Inspection is under development: methods are likely to be similar to those applied to more
conventional metals used in aerospace; including those specifically developed for powder
metallurgy(PM)superalloys.

49.2.4

Availability

Initially, licensing arrangements were offered by Oak Ridge National Laboratory (ORNL), who
conductedmostofthepioneeringworkonintermetallics.
Of the most promising of these materials, titaniumbased compositions are now commercially
availableinEuropeandfindingapplications,Ref.[4921].

[See:49.5Titaniumaluminides;49.11Potentialapplications]

49.3 Nickel aluminides


49.3.1

Characteristics

49.3.1.1

General

The nickelaluminides are based on either the NiAl or Ni3Al compounds. Table 49.3.1 compares the
characteristicsofthebasicnickelaluminidesystemsunderdevelopment,Ref.[494].

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Table49.31Nickelaluminides:CharacteristicsofNiAlandNi3Alintermetallic
compounds
Compound

Advantages

Disadvantages

NiAl

Density.
High melting point.
Excellent cyclic
oxidation resistance to
1300C.
Good creep resistance.

Brittle.

Ni3Al

Ductility.
Usable strength to
~800C.
Processable.

High density.
Melting point.
Oxygen
embrittled.

Notes

DuctileBrittle
transition
temperature:
300 to 600C, typ.
Aided by adding rare
earth elements.
Comparable to
superalloys.
Ductility by B doping.
In oxidising
atmospheres at
intermediate
temperatures.
Improved by Cr
additions.

49.3.1.2

Effect of micro-alloying or doping

Thelack,sofar,ofasignificantimprovementintheductilityofNiAlwithoutseriouslycompromising
themeltingpoint,servicetemperatureandoxidationresistance,hasprovedastumblingblocktoits
furtherdevelopment.
BorondopingofNi3Alinducessomeductility.Interesthasfocusedonthismaterial,primarilyatOak
RidgeNationalLaboratory(ORNL),USA.
Additions of other elements, at the ppm level, have been shown to improve certain inherent
characteristics of the base compound. Table 49.3.2 details the compositional ranges of two types of
Ni3Al systems and the effects of doping with certain elements,Ref. [495]. Consequentlya family of
doped or microalloyed Ni3Albased materials is under development. Table 49.3.3 lists the
compositionofthevariousmaterials,Ref.[495],[496],[497],[498].

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Table49.32Nickelaluminides:Compositions(basedonNi3Al)under
development
Typicalcompositionrange
(atomic%)

Effectofdopingormicroalloyingelements

Cr
Ni-base; Al 182; Cr 82; Zr
(or Hf)1.00.8; B 0.150.1

Zr or Hf

B
Ni-base; Al 18.51.5; Fe
13.52.5;
Cr 5.52.5; Zr (or Hf) 0.250.15;
B 0.10.04

Fe
C & Ce

Reduces dynamic embrittlement


in oxidising atmospheres at high
temperatures.
Improves high temperature
strength by solid solution
hardening.
Improves grain boundary strength
& ductility at ambient
temperatures.
Improves hot working ability.
Small additions to control grain
size & improve hot ductility.

Table49.33Nickelaluminides:Composition,materialdesignationandsources
Composition

Key:

Materialdesignation
[Company]

BalNi-11.3Al-0.6Zr-0.02B(wt%)

IC50 [ORNL]

BalNi-8.5Al-7.8Cr-0.8Zr-0.02B(wt%)

IC218 [ORNL]

BalNi-8.5Al-7.8Cr-1.7Zr-0.02B(wt%)

IC221 [ORNL]

BalNi-16.6Al-8Cr-1.0Zr-0.1B(wt%)

IC264 [ORNL]

BalNi-23Al-1.0Hf-0.2B(at%)

IC72 [ORNL]

BalNi-21.5Al-0.5Hf-0.18B(at%)

IC145 [ORNL]

77Ni-22.5Al-0.5Hf + 0.1B(at%)

IC137 [ORNL]

66Ni-24Al-10Co + 0.25B(at%)

Research Alloy [GE]

66Ni-24Al-10Co + 0.75B(at%)

Research Alloy [GE]

76.4Ni-23.1Al-0.5Hf + 0.10B(at%)

Research Alloy [GE]

BalBalance;at%Atomicpercent;wt%Weightpercent

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49.4 Nickel aluminides: Properties


49.4.1

General

The data for the Ni3Al systems given here are indications of the range of properties which can be
offeredbythesematerials.

49.4.2

Mechanical properties

49.4.2.1

Tensile strength (Yield and UTS)

Ni3AlshowsanincreaseinYieldStrengthwithincreasingtemperatureuptoapproximately500Cto
600Candthendecreases,Ref.[495],[499].Theexacttemperaturevarieswiththecompositionofthe
material.
As with all engineering metals, the strengths attainable are dependent on both composition and
condition.
Table49.4.1presentstypicalpropertiesfortheORNLIC50alloyatelevatedtemperaturesforvarious
thermomechanicalorcoldworkconditioning;including,forcomparativepurposes,basicdataonthe
IC218 and IC221 materials, Ref. [496]. These have yet not been subjected to such a detailed
investigationasIC50.

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Table49.41Nickelaluminides:Mechanicalpropertiesatelevatedtemperatures
withvariousconditioning
Temp

YS

UTS

Elong

RofA

(C)

(MPa)

(MPa)

(%)

(%)

25
400
600
800
1000
25
400
600
800
1000
25
400
600
800
1000
RT
200
400
600
800
1000
RT
200
400
600
800
1000
RT
200
400
600
800
1000
RT
200
400
600
800
1000

337
393
447
468
527
610
494
136
1260-1430
1150
920-940
555
165
432
452
467
606
583
223
1355
118
786
696
234
1454
1306
629
168
1685
1597
1143
689
141

587
487
452
455
181
1307
1049
688
549
159
1514-1592
1253
923-998
603
188
1205
1081
858
735
612
265
1498
1276
803
729
325
1560
1373
876
631
700
169
1179
1678
1441
1310
775
190

RT
427
649
760
871
982

586
724
793
758
586
310

1310
1241
965
931
690
379

IC50[ORNL]
13.1
16.8
4.3
9.5
6.2
12.2
2.7
0.8
4.0
0.0
41.8
48.4
26.8
20.4
5.6
7.8
2.7
4.4
63.5
46.6
3.0-10.0
4.4-18.7
2.4
5.6
1.4
0.5-2.7
1.4
0.5
7.0
14.3
32.13
23.25
21.52
16.90
12.38
10.71
3.64
6.18
3.25
3.81
11.62
8.73
5.75
7.35
2.46
5.03
5.17
1.37
2.41
1.13
6.50
7.78
3.33
7.31
3.31
2.83
1.07
1.33
1.70
0.85
1.65
3.60
0.72
1.25
0.25
2.81
1.69
4.13
4.05
0.39
5.77
4.50
8.78
6.83
33.58
38.73
IC218/221
20
17
15
15
15
10

18
15
15
17
17
17

Condition

Direct cast bar.


As-cast condition.
Direct cast bar annealed
after casting
60% swaging + anneal +
60% -swaging + annealed
at 1100C.
Direct cast bar. 60%
swaged + 1100C anneal +
60% swaged +
1100C anneal + 20% cold
reduction.

Annealed 1100C/1 hour.

10% Cold work.

20% Cold work.

40% Cold work.

Not stated.

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49.4.2.2

Modulus

Table49.4.2showstheeffectoftemperatureonthemodulusoftheORNLICmaterials,Ref.[496].The
retentionofstiffnessatelevatedtemperatures,suchasat600C,isviewedasoneoftheiradvantages.

Table49.42Nickelaluminides:Modulusatelevatedtemperature
Alloy

IC50

IC218

IC221

Temperature

Modulus

(C)

(GPa)

25
400
600
800
1000
1075
1097
25
400
600
800
1000
1075
1097
25
400
600
800
1000
1075
1097

171
150
148
118
93
53
226
167
171
80
216
-

49.4.2.3

Ductility

ForNi3Alborondopedmaterials,theductilitydecreasessubstantiallywithincreasingtemperature.A
pronouncedminimumisobservedbetween600Cto850Cfortestsconductedinair.Thiseffecthas
beenattributedtoembrittlementbygaseousoxygen.Itisimprovedwithchromiumadditionswhich
promoteformationofachromiumoxidefilmwhichactsasabarriertooxygen.
Ductility is affected by the processing route used. This too is linked with the presence of oxygen,
usuallyretainedinpowders.

49.4.2.4

Fatigue

Dataarelimitedonfatigueperformanceofthenickelaluminides.Table49.4.3givessomepreliminary
datafortheIC218andIC221materials,Ref.[496].

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Table49.43Nickelaluminides:PreliminaryfatiguetestdataforIC218andIC221
Fatiguedata
Alloy

IC218

Nf

(MPa)

(cycles)

605
641
690
793
862
690
741
793
862
910

>10-7
1.6 x 10-6
3.9 x 10-5
6.7 x 10-4
1.1 x 10-4
9.8 x 10-6
2.0 x 10-6
4.5 x 10-5
1.23 x 10-5

Condition

Hot extruded, cast billet.


Cold swage at RT.
+ 1050C/1 hour anneal
+ 800C/1 day

IC221

Testconditions:

1.5 x 10 4

Temperature600Cvacuum.
Triangularwavefunction,frequency20Hz.
R=min/max=1

49.4.2.5

Creep

Firstindicationsarethatnickelaluminidesinthecastconditionofferahighercreepresistance(700C
to900C)thanwroughtWaspalloy,butonlyamoderateimprovementinthewroughtcondition.This
observationrequiressubstantiationduringafulltestingprogramme.

49.4.3

Oxidation resistance

The ability of Nickel aluminide materials to produce an alumina (Al2O3) film at 100C to 1100C
provides resistance to oxidation. However, nonchromiumcontaining alloys are sensitive to
embrittlement by gaseous oxygen causing a significant loss in ductility. The Crcontaining alloys
produceamixedAl2O3Cr2O3protectivecoatingtohelpresistembrittlement.

49.4.4

Aqueous corrosion

Nickelaluminides,notableNi3Aloffergoodresistancetothemajorityofcorrosivemedia.

49.4.5

Coefficient of thermal expansion (CTE)

Table49.4.4givessometypicalvaluesofCTEmeasuredforaNi3Albasedmaterial,Ref.[494],[496].
Themeasurementsweremadeaspartofaresearchprogrammeandarethereforeforguidanceonly.

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Table49.44Nickelaluminides:Coefficientofthermalexpansion
Alloy

Temperaturerange

CTE

(C)

(106/C)

27-327
427-727
727-1027
27-327
427-727
727-1027
Not stated

12.5
14.8
16.8
12.5
14.8
16.8
14.5

76%Ni-24%Al

75%Ni-25%Al
NiAl

49.5 Titanium aluminides


49.5.1

General

Thetitaniumaluminidematerialsarebasedoncompoundsof:

TiAl:titaniumaluminides(orderedfacecentredtetragonalL10structure)

Ti3Al:or2titaniumaluminides(orderedhexagonalD019structure).

Initialworkconcentratedonsinglephaseintermetallics,whicharedescribedinliteraturebytheirbase
compound,e.g.Ti3Al,orbytheirmetallurgicalstructure,e.g.2Ti3Al.
Furtherworkhasconsideredtwophaseintermetallicsinwhichthelimitationsofonecompoundcan
in theory be offset by the other. These tend to be described as titanium aluminides and are
technicallyadvancedandcommerciallyavailable.

[Seealso:49.9fororthorhombictitaniumaluminides]

49.5.2

Characteristics

Table49.5.1comparesthecharacteristicsofthetitaniumaluminidesystems,Ref.[494],[4924].

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Table49.51Titaniumaluminides:Comparisonofcharacteristics
Compound

Singlephase
-TiAl

Advantages Disadvantages

Density

Singlephase
-Ti3Al

Density

Two-phase
-TiAl

Density

Notes

Brittle
Oxidation
tolerance.
-

Additions of Nb to achieve
ductility but increase density.
For applications >700C, coating
advised.
Contains both TiAl and Ti3Al
compounds giving a controlled
amount of each phase, i.e. and 2
in the resulting microstructure.

Forspaceapplications,otherimportantcharacteristicsinclude,Ref.[4924],[4925]:

highelasticmodulus,

lowdensity,

highresistancetohydrogenabsorption,

goodoxidationresistance,

burnresistance(noselfignition).

Subsequent alloy developments (TiAl) have improved creep resistance and specific strengths such
thattheirpotentialservicetemperaturecanbeconsideredintherangeof700Cto950C,Ref.[4924].

49.5.3

Effect of micro-alloying or doping

49.5.3.1

General

Both the basic TiAl or Ti3Al compounds are inherently brittle from room temperatures up to
approximately600C.
Small additions of niobium, tungsten and vanadium (typically 0.5 to 10.0 atomic percent) doped or
microalloyedwiththebasecompoundsinducemoreusableductilities.
Table49.5.2liststhevarioustitaniumaluminidematerialsunderexamination,Ref.[4924].

49.5.3.2

Experimental alloys

Ofthese,theTi3Al+Nbserieswerethemostprominent.Althoughtheniobiumadditionsalsoassisted
inoxidationandcreepresistance,interestinthevarioustypematerialshasdiminishedinfavourof
theseries,Ref.[4922].
The molybdenum and vanadium additions assist rapid solidification by retaining certain
metallurgicalphases.Someofthesealloyshaveadditionsofrareearthelements.Theseareaddedto
enhancestrengthbydispersionhardening.

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Table49.52Titaniumaluminides:Typicalcompositions
Status

Experime
ntal
[1]

Nominalcomposition

Company/Organisation

Ti3Al-5Nb-1W(at%)

Ti3Al-15Nb(at%)
TiAl-2W(at%)
Ti3Al-1V(at%)
Ti-(17 to 37)Al-1Ru(at%)
Ti-(20.5 to 23.7)Al-(5 to 15)Nb3Zr + (0.3 to 0.9)Er2O3

Imperial College, UK.


Marko Materials Inc.
Wright-Patterson
AFB/Calspan
Wright-Patterson
AFB/Calspan
Wright-Patterson
AFB/Calspan
FESTIP (protective
coatings)
FESTIP (protective
coatings)

Ti-24Al-4Nb-4Mo-4V-0.45O
Ti-24Al-4Nb-4Mo-4V-0.2Er0.2Ce-0.20S-0.2Y-0.45O
Ti-24Al-4Nb-4Mo-4V-0.3Er0.3Ce-0.30S-0.2Y-0.45O
Ti-47Al-2Cr-0.2Si
Ti-47Al-2Cr-2Nb
Two-phase Ti - 45 to 48 Al - 0 to 3 (Cr, Mn,
V) - 0 to 5 (Nb, W, Ta) - 0 to 1
-TiAl
(Si, B)
[2]
Ti-48Al-2Cr

Typical Composition
Range (at%)

GE Alloy: Ti-48Al-2Cr-2Nb

Plansee GmbH
Developed by General
Electric, USA. [3]
Plansee GmbH

Key:[1] Underinvestigationinthe1980s.FESTIPevaluationcontinuedinthemidlate1990s.
[2] Technicallyadvancedandcommerciallyavailable.
[3] AsecondgenerationalloyforGE90aircraftenginepartsforBoeing777.

49.5.3.3

Two-phase alloys

Twophase TiAl based alloys contain both the TiAl phase and the 2Ti3Al phase. Their
metallurgicalcompositioncharacteristicscanbesummarisedas,Ref.[4924],[4925]:

The2Ti3Alphasescavengesoxygen,soincreasesthepurityhenceductilityofthephase.

Theamountof2phaseiscontrolledbytheAlcontentandadditionalelements.

AdditionsofCr,MnandVincreaseroomtemperatureductility.

AdditionsofNb,Wand,toalesserextentTa,improveoxidationresistanceandenhancecreep
propertiesbysignificantsubstitutionalsolidsolutionstrengthening.

AdditionsofB,SiandCprovideeffectivedispersionorprecipitationhardeningeffects.

IfBorSiexceedcertainlevels,boridesorsilicidesarepresent.

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Interstitial elements, such as O, N, C and B reduce ductility if levels exceed ~1000 ppm (by
weight).

Thecharacteristicsofthesealloysaredeterminedbytheirchemicalcompositionandmicrostructure.
[See:49.6].

49.6 Titanium aluminides: Properties


49.6.1

General

Dataarepresentedfor:

Experimental alloys (pre1990): Extracted from various research publications; mainly of US


origin.Theseshowthebasiccharacteristicsoftitaniumaluminidesandprovideabackground
tothefurtherdevelopments.

Twophase alloys (post1990): These compositions developed from the most promising
experimentalalloysandaresubjecttomoredetailedinvestigationsforaerospaceapplications.
Dependingonthecompositionandcondition,theinfluenceofthemicrostructureonproperties
canbesummarisedas,Ref.[4925]:

Coarsegrained, fullylamella: relatively good fracture toughness, excellent creep


resistancebutpoortensileductilityandstrengthespeciallyatRT.

Finegrained, near and duplex (low volume fractions of lamella grains): low fracture
toughness and creep resistance, but moderate tensile ductility and strength at RT and
elevated temperatures. An optimised finegrained lamella microstructure can provide
acceptablemechanicalperformance.

Orthorhombic phase alloys: Mainly under investigation as matrix phases for intermetallic matrix
composites(IMC),[See:49.10].

49.6.2

Mechanical properties

49.6.2.1

Tensile strength (Yield and UTS)

Table49.6.1givesexperimentalalloydatafromvariousresearchpublicationsontitaniumaluminides,
Ref.[491],[4910],[4911],[4912],[4913],[4924].

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Table49.61Titaniumaluminides:Mechanicalpropertiesformaterialsprocessedbydifferenttechniques
Temp
(C)

YS
(MPa)

UTS
(MPa)

Modulus
(GPa)

Elong
(%)

R of A
(%)

TiAl

335*

450

0.9

Ref. [49-10]

TiAl

176

L10 crystal structure,Ref. [49-1]

TiAl

176

Ti3Al

145

DO19 crystal structure, Ref. [49-1]

Ti3Al

145-110

Ref. [49-13]
Ref. [49-10]

Alloy composition

Notes
[Reference]

Condition

Experimental alloys

Ti3Al

Ti-14.2Al-21.5Nb(wt%)
TRW/PWA

Ti3Al Niobium Modified.


Crucible Materials Corp.
USA

550

20

709

743

1.4

0.7

"

696

759

1.5

1.6

"

689

791

1.6

2.4

204

578

748

3.9

4.0

"

588

731

3.0

3.2

"

601

695

2.0

2.8

649

429

686

18.4

23.3

"

426

683

18.8

27.2

"

444

650

19.1

17.5

20

608

722

1.3

1.6

"

608

728

1.2

4.3

649

385

601

13.0

21.5

"

385

576

16.0

24.8

RT(a)

510

606

RT(c)

530

592

<1

RT(d)

661

772

760(d)

303

558

14

20

425(b)

344

572

11

12

Powder Consolidation by HIP:


927C/207 MPa/2 hour 1177C/1
hr/Fan Cool. 760C/1 hr/Air Cool.

Precision Cast Part Corp. Ref. [49-12]

Cast + isoforged at 1068C +


1093C/0.5 hr/ Cool 260C/minute
760C/1 hr/Air Cool.

Exact composition not stated.


Data used for comparison with Powder Met
TRW experimental, Ref. [49-12]

1175C/0.5 hr/Air Cool +760C/1 hr/AC Powder Production by Plasma Rotating


+595C/8 hr/Vac Cool.
Electrode Process (PREP) consolidated by
HIP @ 1065C, Ref. [49-1]
1205C/0.5 hr/Fan Air Cool +760C.
Different Cooling Rates from Solution
Treatment Temperature:
1205C/0.5 hr/AC +760C/1 hr/ Vac
Cool.
(a) 50C/min

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Temp
(C)

YS
(MPa)

UTS
(MPa)

Modulus
(GPa)

Elong
(%)

R of A
(%)

540(b)

324

517

12

15

650(b)

282

468

13

20

760(b)

248

400

18

22

760(d)

241

386

14

15

Ti3Al-5Nb-1W

796*

920

0.4

Ti3Al-15Nb

4.9

TiAl-2W

642*

790

0.8

TiAl-1V

400

2.2

Ti-23.75Al-5Nb (at%)

650

270*

587

8.3

10.3

Alloy composition

Ti-21.25Al-15Nb (at%)

650

449

840

1.8

5.2

Ti-20.50Al-15Nb-3Zr

650

518

962

1.6

3.5

Ti-21.24Al-15Nb-0.3Er2O3

650

321

651

1.8

3.9

Ti-21.10Al-15Nb-0.6Er2O3

650

456

795

4.7

8.7

Ti-21.03Al-15Nb-0.9Er2O3

650

388

702

9.1

13.8

-196

577

172

Notes
[Reference]

Condition

1205C/0.5 hr/Oil Q + 760C/1 hr/Vac


Cool.

Not stated.

As-extruded.

(b) 60C/min
(c) 120C/min
(d) >280C/min
(e) >17000C/min

Ref. [49-10]

Melt Spun Ribbon-Pulverised-Hot Extruded,


Ref. [49-11]

Two-phase -TiAl alloys

Ti-48Al-2Cr

Ti-48Al-2Cr

Ti-48Al-2Cr

25

421*

432

109

600

323*

457

128

700

322*

512

115

31

700V

350*

562

56

800

292*

357

97

93

-196

559

160

25

407

162

0.4

600

376*

540

145

700

363*

524

112

54

700V

336*

508

66

800

313*

339

105

65

-196

625*

622

149

0.2

Ingot metallurgy.
Near- microstructure.

Ingot metallurgy.
Near- microstructure.
Annealed: 700C/100hrs.

Ingot metallurgy.

Sheet test specimens,Ref. [49-24]

Sheet test specimens, Ref. [49-24]

Sheet test specimens, Ref. [49-24]

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Alloy composition

Temp
(C)

YS
(MPa)

UTS
(MPa)

Modulus
(GPa)

Elong
(%)

R of A
(%)

25

440*

457

150

600

371*

567

136

700

366*

512

120

100

700V

394*

640

65

800

295*

327

104

89

-196

561

173

25

450*

453

146

600

345*

546

129

700

368*

487

100

112

700V

388*

509

65

800

281*

318

90

91

-196

617

171

25

451*

455

128

600

339*

499

119

700

356*

553

122

15

Ti-48Al-2Cr

Ti-48Al-2Cr-2Nb

700V

375*

620

19

800

337*

406

95

58

-196

526

170

153

600

338*

435

120

700

341*

498

93

10

359*

466

94

71

-196

625

169

25

518*

528

101

0.3

600

439*

632

92

700

392*

558

85

98

25
Ti-48Al-2Cr-2Nb

424*

426

700V
800
Ti-48Al-2Cr-2Nb

308*

370

Notes
[Reference]

Condition

PA - Primary annealed (after sheet


rolling):
1000C/2 hrs/vacuum.

Ingot metallurgy.
PA - Primary annealed (after sheet
rolling):
1000C/2 hrs/vacuum.
Annealed: 700C/100hrs.

Powder metallurgy.
Near- microstructure.

Powder metallurgy.
Near- microstructure.
Annealed: 700C/100hrs.

Powder metallurgy.
PA - Primary annealed (after sheet
rolling):
1000C/2 hrs/vacuum.

Sheet test specimens, Ref. [49-24]

Sheet test specimens, Ref. [49-24]

Ref. [4924]

Sheet test specimens, Ref. [49-24]

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Alloy composition

Temp
(C)

YS
(MPa)

UTS
(MPa)

Modulus
(GPa)

Elong
(%)

R of A
(%)

Condition

Notes
[Reference]

700V
800

Ti-48Al-2Cr-2Nb

Key: * : 0.2% Yield Stress

420*

693

67

315*

418

79

80

-196

510

149

25

464*

466

119

600

443*

570

122

700

379*

543

102

89

700V

400*

550

66

800

357*

404

81

83

: Specimen failed near gauge clamp.

Powder metallurgy.
PA - Primary annealed (after sheet
rolling):
1000C/2 hrs/vacuum.
Annealed: 700C/100hrs.

Sheet test specimens, Ref. [49-24]

V: Test temp., in vacuum.

At room temperature, the base TiAl and Ti3Al compounds are


brittle.

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ThedatafortwophasealloysaremeanvaluestakenfromaEuropeanmaterialcharacterisationstudy
forpotentialspaceapplications,Ref.[4924],[4925].Keyfeaturesinclude:

Ultimate tensile strength is temperature dependent. It reduces from 196C to RT, and then
surprisingly increases up to ~600C to 700C. Above this temperature, UTS reduces; as seen
withconventionalmetallicmaterials.

Yieldstressdecreasesby~28%betweenRTand~800CThissofteningbehaviourisdifferentto
thatofconventionalmetals.

49.6.2.2

Modulus

Forthebasicintermetalliccompounds,TiAlhasahighermodulusthanTi3Al,[See:Table49.6.1].For
twophasealloys,Ref.[4924],[4925]:

Asexpected,themodulusishighestat196C.

Stiffness generally decreases as temperature increases, as shown in Figure 49.6.1, Ref. [4924].
Thistrendwasdeterminedbymechanicaltesting(takingintoaccountscatteroriginatingfrom
strainmeasurements)andconfirmedbysonicmeasurements.

Mean values for PM and IM two-phase -Ti Al alloys, all conditions

Figure49.61Titaniumaluminides:EffectoftemperatureonYoungsmodulus

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49.6.2.3

Ductility

TheexperimentalalloyshavelowductilitiesatRTandintermediatetemperatures,[See:Table49.6.1].
Twophasealloysshowaductiletobrittletransition(DBTT)atabout700C,asshowninFigure49.6.2,
Ref.[4924].

Figure49.62Titaniumaluminides:TwophasealloysDuctilityversus
temperature

BelowtheDBTT,bothtwophasealloyshavelowductilities.AbovetheDBTT,plasticflowoccursthat
canresultinelongationsof120%ormore.
Ductilityisalsoinfluencedbytheprocessingroute(ingotorpowdermetallurgy)andmicrostructure
(conditionheattreatments),e.g.theneargammamicrostructureofPMTi48Al2Cr2Nbisgenerally
lower than for the primary annealed condition. Likewise the elongation behaviour of the near
structureandprimaryannealedconditiondifferbetween600Cand800C.
Nosignificantdifferenceinductilitywasseenwhentestedinairorinvacuum.
A typical elongation value of 1% to 2% at RT and 4% to 6% at 600C are intrinsic of intermetallic
materialsandshouldbetakenintoaccountinthedesign,Ref.[4924].

49.6.2.4

Fatigue

Limiteddatahavebeenpublishedonthefatiguebehaviouroftitaniumaluminidematerials.
A study on an experimental alloy (Ti16Al10Nb wt.%) showed that the fatigue crack growth
behaviourat650Cwasindependentofthemicrostructure.Anapparentthresholdof6.5MPamwas
determined. When compared with Rene 95 superalloy, as shown in Figure 49.6.1, the shapes of the
curvesaresimilarbutthecrackgrowthwasanorderofmagnitudehigherforthealuminide,Ref.[49
9].

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Figure49.63Titaniumaluminides:Comparisonoffatiguecharacteristicswith
Rene95superalloy
For-TiAlmaterialsatbothRTandelevatedtemperatures,fatiguecrackgrowthratesareconsiderably
higher than for superalloys. Finegrained materials(near and duplex) have considerably higher fatigue
crack growth rates (constant amplitude loading) than coarsegrained lamella structures, Ref. [4925]. [See
also:Fracturetoughness].

49.6.2.5

Fracture toughness

TheTiAlmaterialsexhibitaninverserelationshipbetweentensileductilityandfractureresistance.
Consequently,improvedductilitydoesnotconferimprovementsinfracturetoughness,Ref.[4925].
ForTiAlmaterials,fracturetoughnessisstronglylinkedtothemicrostructureand,inparticular,the
volumefractionoflamellagrainspresent.
For sheet materials, the relationship between fracture toughness and microstructure can be
summarisedasRef.[4925]:

Near-(0%lamella):12MPam

Duplex (20% lamella): 15MPam

Lamella(95%lamella):22MPam

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49.6.2.6

Creep

Table49.6.2indicatesthecreepperformanceofanexperimentalTi3Al+Nballoy,Ref.[492]andatitanium aluminide (Ti-48Al-2Cr) withanear microstructure, Ref. [49-25].

Table49.62Titaniumaluminides:Indicationofcreepproperties
Experimental alloy
Alloy

Condition

Ti3Al + Nb

PREP Powder HIP @


1065C+1205C/hr/A
gC 760C/1 hr/Vac.C

Key:

Plasticdeformation(%)
Stress
(MPa) 23hour 50hour 165hour

138

0.95

1.53

3.55

AgC:Argoncool.Testtemperature:760C.Vac.C:Vacuumcool

Two-phase -TiAl alloy


Max.stress(MPa)
Alloy

Ti-48Al-2Cr
Ti 1100

(0.2%creep/10hrs)

Condition

Near- microstructure
Sheet specimen
Conventional Ti-alloy
[For comparison]

700C

800C

~245

~140

~40

49.6.3

Oxidation resistance

Ingeneral,thebasetitaniumaluminidecompoundsoffergoodoxidationresistancetoapproximately
650C. To enhance oxidation resistance of Ti3Al base experimental alloys, the creation of a TiAl3
surfacecoatingwassuggested.
Forlongtermexposureinanoxidisingenvironmentatabove700C,themechanicalperformanceof
twophasealloysislikelytodeteriorate.
ThetypesofoxidationresistantcoatingsconsideredwithinFESTIPare,Ref.[4923]:

preoxidation(SiO2pack).

silicide(SiCrB)bypackcementation.

aluminising(AlCrNb)byslurrydeposition.

coating(CoCrAlY)byplasmaspraying.

Coatings reduced the oxidation rate (by about 2 orders of magnitude) compared with the uncoated
alloy.
Modifiedaluminidecoatingsshowedgoodresistanceundercyclicoxidationtests.
[Seealso:Chapter74Protectivecoatings]

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49.6.4

Thermophysical properties

49.6.4.1

General

Thermal characteristics have been evaluated with respect to the potential application of titanium
aluminides on the external surfaces of spacecraft. Their high thermal conductivity enables higher
coolingefficienciesandlowerthermalstresses,whichisconsideredanimportantbenefitoverceramic
basedmaterialsforsimilarapplications,Ref.[4923],[4924].
[Seealso:Chapter82]

49.6.4.2

Thermal diffusivity

Figure 49.6.4 compares the thermal diffusivity of twophase titanium aluminide alloys from RT to
1200C;meanvaluesmeasuredbylaserflashmethod,Ref.[4924].
BetweenRTand~900C,theNbcontainingcompositionshowsa5to8%lowerthermaldiffusivity.
Temp.
[C]
40
100
200
300
400
500
600
700
800
900
1000
1100
1200

Ti48A12Cr (IIVI)
Near Gamma
6.93
7.36
7.72
7.99
8.20
8.52
8.70
8.77
8.81
8.73
7.79
7.16
6.72

Ti48Al2Cr2Nb (PM)
Primary Annealed
Near Gamma
6.51
6.21
6.71
6.50
7.06
6.85
7.46
7.24
7.68
7.49
7.93
7.70
8.16
7.90
8.22
8.02
8.29
8.02
8.26
8.15
7.33
7.30
6.88
6.87
6.44
6.40

Thermal Diffusivity a[cm 2/sec]*100

9
8

6
Ti48A12Cr (IIVI) Near Gamma
5

Ti48Al2Cr2Nb (PM) Primary Annealed


Ti48Al2Cr2Nb (PM) Near Gamma

4
0

200

400

600

800

1000

1200

1400

Temperature [C]

Figure49.64Titaniumaluminides:TwophasealloysThermaldiffusivity
versustemperature
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49.6.4.3

Specific heat

Figure 49.6.5 compares the specific heat of twophase titanium aluminide alloys from RT to 1200C;
mean values measured by Differential scanning calorimeter (DSC), Ref. [4924]. No significant
differenceinspecificheatpropertiesisseenforthetwocompositions.
Temp.
[C]
50
100
200
300
400
500
600
700
800
900
1000
1100
1200

Ti48A12Cr (IM)
Near Gamma
0.619
0.640
0.669
0.689
0.704
0.719
0.735
0.779
0.803
0.847
0.901
0.963
1.109

Ti48Al2Cr2Nb (PM)
Primary Annealed
Near Gamma
0.598
0.609
0.631
0.634
0.655
0.657
0.672
0.673
0.688
0.688
0.701
0.7
0.714
0.713
0.766
0.769
0.791
0.792
0.832
0.829
0.892
0.884
0.958
0.945
1.12
1.072

1.3
1.2
Specific Heat cp [J/g K]

1.1
1
0.9
0.8
0.7
Ti48A12Cr (IM) Near Gamma

0.6

Ti48Al2Cr2Nb (PM) Primary Annealed

0.5

Ti48Al2Cr2Nb (PM) Near Gamma

0.4
0

200

400

600

800

1000

1200

1400

Tempera ture [C]

Figure49.65Titaniumaluminides:TwophasealloysSpecificheatversus
temperature

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49.6.4.4

Thermal conductivity

Figure 49.6.6 compares the specific heat of twophase titanium aluminide alloys from RT to 1200C,
Ref.[4924].
Temp.
[C]
100
200
300
400
500
600
700
800
900
1000
1100
1200

Ti48Al2Cr (IM)
Near Gamma
17.9
19.6
20.8
21.7
23.0
23.9
25.4
26.2
27.3
25.8
25.2
27.1

Ti48Al2Cr2Nb (PM)
Primary Annealed
Near Gamma
16.6
16.1
18.0
17.5
19.5
18.9
20.5
19.9
21.5
20.8
22.4
21.6
24.1
23.6
25.0
24.2
26.1
25.6
24.7
24.4
24.8
24.4
26.9
25.6

30
28
26
24
22
20
18

Ti48Al2Cr (IM) Near Gamma


Ti48Al2Cr2Nb (PM) Primary Annealed

16

Ti48Al2Cr2Nb (PM) Near Gamma

14
200

400

600

800

1000

1200

1400

Thermal Conductivity k
[W/m K] of TiAl (calculated)

Figure49.66Titaniumaluminides:TwophasealloysThermalconductivity
versustemperature

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These values were calculated using the mean measured values for specific heat and density
measurementsatRT.
The small difference seen between the Nbcontaining and the Nbfree composition could be an
accuracyartefact(6%to8%)ratherthanarealeffect.
Changesinthecurveshapeswithincreasingtemperature,especiallythefallat~900Candsubsequent
increase>1100C,isrelatedtomicrostructuralphasechangesoccurringwithinthematerials.

49.6.4.5

Coefficient of thermal expansion

Earlyworkonanexperimentalalloy(Ti3Al+Nb)determinedaCTEof10x106/C.
Figure 49.6.7 compares the coefficient of thermal expansion of twophase titanium aluminide alloys
from RT to 1200C. CTE was measured by dilatometer with samples taken parallel to the rolling
direction,Ref.[4924].
Nosignificantdifferenceisseenbetweenthetwocompositions.

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Temp.

Ti48A12Cr (IM)

Ti48Al2Cr2Nb (PM)

[ C ]

Near Gamma

Primary Annealed

Near Gamma

100
200
300
400
500
600
700
800
900
1000
1100
1200

10.67
10.98
11.25
11.51
11.75
12.00
12.27
12.57
12.90
13.29
13.74
14.27

10.49
10.80
11.06
11.29
11.52
11.75
12.01
12.31
12.68
13.12
13.66
14.31

10.57
10.78
11.00
11.23
11.47
11.73
12.01
12.31
12.65
13.02
13.42
13.87

15

Thermal linear expansion


CTE [1/K x 10 -6]

14

13

12
Ti48A12Cr (IM) Near Gamma

11

Ti48Al2Cr2Nb (PM) Primary Annealed


Ti48Al2Cr2Nb (PM) Near Gamma

10
0

200

400

600

800

1000

1200

1400

Temperature [C]

Figure49.67Titaniumaluminides:TwophasealloysCoefficientofthermal
expansionversustemperature

49.7 Iron aluminides


49.7.1

Characteristics

49.7.1.1

General

InterestintheironaluminideslargelyfocusedontheFeAlcompound.Workonthismaterialandits
derivativeshasbeencoordinatedbyNASA,Ref.[494].
The FeAl system has a number of beneficial characteristics, notably the level of ductility at room
temperature.

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Table 49.7.1 compares the advantages and disadvantages of FeAl, Ref. [494]. Initial studies
concentratedontheFe40Al(atomicpercent)materials.

Table49.71Ironaluminides:Characteristics
Advantage
Ductility: 3 to 5% at RT
Cyclic oxidation resistance at 1000C.
Not susceptible to oxygen embrittlement at
intermediate temperatures.
Key:

Disadvantage
Melting point: 1340C
Density
Strength and creep resistance decreases
significantly at >700C

:Fe40Al(atomic%)isoneofthefewaluminidecompoundswithmeasurableductilityatRT.

Table 49.7.2 lists some of the alloys undergoing investigation, Ref. [494], [4914]. In general, iron
aluminidesareconsideredapossiblereplacementforsomestainlesssteelcomponents,perhapsalso,
innonaerospaceapplications.

Table49.72Ironaluminides:Compositionofdevelopmentmaterials
Composition
Fe-40Al (at.%)

Company
-

Fe-40Al-0.1Zr-0.2B (at%)

Case Western
Uni/NASA-Lewis

Notes
Zr (or Hf):
B:

Fe-40Al-0.1Zr-0.2B +
1vol%Y2O3
Key:

Case Western
Uni/NASA-Lewis

Y2O3:

Increase strength to
700C, typ. & maintain
ductility.
Aid low temperature
ductility.
Improve high
temperature strength by
ODS, but maintain
ductility.

at.%Atomicpercent;
vol%Volumepercent;
ODSOxidedispersionstrengthened.

49.7.1.2

Material properties

Figure49.7.1showstheroomtemperaturebehaviourofFe40Al(atomicpercent)withboronadditions
andindifferentconditions,Ref.[493].
Forcomparativepurposes,Figure49.7.2showstheeffectofconditioningandelevatedtemperatureon
thestrengthofY2O3oxidedispersionhardenedalloysystems,Ref.[4914].
Attempting to enhance mechanical properties above 700C by further alloy modifications can
seriouslyaffecttheotherbeneficialpropertiesoftheFeAlsystem.

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Figure49.71Ironaluminides:RoomtemperaturebehaviourofFe40Al(at.%)+
boronadditionsindifferentconditions

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Figure49.72Ironaluminides:Effectofconditioningandelevatedtemperatureon
strengthofYttriaODSalloysystem

49.8 Processing
49.8.1

Development

Thedevelopmentofintermetallicmaterialshasbeencoupledwithasignificanteffortdevotedtotheir
processing technology. This has partly been in an effort to find a method which did not cause a
deleteriouseffectonthepropertiesachievedbydopingormicroalloying,andpartlywiththeaimof
findingacosteffectivemethodofprocessingmaterialswithhighmeltingpoints.
Experience of processing conventional hightemperature materials, such as superalloys, has been
appliedtointermetallics.

49.8.2

Material processing

49.8.2.1

General

Manytechniqueshavebeenconsidered,including:

conventionalmetalprocessingmethods.

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ECSSEHB3220Part5A
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standardpowdermetallurgytechniques.

rapidsolidification.

Table 49.8.1 shows general guidelines as to the material processing methods applicable to the
aluminides, plus any obvious problems encountered, Ref. [491], [497], [4915], [4916], [4924], [49
25]. Each method has its own pros and cons. Most of the processing routes investigated require
optimising,e.g.temperaturesandtimes,coupledwithafullevaluationofthemechanicalproperties
attainedfromamaterialprocessedinaparticularway.ProcessingofTiAlmaterialshasundergone
significantlevelsofevaluation,Ref.[4925].

Table49.81Aluminides:Summaryofmanufactureandconsolidationtechniques
Manufacture

Consolidation

Notes

Nickelaluminides
Ingot by conventional
casting in air, vacuum &
argon.
Melt spinning for rapid
solidification ribbons.
Spray or plasma deposition
for near-net shapes.
Conventional powder
metallurgy processes.
Reactive sintering.

Hot extrusion, if
canned.
HIP.
Difficult to hot work
due to low ductility at
high temperatures +
oxygen embrittlement.
Cold work + anneal.

Materials produced by
rapid solidification/powder
routes tend to have
significant levels of oxygen
(surface:volume effect)
compared with those
produced by conventional
casting. Material
embrittlement by residual
oxygen has been noted.
Rapidly work hardens.

Titaniumaluminides
Conventional casting (to
815kg ingot).
Conventional powder
metallurgy processes.
PREP powder route.
Melt spinning for rapidly
solidified ribbons.

Hot extrusion, if
canned.
HIP.
Hot pressing.

Wrought material
processing (rolling to thin
sheet and foil).
Sheet forming:
conventional &
superplastic forming.

Ironaluminides
Conventional casting.
Powder metallurgy (also
ODS alloys).

Hot workable.
Hot extrusion.

These materials are


usually easier to fabricate.

49.8.2.2

Conventional techniques

TheTiAlmaterialscanbeprocessedby,Ref.[4925]:

Ingot metallurgy: using techniques that provide ingots with low interstitial impurity concentrations, such
as skull melting, vacuum arc melting, plasma melting.

Casting: ingots, investment casting, permanent die moulding casting(gravityorcentrifugalmethods)


to produce demonstrator nearnet shape components, such as compressor or turbine blades,
turbochargers, automobile exhaust valves. Porosity in castings is often consolidated by hot
isostaticpressing(HIP).

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Hot working:eitherassingleor,morerecently,multistepprocesses:

forging:gatorising,isothermalorquasiisothermal.

extrusion.

dieforging.

Hot working of cast products to provide wrought materials and semiproducts is usually
carriedoutbetween1100Cand1300Ctogiveafinegrainstructurethatcanthenbeoptimised
byfurtherheattreatment.

Heat treatment: used to create a variety of microstructures and therefore mechanical properties, [See also:
49.6].

Rolling:

sheet(<2mmthick)

foils(~100mthick).

Optimisingrollingprocessesisimperativeinordertoproducesheetandfoilofadequatesizes
and quality (crackfree, reliable mechanical performance) for the intended structural
componentsforhotsurfacesofspacevehicles.

49.8.2.3

Powder metallurgy (PM) techniques

Production of TiAl materials by PM techniques is an attractive alternative to the ingot route,


providedthatthelevelsofinterstitialelements(O,N,C,H)isstrictlycontrolled.Thishasmeantthe
useofcleanroomtypefacilitiesandimprovedconsolidationtechniques.Thestartingmaterialscanbe
either,Ref.[4925]:

Prealloyedpowders:producedby:

PREP(PlasmaRotatingElectrodeProcess).

TGA(TiGasAtomisationProcess).

Blendedelementalpowders.

Processingtechniquesusedtoproduceintermetallicphasesare,Ref.[4925]:

Reactivesintering:priortotheconsolidationprocess.

Reactivehotisostaticpressing(HIP):duringtheconsolidationprocess.

HotworkingprocessesusedforingotmetallurgyarealsoappliedtoHIPpedprealloyedpowders.

49.8.2.4

Sheet forming

Conventional metal forming techniques can be applied to TiAl materials, provided that their
deformationcharacteristicsarefullyconsidered.Onestepsheetbendingoperationshavebeenusedto
produce500mmlonghatstiffenercomponentsinTi48Al2Cr(near)alloy,Ref.[4925].
Dependingontheircomposition,grainsizeandstrainrate,TiAlmaterialsexhibitsuperplasticityin
thetemperaturerange800Cto1300C.InvestigationofTi48Al2Cralloysheetshasshownthatitcan
be superplastically formed (SPF) at temperatures <1000C. This means that SPF facilities used for
conventionaltitaniumalloyscanalsobeusedforcertainTiAlmaterials,Ref.[4925].

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49.8.3

Joining

49.8.3.1

General

Sincetheintermetallicsareintendedforhightemperatureservice,joiningtechniquessuchaswelding
ordiffusionbondingaremoreappropriatethanadhesivebonding.Significanteffortisbeingapplied
todevelopingtechniquesthatcanproducereliable,acceptablequality,durablejoints.Thisisseenkey
tothesematerial,especiallyaluminides,findingapplications.

[Seealso:Chapter58forjoiningofhightemperaturematerials]

49.8.3.2

Welding

For TiAl materials, methods that provide reliable joints exhibiting good mechanical performance,
especially below the ductiletobrittle transistion temperature (DBTT) have been evaluated, Ref. [49
25].
Owing to the relatively low ductility of the alloys, methods that minimise heat input, and therefore
residualstressesareappropriate,suchasCO2LaserWelding.Preheatingtheworkpiecetoabovethe
DBTT is also required to obtain sufficient material ductility to accommodate thermal loads without
crackingoncooling.
Other possible welding techniques that could prove suitable for TiAl are electronbeam (EB) and
frictionwelding.

49.8.3.3

Brazing

Hightemperature brazing can be an appropriate joining technique provided that the ductility of TiAl materials is taken into account in the selection of a suitable processing temperature, Ref. [49-25].

49.8.3.4

Diffusion bonding

TheabilitytodiffusionbondmaterialsduringSPFisasimportantforintermetallicsasitisforallother
materials.A-TiAl alloy (Ti-47Al-2Cr-0.2Si) has been successfully diffusion bonded at its SPF temperature,
Ref. [49-25].

49.9 Further developments


49.9.1

Intermetallic compounds

49.9.1.1

General

Table49.9.1summarisessomeotherintermetalliccompounds,Ref.[4914].Refractorymetalsilicides
(MoSi2,NbSi2)werenotconsideredundertheFESTIPprogrammeduetotheirlimiteddevelopment,
Ref.[4923].

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Table49.91Furtherdevelopment:Intermetalliccompounds
Group

Compound

Advantages

Nb3Al

Melting point

NbAl3
Aluminide

TiAl3
Ti2AlNb *

Silicide

Berylide

Melting point
Density
Density
Oxidation (1)
Creep (1)
Ductility (2)

MoAl3

Melting point

Ti5Si3

Density

Nb5Si3

Melting point

Nb2Be17

Melting point

ZrBe13

Melting point

Key:

Oxidationindicatesmodestresistancetooxygen.

*Orthorhombicphase

(1)comparedwithconventionalneartitaniumalloys.

(2)comparedwithTiAl.

Disadvantages

Brittle
Oxidation
Brittle
Oxidation
Brittle
[Not stated]
Brittle
Oxidation
Brittle
Brittle
Oxidation
Brittle
Oxidation
Brittle
Oxidation

49.9.1.2

Titanium aluminides

Of the aluminides, titaniumbased compositions are undergoing significant further developments in


chemicalcomposition,processingandpropertycharacterisation,Ref.[4923].
The main disadvantage of intermetallics is their brittleness. The orthorhombic titanium aluminides
(based on the Ti2AlNb compound) offer improved ductility at ambient temperatures, e.g. ~16%,
dependingontheirmicrostructure,Ref.[4919].
Oxidation resistance remains an important characteristic for the applications currently under
consideration for intermetallics, i.e. in engines and spaceplanes. Those materials having modest
oxidationresistancerequiredevelopmentofsuitableprotectivecoatingsiftheyaretobeused.

49.9.2

Intermetallic matrix composites (IMC)

Mainlyowingtotheirductilityatambienttemperatures,orthorhombictitaniumaluminides,basedon
Ti2AlNb,arebeingconsideredforthematrixphaseofSiCreinforcedcompositematerials,Ref.[4919].

[See:49.10IntermetallicMatrixComposites]

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49.9.3

Protective coatings

Multilayertitaniumaluminidecoatingsareunderdevelopmentfortitaniumbasedmaterials.Theaim
is to improve the oxidation resistance of either conventional alloys or titanium matrix composites
(TMC), Ref. [4919]. These multilayer coatings are applied by a magnetron sputtering technique,
developedbyDLR.Theyconsistof,Ref.[4919]:

singlelayers:sequenceofTi3Al,TiAlandTiAl3,

gradient coatings: continuously increasing Alcontent towards the coatingenvironment


interface.

Multilayercoatingshavedemonstratedtheireffectivenessasoxidationprotectionforshorttermhigh
temperaturesandlongtermapplicationsattemperaturesupto600C,Ref.[4919].
For high temperature applications (between 600C and ~900C), coatings based on phase
(Ti25Al67Cr8) and twophase TiAl+Laves phase compositions were investigated. Of these, the
chromiumcontainingcoatingsareundergoingfurtherevaluation,Ref.[4919].

49.10 Intermetallic matrix composites


49.10.1 General
The IMC materials could provide opportunities to save weight on components destined for high
temperatureapplications.Theirpotentialroleis:

replacingconventionalmetals,whichtendtobecomparativelydense,suchsuperalloys.

extendingtheoperationalservicetemperatures,e.g.titaniumbasedmaterials.

Thereareongoingresearchanddevelopmentstudiesaimedatestablishingwhetheritistechnically
andeconomicallyviable.

49.10.2 Development
Higherspecificpropertiescanbeobtainedfromintermetalliccompoundsiftheyarecombinedwitha
reinforcementtoproduceanintermetallicmatrixcomposite(IMC).
Table 49.10.1 summarises the reinforcements and matrix material combinations, Ref. [494], [4917],
[4918],[4919],[4926].

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Table49.101Intermetallicmatrixcomposites:Summaryofcompoundsand
reinforcements
Matrix
Nickel aluminides:
[1]

Reinforcements
NiAl
Ni3Al

TiAl
Ti3Al

SiC
TiB2
TiC
C
Al2O3

Titaniumaluminides:
[2,3]

Ti2AlNb

SiC[SCS6]

[4]

SiC[SigmaSM1140+]

Iron aluminides:

FeAl

Niobium aluminides:

Nb3Al
NbAl3

Key: [1]

IC221/TiC particulate reinforcement. IC221/Al2O3 fibre reinforcement,


Ref. [49-17].
[2] Ti3Al + Nb/Al2O3 fibre reinforcement. These materials have comparable
CTE values of 10x10-6, typically. Ref. [49-4].
[3] Ti3Al + Nb/SiC fibre reinforcement, Ref. [49-18].
[4] Orthorhombic phase: Composition Ti-22Al-25Nb, Ref. [49-19] or Ti25Al-25Nb, Ref. [49-26].

Ofthese,titaniumaluminidesareconsideredthemostpromisingoptions.InitialstudiescoveredTiAl
andTi3Alcompoundswhichsufferedfromanumberofproblems,including,Ref.[4926]:

lowductilityandtoughnessatRT.

lackofductilityatthefibrematrixinterface.

embrittlementwhenexposedtoairatelevatedtemperatures.

More recent European work has concentrated on the Ti2AlNb compound which offers improved
propertycombinationsatRTandelevatedtemperatures,Ref.[4919],[4926].
Table49.10.2liststheperceivedrequirementsofareinforcementforIMCmaterials,Ref.[494],[4917].
These are very exacting, e.g. CTE matching between fibre and matrix, and it is likely that a
compromiseisneededtobereachedindevelopingsuchfibres.

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Table49.102Intermetallicmatrixcomposites:Requirementsforareinforcement
fibre
Mechanical

Physical

Other

High stiffness.
High temperature.
High melting point.
Low density.
CTE to match matrix.
Chemical compatibility.
Good oxidation resistance.
Ease of handling (spoolability).
Capable of mass production.

49.10.3 High temperature Ti-based IMC


49.10.3.1 General
Longtermoperationattemperatures>500Ccannotbeachievedbyconventionalnearalphatitanium
alloyMMC.Fortemperaturesupto700C(longterm)or1000C(shortterm)thekeycharacteristics
are,Ref.[4919]:

matrixhightemperatureproperties,

oxidationresistance,

fibrematrixinterfacestability,

creepresistanceofthematrix.

Additionally,thematrixrequiresalevelofductilityatambienttemperaturesinordertheexploitthe
potential reinforcement strength. A brittle matrix phase, or brittle surface layers, drastically reduces
thecompositetensileproperties,Ref.[4919].

49.10.3.2 Matrix
In general terms, TiAl and Ti3Al compounds exhibit a high modulus, ductilities <3% at ambient
temperaturesandhighCTE.Thecompositesproducedwiththesematriceshavehighresidualstresses
thatnegatethebenefitofthematrixoxidationresistance,Ref.[4919].
Dependingonthemicrostructure,orthorhombicphaseTi2AlNbcompoundscanprovideductilitiesof
up to 16% at RT, i.e. comparable with conventional near titanium alloys, but with improved
oxidationandcreepresistance,asshowninFigure49.10.1,Ref.[4919].

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Figure49.101Intermetallicmatrixcomposites:Characteristicsoforthorhombic
phasetitaniumaluminidematrix

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49.10.3.3 Reinforcement fibre


The development of orthorhombic TiAl matrix IMC has used SiC monofilaments, mainly because
thesehavebetterchemicalcompatibilityforTibasedintermetallicmatrices:

standard grade SCS6 silicon carbide monofilament (140m dia.). This fibre has also been
evaluatedinconventionaltitaniumalloymatrixcomposites(TMC),Ref.[4919].

carboncoated(4.5mthick)SigmaSM1140+SiCmonofilament(100mdia.),Ref.[4926].

Theinclusionofthereinforcementgenerallyreducesthematrixductility.Thiseffecthasbeenseento
be more severe for high monofilament diameters. The monofilament protective coating can be
consumedduringprocessing.Useofathickercoatingisseentoprotectthefibrewithoutstrengthloss,
Ref.[4926].

49.10.3.4 Processing
Amagnetronsputteringmethod,developedasafibrecoatingtechniquebyDLR,wasusedtodeposit
thematrix.Theasprocessedmatrixcontainsthreeorderedphases(2,andorthorhombic),Ref.[49
19].
A foilfibrefoil technique, developed by Insamet, was used to produce layups with 5 matrix foils
(125mthick)and4unidirectionalreinforcementplies.Thesewerethenconsolidatedbyhotpressing
undervacuum.
Figure49.10.2summarisesthevariousmanufacturingsteps,Ref.[4926].Theconsolidatedcomposite
containedthreematrixphases(2,0andorthorhombic),plussomeunwantedcarbidesattributedto
incompletebinderremoval.

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Monofilament winding

Filament wound onto a mandrel.

Winding pitch to give 35% volume fraction (taking into


account foil thickness & monofilament diameter).

Spray-applied polystyrene-based.

Used to maintain monofilament spacing during ply cutting


and lay-up stages.

Binder

Binder removed before consolidation, by typical heat-treatment:


400C for 2 hrs.

Lay-up

Matrix foils cleaned and degreased.

Chemical pickling (Krolls reagent) to promote bonding.

4-ply
[0] 4 SM1140+/Ti-25Al-25Nb (35% volume
fraction).
Alternate plies of reinforcement and matrix foils:

Reinforcemnt direction corresponds to rolling direction of matrix


foil.

Consolidation

Graphite mould (lower cost, easily machined & less


reactive with matrix than Ni-, Cr- or Co-based hightemperature mould materials).

Thin boron nitride layer applied to mould surface (to


prevent chemical reaction between matrix and mould).

Typical processing conditions for acceptable


composite: 1050C, 100MPa, 2 hrs.

Post-consolidation slow cooling (5C/min) to 650C


to relax residual stresses forming at the
reinforcement/matrix interface.

Acceptable composite: fully densified, good bonding with <0.5m


matrix/reinforcement reaction zone.

Figure49.102Intermetallicmatrixcomposites:TiAl/SiCcompositeInsamet
foilfibrefoilprocessingsteps

The effect of processing parameters (temperature, pressure, time) on composite consolidation were
investigatedandcanbesummarisedas,Ref.[4926]:

Temperature: Between 1000 to 1100C (under transus) was selected to be high enough to
produce acceptable matrix flow, but as low as possible to limit oxygen contamination and
deleteriouschemicalreactions.

A reaction zone 1m can seriously affect mechanical performance, whereas >0.5m can be
beneficial.Highlyreactivematrixphasescouldrequirelowerthicknessreactionzones.

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Pressure: 100MPa is high enough to enable acceptable matrix flow, but low enough to limit
reinforcementdamageandmovementofthereinforcement.

A gradual pressure increase was used to prevent damage to the reinforcement or graphite
mould.

Time:Between1to4hrs,relatedtotemperatureandpressureincludinga2hrisothermal(400C
or 500C) binder removal step. Postconsolidation slow cooling enables relaxation of residual
stresses(atthefilamentmatrixinterface).

Properbinderremovalisessentialtoavoidincorrectcompositeconsolidationorformationofbrittle
phasesatreinforcementmatrixinterfaces.

49.10.3.5 Composite properties


A tensile strength at RT of up to 2080MPa gives a broad indication of the mechanical performance
possibleforSCS6/Ti22Al25Nbcomposite,producedbythesputteringmethod,Ref.[4919].
For 4ply [0]4 SM1140+/Ti25Al25Nb composites (35% volume fraction), threepoint bend tests
providedsomepreliminaryvaluesfromtheprocessingstudy,Ref.[4926]:

Flexuralmodulus:120GPa

Maximumstress:1700MPa

Theflexuralmoduluswasconsideredtobelowerthanexpectedduetotheincompletebinderremoval
causingformationofcarbidesandreducingloadtransferfromthematrixtothereinforcement.
Publishedmechanicalpropertydataislimited.

49.11 Intermetallics: Potential applications


49.11.1 General
Oftheoriginalgroupsofintermetallics(Ni,FeandTibased),titaniumaluminidesareapproaching
thepositionwheretheycancompetewithsuperalloysbyofferingweightreductions,andtitaniumfor
elevatedtemperatureapplications.
ThetemperaturerangesinwhichTibasedintermetallicscancompetewithconventionalmaterialson
specificstrengthisshowninFigure49.11.1,Ref.[4919].

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CFRP

h
t
g
n
e
rt
S
cif Ti-based Intermetallic
i
Comp osite
c
e
p
S

High Temperature
Ti-based Intermetallic
Composite

Alp ha -Beta

Near-Alp
ha
Tita nium Allo
ys

Titan
ium
Alum
ini d
es

Ni-based Alloys
RT

200

400

600

800

1000

1200

Temperature [C]
Figure49.111Intermetallics:PotentialapplicationsElevatedtemperature
specificstrengthsofmaterials
ThespecificstrengthadvantagesofTiAlcouldreplacesomesuperalloysincompressorcomponents,
andtheirhightemperaturepropertiescouldhavesimilarresultsinotherengineparts.Forexample,
Ref.[4922]:

A demonstrator centrifugal compressor diffuser made of Ti48Al2Nb2Cr to replace IN718


provideda45%weightsaving.

TheUSJointTechnologyAdvancedGasGenerator(JTAGG)includedaTiAldiffuser.

InotherUSprogrammes,atarget80%increaseinpowertoweightratioanda30%reductionin
specificfuelconsumption,impliestheuseoftitaniumaluminidesifthisistobeachieved

Theincreasetheoperatingspeedandtemperatureofturbinedisksatboththerimandthebore
continues. The major US and European engine manufacturers are conducting independent
assessmentsoftitaniumaluminidesforsuchuses,Ref.[4920].

Orthorhombictitaniumaluminidecouldprovetobeasignificantmaterialfortheseapplications.

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49.11.2 Spaceplanes
Initially, the majority of intermetallic developments were in the USA. This largely used NASP
development programmes to progress the technology of these materials. Work continues under the
variousXprogrammevehicles.
InEurope,internationalandnationalbasedspaceplanedevelopmentstudies,includingFESTIP,have
also concentrated on the group of titanium aluminides for high temperature applications. For
example:

TiAl Alloys: for outer skin structures(up to800C). Demonstrator components,asshownin


Figure49.11.2havebeenmanufacturedbyPlansee(Austria),Ref.[4921].

TiAlmatrixcomposites:SiCfilamentreinforcedorthorhombictitaniumaluminide,Ref.[4919],
[4925].

MultilayerTiAlprotectivecoatings:onconventionaltitaniumalloysandTMCs,Ref.[4919].

Figure49.112Intermetallics:PotentialapplicationsOuterskinstructuresfor
spaceapplications

49.12 References
49.12.1 General
[491]

H.A.Lipsitt
TitaniumAluminidesFutureTurbineMaterials
WrightPattersonAirForceBase.AdvancedHightemperaturealloys:
ProcessingandProperties.ProceedingsoftheN.J.GrantSymposium,
June1985,p157164.ASMpublication

[492]

C.F.Yoltonetal
PowderMetallurgyofTitaniumAluminideComponents
TitaniumRapidSolidificationTechnology.EditedbyF.H.Froes&D.
Eylon1986TMSAIMEAnnualMeeting

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[493]

PowderMetallurgyofAluminideIntermetallics
MetalPowderReport,February1987,p8489

[494]

J.R.Stephens&M.V.Nathal
StatusandPrognosisforAlternativeEngineMaterials
NASALewisResearchCentre.TechnicalMemorandum108903
September1988

[495]

C.T.Liu
DevelopmentofNiandNiFeAluminidesforElevatedTemperature
StructuralUse
MiCon86:OptimisationofProcessing,PropertiesandService
PerformanceThroughMicrostructuralControl.ASTMSTP979,p222
237,1988

[496]

NickelAluminidesOakRidgeNationalLaboratoryLiterature,1988

[497]

A.I.Taubetal
EffectsofTestingEnvironmentontheElevatedTemperature
DuctilityofBorondopedNi3Al

[498]

C.T.Liu&V.K.Sikka
NickelAluminidesforStructuralUse
JournalofMetals,May1986,p1921

[499]

M.A.Stucke&H.A.Lipsitt
TheEffectofHeatTreatmentontheFatigueCrackGrowthBehaviour
ofTi3Al+Nb
TitaniumRapidSolidificationTechnology.MetallurgicalSociety
Conference,1986,p255262

[4910]

A.Khateeetal
NewTitaniumAluminiumXAlloysforAerospaceApplications
Journal,MaterialsEngineering,Vol.10,No.1,1988p3744

[4911]

S.C.Jhaetal
MicrostructureofTi3Al+NbProducedviaRapidSolidification
Processing
MaterialsScienceandEngineering,98(1988)p395397

[4912]

PowderMetallurgyofAluminideIntermetallics
MetalPowderReport,February1988,p8890

[4913]

J.Subrahmanyam
CyclicOxidationofAluminizedTi14Al24NbAlloy
JournalofMaterialsScience23(1988),p19061910

[4914]

S.Strothers&K.Vendula
HotExtrusionofB2IronAluminidePowders
MetalPowderIndustriesFederationandAmericanPowder
ProcessingInstituteConference1987,p597610

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[4915]

D.M.Simsetal
ReactiveSinteringofNickelAluminide
1987AnnualPowderMetallurgyConference,Dallas,Texas
May1720,1987.p575596

[4916]

A.I.Taub&KMChang
ElevatedtemperatureEmbrittlementofRapidlySolidifiedNickel
baseAlloysinOxygen
ProcessingofStructuralMaterialsbyRapidSolidificationProceedings
oftheSymposiumonEnhancedPropertiesofStructuralMetalsby
RapidSolidification,Orlando,Florida
Oct.69,1985.p437444.ASMPublication

[4917]

G.E.Fuchs&W.H.Kao
DevelopmentofIntermetallicMatrixCompositesforElevated
TemperatureService
ModernDevelopmentsinPowderMetallurgy.Proceedingsofthe
InternationalPowderMetallurgyConference,Orlando,FloridaJune5
10,1988.Volume20,p531542

[4918]

P.K.Brundley
DevelopmentofaNewGenerationofHighTemperatureComposite
Materials
Aeropropulsion87.Session1AeropropulsionMaterialsResearch.
p7387.ConferenceatNASALewisResearchCenterClevelandOhio.
November1719,1987

[4919]

J.Kumpfertetal:DLRCologne,(D)
AdvancedTMCsforHighlyLoadedComponents
ProceedingsofEuropeanConferenceonSpacecraftStructures,
Materials&MechanicalTesting.Braunschweig,Germany.46
November1998.ESASP428,p315320

[4920]

ExtractfromONERA(F)website:www.onera.fr(April2003)

[4921]

ExtractfromPlanseewebsite:www.plansee.com(April2003)

[4922]

Dr.W.Eisenetal:
PowderMetallurgySuperalloys
MaterialsWorld,Vol.4,(1996),p2224

[4923]

H.Kringsetal:MANTechnologie,(D)
FESTIP:TechnologyDevelopmentinMaterails
ProceedingsofConferenceonSpacecraftStructures,Materials&
MechanicalTesting,Noordwijk(NL).2729March1996.ESASP386
(June1996),p10851096

[4924]

G.Korbetal:Seiberdorf/Plansee,(A)
Characterisationoftitaniumaluminideintermetallics
ESTECContractARCS/SNo.8198/89/NL/PB(WONo.34)
ESAMetallurgyReportNo.2317(December1996)

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[4925]

H.Clemensetal:PlanseeAktiengescellschaft,(A)
IntermetallicGammaTitaniumAluminidesPotentialCandidates
forSpacecraftStructures
ProceedingsofConferenceonSpacecraftStructures,Materials&
MechanicalTesting,Noordwijk(NL).2729March1996.ESASP386
(June1996),p12971304

[4926]

J.Coletoetal:Insamet,(E)
DevelopmentofnewOrthorhombic(Ti25Al25Nb)/SiCIntermetallic
CompositesforAdvancedSpaceApplications
ProceedingsofEuropeanConferenceonSpacecraftStructures,
Materials&MechanicalTesting.Braunschweig,Germany.46
November1998.ESASP428,p301308

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50 Refractory and precious metals


50.1 Introduction
This chapter provides a basic description of the Refractory Metals and Precious Metal Group
(PMG). They all have high melting points (1800C to 3500C) and are of primary interest for
propulsionsystemsandthinfilmprotectivecoatings.
[Seealso:Chapter74forprotectivecoatings]

50.2 Materials
50.2.1

General

Thekeymaterialsare:

Platinum

Rhodium

Iridium

Rhenium

Molybdenum

Tungsten

Tantalum

Niobium

50.2.2

Characteristics

Thematerialsareofinterestforsuchcharacteristicsas:

veryhighthermalstability.

inertness.

oxidationresistance.

corrosionresistance.

Thematerialslistedhavethesecharacteristicstovaryingdegrees,withsomebeingbetterthanothers.
Theyallhavehighdensities.Table50.2.1identifiestheirmainfeatures.

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Table50.21Refractoryandpreciousmetals:Attributesanddisadvantages
Metal

Niobium (Nb)
Molybdenum
(Mo)
Tantalum (Ta)
Rhenium (Re)

Tungsten (W)
Platinum (Pt)
Rhodium (Rh)
Iridium (Ir)

Attributes

Disadvantages

Ductile
High melting point
Ductile
High melting point
Ductile
Very high melting point
Good thermal conductivity
Ductile
Very high melting point
High strength
Ductile
Very high melting point
High thermal conductivity
High strength
Ductile
Very oxidation resistant
High thermal conductivity
High strength
Very oxidation resistant
Ductile
High strength
High melting point

Modest oxidation
resistance
Modest oxidation
resistance
Modest oxidation
resistance
Modest oxidation
resistance
High density
Brittle below 400C
High density
Expensive
High density
Very expensive
Expensive
High density

50.2.3

Basic properties

Table50.2.2liststhebasicpropertiesoftherefractoryandpreciousmetalsgroup.PtRhcompositions
areusedforthermocouples.

Table50.22Refractoryandpreciousmetals:Basicphysicalproperties
Metal

Niobium (Nb)
Molybdenum
(Mo)
Tantalum (Ta)
Rhenium (Re)
Tungsten (W)
Platinum (Pt)
Rhodium (Rh)
Iridium (Ir)
Key

Density

MeltingPoint

CTE

ThermalConductivity

(kgm3)

(C)

(106C1)

(Wm1C1)

8570

2468

7.2

53.7

10220

2617

5.1

138

16600
21000
19300
21450
12400
22400

2996
3180
3410
1772
1965
2410

6.5
6.6
4.5
9.0
8.5
6.8

57.4
48.0
173
71.6
150
147

:Indicativepropertiesatroomtemperature.
:PreciousMetalsGroup

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50.2.4

Alloys

Themetalsareusedinalloyform.CommonexamplesareshowninTable50.2.3.

Table50.23Refractorymetalalloys:Examples
Composition

Alloy

Nb-10Hf-1Ti
Nb-10W-10Hf-0.1Y
Mo-0.5Ti-0.02C
Mo-1Ti-0.3Zr
Mo-0.5Ti-0.1Zr
Ta-2.5W
Ta-7.5W
Ta-10W

C-103 for Thrusters


C-129Y
Alloy 362
TZC
TZM
Tantaloy 63
Tantaloy 61
Tantaloy 60

50.3 Applications
Forspaceapplications,refractoryandpreciousmetalsareprincipallyusedfor:

Propulsionsystemitems(hotgasenvironment),and

Thinfilms,i.e.protectiveandinertcoatings.

The combination of good thermal conductivity and very high temperature stability continues to
dictate the use of these materials in close proximity to hot gas streams within propulsion systems.
Theirveryhighdensitiesremainarestrictingfactorandsoprecludesthemfromstructures.
[See:Chapter48forcoatingsappliedtosuperalloys;Chapter74forprotectivecoatings]

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51 Beryllium
51.1 Introduction
As a structural material, beryllium has a number of highly desirable characteristics. These are,
however, offset by some significant disadvantages. This has left beryllium as an underutilised
materialrequiringspecialistexpertiseandfacilities.
Thischapterdescribesthecharacteristicsofthevariousberylliumgrades,alongwithtypicalproperty
data.Theeffectoftemperatureonbothmechanicalandphysicalpropertiesisgiven.
Comments on the safety aspects of working with beryllium are summarised, along with a list of
Europeanorganisationswithexpertiseinthefabricationofberylliumstructures.

Fordesigndata,refertoMILHDBK5,Ref.[514].

51.2 Characteristics
51.2.1

Features

Table51.2.1summarisestheadvantagesandproblemsassociatedwithusingberyllium.

Table51.21Beryllium:Characteristics
Attributes

Limitations
3

Low density: 1860 kg/m


Exceptional strength & stiffness: E = 303 GPa.
High temperature stability
Excellent electrical & thermal conductivity
Low coefficient of thermal expansion

Brittleness
Notch sensitivity
Modest fracture toughness
Toxicity of beryllium oxide

51.2.2

Applications

Theattributesindicatesuitabilityforapplicationsrequiring:

dimensionalstability,

rigidity,and

thermalresistance.

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Thelimitationsimply:

damageintolerance,

joiningproblems,and

uncertaintyonstructuralintegrity.

Successfulapplicationsshowthatthesedisadvantagescanbeovercome.Thetoxicityissueisresolved
byusingdedicatedmachiningfacilities.

51.3 Products and facilities


51.3.1

Source

Allberylliummaterialproductsoriginatefromasinglesource:BrushWellmanInc.,USA.

51.3.2

Materials

51.3.2.1

Processes

Hotpressedpowders:Themajorityofgradescanbesubsequentlyworked.

Castingfrommeltsisalsofeasible.

Metalworking,toachievetherequiredfinalproductform,e.g.:

rolling,

extrusion,

forging,

forming,or

machining.

51.3.3

Grades

Table51.3.1showsavailableberylliumgrades,optimisedforspecificapplications.

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Table51.31Beryllium:Grades
Grade

S-200-E
S-200-F
S-200-FH
SR-200-E
S-65
O-50
I-70
I-220
I-400
PF-10
PF-60
B-26-D
SP-200F
SP-65
IP-70
Beryl-coat

Quality

Standard
Sheet
Structural (ductility)
Optical (isotropic)
Instrument (stability)
Foil (purity)
Foil
Casting
Structural
High purity
Optical
Corrosion resistance

Production

Hot pressed
Vacuum hot pressed (VHP)
Hot isostatic pressed (HIP)
VHP & Hot rolled
Hot pressed
HIP (high density)
Hot pressed
Hot pressed
Hot pressed
Hot pressed & rolled to <3mm
Hot pressed & rolled to <3mm
Vacuum melted
Impact grinding
Coating of Be

Key Powder

Certainpropertiescanbeselectivelyenhanced,e.g.:

ductility,

isotropy,

stiffness,

purity,

thermalordimensionalstability.

51.3.4

Fabrication

51.3.4.1

General

Variouspointscanbemadetoclarifyaspectsofberylliumtechnology:

The properties of powderbased beryllium are influenced by particle size, oxide content and
impurities.

Vacuumhotpressingistheprincipalformofpowderconsolidationwithhotisostaticpressing
(HIP)usedforhighpuritygradestominimiseporosity.

Machiningofberylliumrequiresprecisionandsharpcuttingtoolstoavoidsurfacedamage.

Machiningisundertakeninacleanenvironmenttoavoidmaterialcontaminationandtorestrict
thetoxicmaterial.

Toavoidmechanicaldamage,electricaldischargemachining(EDM)orelectrochemicalmilling
(ECM)canbeusedforcutting.

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Machined beryllium is always etched to remove a surface layer (0.1 to 0.25 mm) to eliminate
surfacedefects.

Beryllium can be worked by hot forming, preferably by bending and rolling, which utilise
compressiveratherthantensilestresses.

Brazing is an accepted form of joining, with aluminium as the principal braze material. Zinc
andsilvercanalsobeused.

Acompletedberylliumassemblycanbecoated(Berylcoat)toprovidecorrosionprotectionand
sealthesurfaceoxide.

Asizerestrictionof1.2m2existsonmaterialobtainableinhotpressedform.

Berylliumproductsaresensitivetomachininginducedsurfacedamage,i.e.possiblesourcesof
fractureinitiation.

51.3.4.2

Facilities

In the USA, the major source is Brush Wellman. Within Europe, organisations with expertise in
Berylliumare:

W.C.Heraeus(D):

SAGEM(F):

51.3.4.3

Joining

Mechanical fastening can be used for joining despite the weaknesses that machined holes induce in
thematerial.Brazingandadhesivebondinghavebeensuccessfullyapplied.

51.4 Properties
51.4.1

Influence of microstructure

Thepropertiesofberylliumgradesareprincipallydeterminedbythemicrostructure,inparticular:

grainsize,

oxidecontent

Twoparametersdominate:

Yieldstrengthandelongation(ductility)increaseasgrainsizediminishes,withdependenceon
(grainsize)

Increaseddispersedoxidecontentimprovesthemicroyieldstrength,i.e.thestressrequiredto
producethefirstpermanentstrainof1x106or1x104%.

51.4.2

Grades

Therearethreebasicgradesofberyllium:

Structural.

Optical.

Instrument.

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51.4.3

Mechanical properties

Table51.4.1providesmechanicaldataonarangeofberylliumgrades.

Structuralgrades:S200E,S200FandS65arewidelyused.SheetgradeSR200Eexhibitshigh
strengthsandductility.

Instrument grades: Use both fine grain and highly dispersed oxide content to ensure high
microyieldstrengths.I220andI400arethemostrecognisedgrades.

Optical grades: e.g. I70, are a high purity composition and hot pressed to give an isotropic
material.

Table51.41Berylliumgrades:Compositionandtensileproperties
Composition
Grade

TensileProperties

Be
(min)

BeO
(max)

UTS
(MPa)

YS
(MPa)

Elong
(%)

Note

Bal.

S-200-E

98.0

2.0

<0.2

276

207

S-200-F

98.5

1.5

<0.2

325

242

S-65

99.0

1.0

<0.1

290

207

I-70

99.0

0.7

<0.2

242

173

I-220

98.0

2.2

<0.2

380

276

I-400

94.0

4.3

<0.3

346

Standard
Quality
High
ductility
High purity
High
stability
Regular or
selected
grade

SR-200E

98.0

2.0

<0.2

484

346

10

Sheet 7mm

51.4.4

Effect of temperature

51.4.4.1

General

Berylliumhasameltingpointof1285C,whichisnotparticularlyhigh,butdespitethisitisusedin
hightemperature(to760C)applicationsforitsexcellentthermalconductivityandheatcapacity.

51.4.4.2

Mechanical properties

For hightemperature applications, the residual mechanical properties of beryllium should be


established.Aswithallmetals,propertiesarealsodependentonthethermalandmechanicalworking
history. Table 51.4.2 and Figure 51.4.1, Figure 51.4.2 and Figure 51.4.3 indicate mechanical property
changesoverthetemperaturerange200Cto+800C.

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Table51.42BerylliumgradesS200FandSR200E:Mechanicalpropertiesat
varioustemperatures
Temp

YS

TS

(C)

(MPa)

(MPa)

(%)

0.2%/3min

0.5%/3min

1.0%/3min

240
[345]
240
[345]
240
[345]
240
[345]
240
[345]
240
[345]
237
[-]
230
[310]
208
[-]
178
[240]
142
[-]
124
[-]
102
[140]
80
[-]
58
[-]
30
[-]
<10
[-]

324
[483]
324
[483]
324
[483]
324
[483]
324
[483]
324
[483]
308
[-]
290
[420]
248
[-]
210
[305]
168
[-]
144
[-]
115
[170]
95
[-]
60
[-]
30
[-]
<10
[-]

0.5
[0.5]
1.2
[1.2]
2
[2]
2
[5]
2
[5]
2
[10]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]

[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
40
[-]
30
[-]
16
[-]
8
[-]
[-]

[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
55
[-]
38
[-]
22
[-]
10
[-]
[-]

[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
[-]
160
[-]
105
[-]
80
[-]
50
[-]
32
[-]
18
[-]
5
[-]

-200
-150
-100
-50
0
RT
100
200
300
400
500
550
600
650
700
750
800
Key

CreepStrength(MPa)

YS:YieldStrength;TS:TensileStrength;D:Ductility
DataforSR200F;[DataforSR200E]

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Figure51.41BerylliumS200grades:Effectoftemperatureon0.2%yieldstrength

Figure51.42BerylliumS200grades:Effectoftemperatureonultimatetensile
strength

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Figure51.43BerylliumS200grades:Effectoftemperatureonelongation

51.4.4.3

Physical properties

Table 51.4.3, Figure 51.4.4, Figure 51.4.5, Figure 51.4.6 and Figure 51.4.7 show how the physical
propertiesvarywithtemperature,whichareimportantforthermalmanagement.

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Table51.43Beryllium:Effectoftemperatureonmodulusandphysicalproperties
Property
Temp
(C)

CTE (10-6/C)

Specific Heat
(J/kg/C)

Thermal
Conductivity
(W/m/C)

Thermal
Diffusivity
(m2/s)

Tensile Modulus
(GPa)

Differential

Linear

-200

0.2

5089

293

1500

300

-150

1.9

7.32

419

830

300

-100

4.5

7.74

1004

480

300

-50

7.5

8.98

1298

310

300

10.0

9.95

1694

240

300

RT

10.2

2009

200

300

100

11.6

2135

163

0.15

297

200

12.75

2386

141

0.12

291

300

13.6

2553

127

0.10

283

400

14.3

2679

116

0.09

268

500

14.8

2763

107

0.08

242

600

15.25

2846

98

0.07

180

700

15.55

2930

89

0.06

(80)

800

15.8

3014

80

0.05

(40)

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Figure51.44Beryllium:Effectoftemperatureonthermalconductivity

Figure51.45Beryllium:Effectoftemperatureondiffusivity

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Figure51.46Beryllium:Effectoftemperatureonexpansion

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Figure51.47Beryllium:Effectoftemperatureonspecificheatcapacity
51.4.4.4

Corrosion

Finished beryllium components are normally varnished to seal the surface. This provides corrosion
protectionandamoisturebarrier.

51.5 Health and safety


51.5.1

Facilities

The machining and handling of beryllium needs to be undertaken in dedicated facilities and with
protectionforpersonnelagainstberylliumoxide,whichisahazardous,toxicmaterial.

51.5.2

Health aspects

Longterm exposure increases the risk of contracting `berylliosis. Inhalation of beryllium and
beryllium oxide dust is the most hazardous form of contact. Handling beryllium parts is safe,
providingdirectcontactwiththeskinisavoidedthroughtheuseofgloves.

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51.5.3

Extraction

Machineshopsrequireseparateventilationandfilteringsystemswithlocalisedextractiontocapture
aerosols and fumes. Machining is generally performed under wet conditions, to minimise powder
particles entering the air. Regulatory exposure limits are defined for operatives working with
beryllium.

51.6 Potential applications


51.6.1

Resum

Berylliumisunderutiliseddespiteitsobviousstiffnesstoweightadvantageoverothermaterials.The
necessityfordedicatedmanufacturingcapabilitiestocontaintheperceivedhealthhazardremainsan
inhibitingfactor.However,theexpandinguseofsocalledbrittlematerialscanhelpinovercomingits
traditionallyperceivedweaknessofbeingadamageintolerantengineeringmaterial.

51.7 References
51.7.1

General
[511]

D.P.Bashford
GuidelinesfortheUseofBerylliuminSpacecraftApplications
FulmerResearchReportR878/4A/January1982
ESTECContract4389/80/NL/AK(SC)

[512]

Interatom
BerylliumThermalProtectionTechnology(TPT)
FinalReport.May1991.ESTECContract8824/90/NL/PP

[513]

T.E.H.Leman&W.R.Newell
AStudyontheStructuralApplicationsofBeryllium
BritishAircraftCorporation,1974
ESROContractorReportCR209.ESTECContractNo.1553/71

[514]

MILHDBK5F:MetallicMaterialsandElementsforAerospace
VehicleStructures
Vol.1&2.November1990

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52 Ceramic matrix composites


52.1 Introduction
Ceramicmatrixcompositesformtwomaingroups:

Continuousfibrereinforcements.

Whiskerreinforced.

Various combinations of reinforcement and matrix have been assessed, and continue to be studied.
Thischaptersummarisesthematerialsunderdevelopment,alongwithadiscussionoftheproperties
andhowtheseareinfluencedbythehightemperature,oftenoxidising,operationalconditions.
The manufacturing processes used arepresented because they influence the material characteristics.
Whilst silicon carbide fibre reinforced silicon carbide composite (SiCSiC) were the first group to
becomecommerciallyavailable,interesthasmovedtocarbonfibrereinforcedsiliconcarbide(CSiC)
composites.Thisislargelyduetotheirpotentialapplicationsforthehotstructuresofreuseablelaunch
vehicles (RLVs) in areas where the temperature exceeds 1200C, i.e. with carboncarbon (CC)
materials,[See:Chapter54].SiCSiCremainsanoptionforlowertemperatures,Ref.[5261].
Thecharacteristicsofdevelopmentmaterialsarelikelytochange.

52.2 Continuous fibre composites


52.2.1

Matrix groups

52.2.1.1

General

Theprospectivematricesaredescribedbygenericgroupswhichdefinetheprincipalconstituent,but
donottakeintoaccountanymodifyingelementsorcompounds.Themainoptionsare:

carbides.

nitrides.

oxides.

Oxidesappeartobepreferableforuseinoxidisingenvironments.

[Seealso:Chapter54forcarbonfibrereinforcedcarbonmatrix(CC)composites]

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52.2.1.2

Silicon carbide

SiC is attractive for the thermal stability offered and is, in theory, capable of operating to 1650C
whilstretainingstrength.Thecarbideformsathinprotectiveoxidelayerinoxidisingenvironmentsto
preventfurthergrossoxidation.Itisveryhard,andhasexcellenterosionandcorrosionresistance.Its
thermalconductivityisgreaterthanthatofSi3N4orAl2O3.

Technology studies have examined the technical feasibility and cost effectiveness of various
processingmethodscomparedwithpreviouslyusedCVItechnique.
Themainprocessingmethodscanbegroupedas,Ref.[5261]:

gasphaseinfiltration.

liquidphaseinfiltration(prepregtechnology).

liquidsiliconimpregnation.

solidstateprocessing(sintering).

[See:52.3]

52.2.1.3

Silicon nitride

Si3N4 possesses marginally poorer thermal stability than SiC. However, unreinforced powderbased
Si3N4 shows greater strength and toughness than its powderbased SiC counterpart. In addition, its
thermal shock resistance is better than that of SiC, not least because the coefficient of thermal
expansionislower.Thatsaid,theissueissomewhatconfusedinthecaseofcomposites,ascontinuous
reinforcedSi3N4hasbeenmadebythreeroutes.Theseare:

PressurelessReactionBonded(RBSN)

HotPressedPowder(Si3N4,withsinteringaids)

CVI/CVD

TheRSBNcanbeformedat1450Cbynitridingsiliconpowder,whilstthehotpressedSi3N4requires
1750C. The RSBN tends to pose problems with excessive porosity if fibres are present, and the hot
pressedpowdergivespoorerthermalstabilityassinteringaidsareadded.ThisleavesSi3N4prepared
bychemicalvapourreactionsasofferingamatrixwithreasonablestabilityprovidedbycompositional
control.

52.2.1.4

Alumina

Alumina is promoted on the grounds that it is an oxide with good thermal stability. The main
drawback of alumina as a matrix is brittleness and the difficulties in toughening the material with
reinforcements,suchthatthermalshockdoesnotresultincatastrophicfailure.Thetendencyhasbeen
to include additional compounds, such as silica, to provide better fracture characteristics but which
reducethermalcapabilities.Todate,aluminamatriceswithcontinuousfibreshavebeenpreparedby
CVIandSolGeltechnology.Theamountofworkdoneontheserouteshasbeenmodest.

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52.2.1.5

Zirconia

OnlyamodestamountofworkhasbeendevotedtocompositespreparedbySolGelandHotPressing
routes. In the powderbased monolithic form, zirconia is noted for its toughness in the partially
stabilised(PSZ)andtransformationtoughened(TTZ)forms.Thetoughnessismodestattemperatures
upto1000C.Thisisamatrixwithpotential,ratherthanproven,capabilitiesbeyond1000C.

52.2.1.6

Other nitrides and carbides

BN, TiC, B4C and AlN have been tried as matrices, but not developed. They may have supporting
rolesas:

BN:Softceramicfibrecoatings

TiCandB4C:Veryhardceramicswithgoodabrasionanderosionresistance.

AlN: Hard ceramic with good thermal conductivity and the ability to form a stable surface
oxide.

52.2.2

Composite development

ThedevelopmentofcontinuousfibreCeramicMatrixComposites(CMC)hascentredonthegroups
showninFigure52.2.1.

Silicon Carbide (SiC)


Principal matrices studied

Silicon Nitride (Si 3N 4)


Alumina (Al 2O 3)
Zirconia (ZrO2)

Boron Nitride (BN)


Limited evaluation for matrices

Titanium Carbide (TiC)


Boron Carbide (B4C)
Aluminium Nitride (AlN)

Figure52.21CMCcompositedevelopment

Asaresumoftheworkundertakenoncontinuousfibrecomposites,Table52.2.1identifiesthemain
fibre/matrixcombinationsandthoseorganisationsundertakingthework.

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Table52.21Ceramicmatrixcomposites:Fibreandmatrixcombinationswithsourcesofdevelopment/investigation
Reinforcement
Carbon fibres
SiC fibres

Matrix

SiC

SiC (Nicalon yarns)

SiC

Carbon, Nicalon,
Alumina fibres (Saffil)

SiC

Carbon, Nicalon,
Nextel 312

SiC

Nextel 312

SiC

SiC monofilament

Si3N4 or RSBN

SiC monofilament

RSBN

SiC monofilament

Si3N4 direct from


powder

SiC (Nicalon yarn fabric)

Si3N4

Source [Ref.]

Comments

SEP, France.
Ref. 52 [1 to 10]

C-SiC & SiC-SiC traded as SEPCARBINOX & CERASEP. Produced by CVI


techniques. SEP has the most advanced production capability in the world.
Their ceramic matrix composites are applied to a wide range of propulsion
units & thermal protection systems for space vehicles. Reasonable property
data available. Technology licensed to DuPont.

ORNL, USA.
Ref. 52 [11 to 20]

CVI techniques for infiltrating SiC into Nicalon fabrics. Work has
concentrated on reducing processing times. Limited mechanical property
data available. Pyrolytic graphite coating on fibres prevalent. There is a
commercial link with Babcock & Wilcox. Proposed uses in heat exchangers,
turbine engines & Space Power Systems (SDI).

RECOMP-201 for the C-SiC version. Nicalon fabrics form the principle SiC
Refractory Composites
reinforcement. Published papers by RCI are scarce. Work supported by
Inc., USA. Ref. 52 [21,22]
USA Department of Energy.
Thermo Electron Corp.,
USA. Ref. 52 [23,24]

A range of composites prepared by CVI/CVD, including SICONEX 3M,


with Nextel fibres. Intended use in a combustion environment at 1450C.
Tungsten coating included.

3M Co & Amercom, USA. SICONEX composite produced by CVI/CVD. Amercom have interests in
Ref. 52 [25]
Thermal Protection Systems for space vehicles.
AVCO SCS-6 derivative fibre used. Composites formed by reaction bonding
NASA-Lewis Research
(nitriding) silicon powder/fibre compacts; giving composites of high porosity
Center, USA. Ref. 52 [26]
(30 to 40% of matrix). Fibre volume fractions up to 40% possible.
Norton Co., USA.
Ref. 52 [27]

AVCO SCS-2 & SCS-6 monofilaments used. SCS-6 with the thicker carbonrich SiC outer coating gave the highest strength. Processed at 1450C.

Battelle Columbus, USA. Commercial grade Si3N4 powder with 8wt.% Y2O3 & 4wt.% Al2O3 as
sintering aids. Slurry coating & filament winding used followed by hot
Ref. 52 [28]
pressing at 1750C, under vacuum.
ORNL, USA. Ref. 52 [14] Initial work on CVI processing.

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Reinforcement

Matrix

Alumina-based fibres:
AB-312 [3M], Saffil [ICI],
FP [DuPont], -Al2O3

Alumina (Al2O3)

Nicalon fabric
Alumina (Saffil)
Zirconia fibres (ZrO2)

Al2O3

Alumina (FP), Nicalon

Al2O3

SiC monofilament [AVCO]

Zirconia (ZrO2)

Nicalon

Al2O3

Source [Ref.]

CVI processing route. -Al2O3 fibres gave the best results. Brittleness
SEP, France. Ref. 52 [29] proved a problem, owing to good fibre:matrix bonding. Interface
modifications needed to improve toughness.
University of Florida,
Preliminary processing by Sol-Gel route with high temperature
Ceramics Division, USA.
densification at 1200C.
Ref. 52 [30]

Aerospatiale Aquitaine,
France. Ref. 52 [31]
ONERA, France.
Ref. 52 [32]

Zirconia:
Nicalon fibres, with &
without BN coatings

Carbon fibres

ZrO2 + 50mol%SiO2
(Zircon)
ZrO2 + 50mol%TiO2
(Titanate)
Boron Nitride(BN)
Titanium Carbide (TiC)
Boron Carbide(B4C)

Carbon fibres

SiC

Comments

Naval Research Labs,


USA. Ref. 52 [33]

SEP, France.
Ref. 52 [4,5,34]
University of Bordeaux,
France. Ref. 52 [35]
MAN Technologie,
Germany. Ref. 52 [60]
DASA, Germany.
DLR, Germany.

Preliminary processing by Sol-Gel route. Problems noted with fibre wetting,


fibre degradation & matrix cracking on cooling.
Composites achieved by colloidal infiltration & pressureless sintering at
1235C. Theoretical densities of 70% achieved with 20% by volume of fibre.
Initial work noted problems in thermal expansion mis-match between pure
Zirconia matrix & fibre. Processing by vacuum hot-pressing & nitrogen hot
pressing at 1200 to 1600C. Significant improvements noted with coated
fibres and Zircon & Titanate matrices.
Porous preforms of 2-D Carbon-Carbon densified by CVI. The preforms
consisted of carbon fibre fabric held together with a small quantity of
carbon (pyrolysed methane). The three matrices were evaluated, along with
SiC; the last became the eventual choice.
European FESTIP study: Material and technology development for
reusable launch vehicle (RLV) hot structures. Comparison of materials
produced by different processing routes. Includes internal oxidation
protection methods for applications >500C in oxidising atmospheres,
Ref.52 [61].

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52.2.3

Technology status

Figure52.2.2summarisesthetechnologyandrelatedcommercialdevelopmentsofvariouscomposites.
Of these, complex hot structural components have been produced in CSiC composites. Developed
andmanufacturedinEurope,theseitemshaveundergoneextensiveevaluationandqualificationfor
theXprogrammevehicles,i.e.X38andCRV,Ref.[5262],[5263].

Primary systems
Matrix

Fibre

SiC

Carbon

SiC

SiC

Secondary developments
Matrix

Fibre

Si3 N4

SiC

Al2O3

SiC

ZrO2

SiC

Figure52.22CMCcompositedevelopment:Materialcombinations

52.2.4

Characteristics

Table52.2.2summarisesthetypicalpropertiesofanumberofcomposites.

[See:53.3forcharacteristicsofCSiCmaterialsevaluatedunderFESTIP]

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Table52.22Developmentcontinuousfibrereinforcedceramicmatrix
composites:Typicalproperties
Fibre

Matrix

[Source]

[Process]

FibreVol.%
[Type]

SiC
[N]

SiC
[CVI]

45
[U]

SiC
[N]

SiC
[CVI]

40
[B]

SiC
[N]

SiC
[CVI]

40
[B]

SiC
[A]
SiC
[A]

Si3N4
[RSBN]
Si3N4
[RSBN]

40
[U]
50-60
[U]

SiC
[A]

Si3N4
[HP]

44
[U]

Al2O3
[FP]
SiC
[N]
Carbon
[-]

Al2O3
[CVI]
ZrO2
[HP]
SiC
[Various]

40
[U]
[-]

Key

MechanicalProperties
[Reference]

flex @ RT: 500MPa


flex @ 1000C: 280MPa. Ref. [52-11],
[52-16]
flex @ RT: 310MPa
flex @ 1000C: 140MPa (in air)
tens @ RT: 230MPa
tens: 0.75%. Ref. [52-12]
flex @ RT: 350MPa
Fracture Toughness (max): 10MPam.
Ref. [52-22]
flex @ RT: 900MPa
tens @ RT: 530MPa
flex @ RT: 750MPa
Ref. [52-27]
flex @ RT: 900MPa
flex @ RT: 400MPa Ref. [52-28]
Fracture Toughness: 7MPam
(unchanged)
flex @ RT: 250MPa
flex @ 1200C: 100MPa. Ref. [52-29]
flex @ RT: <700MPa
Ref. [52-33]
[See: 52.3]

N:Nicalon.

HP:HotPressed.

A:AVCO(SCS6).

FP:FibreFP,DuPont.

CVI:ChemicalVapourInfiltration.

U:Unidirectionalcomposite.

RSBN:ReactionBondedSiliconNitride.

B:Bidirectional(fabric)composite.

52.3 Carbon fibre reinforced silicon carbide


52.3.1

General

52.3.1.1

Characteristics

CSiC aims to provide a strong composite with better oxidation resistance than an allcarbon
composite.[Seealso:Chapter54forcarboncarbon].CSiCcompositesareanaturalprogressionfrom
carboncarbon (CC) for hot structures and thermal protection systems, [See also: Chapter 70 and

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Chapter71].ThelowdensitycombinedwithacontrolledCTEhavemadeCSiCofinterestforhigh
precisionopticalstructures,Ref.[5264],[Seealso:52.7forapplicationexamples]

52.3.1.2

Product sources

ThecompositeismarketedbySEP(France)asSEPCARBINOXforuseinoxidisingenvironmentsto
1500C.
InGermany,MANTechnologie,DASA(whichbecamepartofEADS)andDLRhaveexpertiseinthe
designdevelopment and manufacture of CSiC complex hot structure components. These
technologies also form the basis for the development of dimensionally stable CSiC materials for
opticalstructures.ThematerialsproducedinGermanyusedifferentprocessingmethods.

52.3.2

Fibres

52.3.2.1

General

The advantage of carbon fibres over all others is their capability to retain good tensile strength at
temperatures approaching 1200C. This strength retention is conferred to the composite to a higher
levelthanispossiblewith,forexample,siliconcarbidefibres.

52.3.2.2

Preforms and near net-shapes

Carbonfibrescanbeconvertedtopreformstoproducecompositesinlarge,complexshapeseitherby:

fabric,

braiding,

3D,

filamentwinding.

Nearnet shape components are feasible. Unlike CC composites, machining of finished CSiC
compositesneedscarefulconsiderationowingtothehardnessofthematrix.

52.3.3

Matrix

52.3.3.1

Processing

Inadditiontochemicalvapourinfiltration(CVI),otherprocessingmethodsdevelopedinclude:

infiltrationandpyrolysisofsiliconpolymersprocess,alsodescribedasPPPpolymerpyrolysis
process,developedbyDaimlerBenzAerospace/DASA,Ref.[5259],[5271].

LPI liquid polymer impregnation, developed by DASA Dornier (now part of EADS ST), Ref.
[5260],[5271].

GradientCVI,developedbyMANTechnologie,Ref.[5260].

CombinedLPI/CVImethod,Ref.[5261].

LSIliquidsiliconinfiltration,developedbyDLR,Ref.[5261].

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[Seealso:88.21and88.22fordescriptionsofCVDandCVI]

The processing route selected is largely dependent on the requirements of the part to be produced,
includingRef.[5261]:

mechanicalperformance,

environmentalconditions,

maximumtemperature,

partcomplexity,

reusability,

serviceintervals.

52.3.3.2

Porosity

CSiCproducedbyCVIhasresidualporosityof~10%.Thisisnotconsideredunacceptablebecausethe
composite possesses sufficient integrity. It can be argued that pores act as crack stoppers, so
controlling the fracture characteristics. A higher porosity level leads to a loss of composite integrity
throughalackofsupportbythematrix.Italsoallowsaccessbytheexternalenvironmentandattack
byoxygenofthefibresandfibre/matrixinterface,[See:Oxidation].

52.3.4

Characteristics

52.3.4.1

Properties

Figure52.3.1showsloaddisplacementcurvesforaCSiCcompositeatRTandat1600C,Ref.[5263].
These illustrate the composites progressive failure characteristic. At high temperature, the material
remainselasticatloadsexceedingthemaximumseenatRT,Ref.[5263].CSiCcompositedeveloped
fortheX38bodyflapbyMANTechnologie,Germany,[Seealso52.7].

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C-SiC composite developed for the X-38 body flap by MAN Technologie, Germany.
Single edge notched beam tests. Crack length to width = 0.45

Figure52.31Ceramicmatrixcomposites:CSiCloadversusdisplacementcurves
atRTand1600C
Theprocessingrouteselectedtocreatethecompositeinfluencestheproperties.Table52.3.1compares
thecharacteristicsofCSiCcompositesproducedbydifferentprocessingroutes,Ref.[5259],[5260],
[5264].

Table52.31Ceramicmatrixcomposites:TypicalpropertiesofCSiCcomposites
producedbydifferentprocessingmethods
SiCMatrixprocessingmethod
Property

LPI

Fibre volume fraction


Porosity
Density
Tensile strength
Rupture strain
Flexural strength
Compression strength
Shear strength
Youngs modulus

Vol.%
Vol.%
g/cm3
MPa
%
MPa
MPa
MPa
GPa

40
23
1.8
260
1.2
365
365
30
55

CTE

10-6 /K

2.3

CTE

10-6 /K

Gradient
CVI

LSI

42 - 47
10 - 15
2.1 2.2
270 330
0.6 0.9
450 - 500
450 - 570
45 - 55
90 - 100
3

3.5 (open)
1.9
160
28
60
-1.0 / 2.5

2.5 / 6.5

PPP
RT
1.8
270
530 *
370
20
60 - 80
-

1500C
1.8
320
610 *
470
20
60 - 80
-

(1)

(1)

Key

LPI:LiquidPolymerImpregnation;CVI:ChemicalVapourInfiltration;LSI:LiquidSilicon
Infiltration;PPP:PolymerPyrolysisProcess.

:longitudinal;:transverse;:[0/90]layup;:ILSS;*:4pointbend;(1):CTE100C/1500C

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52.3.4.2

Oxidation

The inherent weakness of CSiC lies with poor oxidation performance of the carbon fibre. The SiC
matrixprovidesadegreeofencapsulationwhichinhibitsoxidationifexcessivematrixmicrocracking
is avoided. This can be difficult, as the matrix is brittle and prone to cracking. The difference in
thermalexpansionbetweenfibreandmatrixhindersthesituationunderconditionsofthermalcycling
andshock.
Consequently,CSiCcompositesrequireoxidationprotectivecoatingsforapplicationsattemperatures
above 500C, Ref. [5260], [5261], [5263]. Adequate oxidation protection was investigated within
FESTIPandhypersonicvehicleprogrammes.Aneffectivemulticomponentprotectionsystemwith
selfhealingcapabilitieswasdevelopedforLPIandCVIprocessedCSiCcomposites,Ref.[5260],[52
61],[5263].

52.3.5

C/SiC LPI liquid polymer infiltration process

52.3.5.1

Description

The material, processing and properties described here are for a grade of LPI C/SiC with T800 6k
fibres,whichwasqualifiedfortheX38programandappliedfortheC/SiCNoseSkirtsdeliveredby
EADSST(formerlyDASAAstrium),Ref.[5266].
C/SiCmaterialpropertiesdifferinthermalandthermomechanicalpropertiesdependingonthetype
ofcarbonfibreandthecoatingappliedtothecarbonfibre.Ingeneral,mosttypesofcarbonfibrescan
beusedforLPIprepregproduction.
The density of the SiC matrix can be modified by the number of liquid infiltration cycles and
subsequentpyrolysisafterthefirstpyrolysisofthegreenbodycomponent.

52.3.5.2

Manufacturing and inspection

TheLPIroutereliestoaconsiderableextentonconventionalCFRPprocesses.Consequently,specific
investmentandtoolscostsarereducedbecauseexperienceandtechnologiesfromtheCFRPfieldcan
betransferredtoCMCs.
The manufacturing process for continuous fibrereinforced C/SiC material produced by the LPI
technique uses a computercontrolled production system. The LPI manufacturing cycle is
accompaniedbyqualityassurance,inspectionandtests;asshowninFigure52.03.2anddescribedin
Table52.3.2.Therefore,nonconformancescanbeidentifiedateachstageofproduction,e.g.possible
delaminationscanbeidentifiedveryearlyinthegreenstateoftheprocessbyultrasonicinspection
afterautoclavecuring.

The fabrication steps performed by computercontrolled facilities are also accompanied by quality
controlactivities,e.g.FC9.
TheactualstrengthpropertiesofthemanufacturedC/SiCpartsarecomparedwithreferencecoupons
(witnesssamples)toprovideconfidenceintheC/SiCcomponents.

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F 17

Q 17
Q5

Q1

F1

Q3

F3

Q2

F2

Q4

FC 3

F5

F6

Q7

FC 5

FC 4

Q7

F 10

F7

Q8

F 16

F 15

Q 15

Q6

FC 4

Q8

F8

FC 7

F9
FC 9

F 11

FC10

Q 13

F4

Q8

FC11

F 13

F 14

FC13

FC14

Q 16

Key: F Fabrication step; Q Inspection step,


[See: Table 52.3.2]
Figure52.32C/SiCLPI(EADSST):Manufacturingandinspectionflowchart
Table52.32C/SiCLPI(EADSST):Fabricationandinspectionsteps
Fabrication steps

Inspection steps

[See: Figure 52.3.2]


F1
F2

F3

F4

F5

F6

preparing a pre-ceramic slurry


consisting of a solvent polymer and a
ceramic powder
coating of the T 800 fibres with one or
two pyrolytic thin C-layer
manufacturing of the prepregs,
simultaneously with the infiltration of the
continuous carbon fibre rovings with the
polymer slurry, prepared under F1
manufacturing of the laminates in
accordance with the stipulated prepreg
layer-lay-up, shaping the laminates and
joining on the mould tool to form the
integral structure
vacuum bagging of laminates on mould
tool and curing in autoclave to cross-link
the polymer and to form a consolidated
fibre-reinforced, powder-filled polymer
matrix composite green body
preliminary shaping to required outer
dimensions

Q1

inspection of incoming raw materials for


pre- ceramic slurry

Q2

inspection of incoming T 800 fibres

Q3

inspection of slurry, prepared under F1

Q4

inspection of fibre coating

Q5

inspection of prepreg quality, fibre


content

Q6

F7

pyrolysis in inert gas to convert the


polymer into ceramic matrix material

Q7

F8

liquid infiltration and re-infiltration of the


porous CMC via the polymer route

Q8

inspection of lay-up of all layers, vacuum


bagging of laminates on mould tool
inspection of curing in autoclave data
and dimension control and NDI on
green body
inspection of CMC parts after first
pyrolysis, test of witness coupons

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Fabrication steps

F9

F10

F11

F12
F13
F14

F15

F16

Inspection steps
[See: Figure 52.3.2]
pyrolysis of the re-infiltrated structure,
inspection of re-infiltrated CMC parts
Q9
typically 4-6 times, according to density
after last pyrolysis, test of witness
requirements
coupons
final machining of structural part to
inspection of CMC parts after final
required dimensions taking into account Q10
machining, NDI
the coating thickness
application of fundamental layer
oxidation protection coating by means
of Chemical Vapour Deposition (CVD).
visual inspection after CVD coating and
For re-use and multi mission
Q11
weight measurement
applications, the coating is improved
with multi-layer self healing OPS and
final CVD coating (F12-F14)
preparation of slurry for multi-layer
Q12 inspection of OPS coating slurry
coating
application of multi-layer coating and
visual inspection after OPS coating and
Q13
final erosion resistant layer
final CVD coating, weight control
heat treatment for oxidation protective
inspection of transportation container for
Q15
multi-layer coating for each layer
coated CMC parts
manufacture of transportation boxes
and handling fixtures prior first
inspection of pre-assembled and final
transportation of structural part (green
Q16 assembled CMC parts, acceptance for
state)
delivery
assembling if necessary, packing and
transportation

52.3.5.3

Material characteristics

The material properties of C/SiC differ depending on the application, the type of carbon fibre used
and the number of reinfiltration cycles. The material data presented are based on the C/SiC LPI
material applied to the X38 Nose Skirt, which was manufactured by EADS ST (formerly Astrium),
Ref.[5266].
ThecompositewasconstructedinquasiisotropiclayerswithT8006kfibres.Eachunidirectionallayer
hasathicknessofabout0.2mm;theanglebetweenthelayerswas,asfaraspossible,45.

52.3.5.4

Density

ThedensityoftheC/SiCcomponentswas1790kg/m.Thisvaluewasmeasuredonmaterialinafinal
pyrolysedconditionwithouttheCVDcoating.

52.3.5.5

Mechanical properties at different temperatures

The values used for linear static analysis margin calculations over the complete temperature range
fromRTto1600CareshowninTable52.3.3.

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Table52.33C/SiCLPI(EADSST):Mechanicalpropertiesatdifferent
temperatures
E11=E22=47GPa

XT=YT=157MPa

12=0.25

XC=YC=291MPa

G12=19.5GPa

S12=109MPa

=1.83E9Ns2/mm4

S13=S13(T)2MPa

11=22=CTE(T)1

Key:

:DASAC/SiCtestedvaluesfor11=22

:DASAC/SiCtestedvaluesforS13

TemperaturedependentCTEofDASAC/SiC:
T(C)

11= 22

(10-6/K)

20

100

1000

1500

0.08

1.45

2.28

DASA-C/SiC test
values

TemperaturedependentILSallowableofDASAC/SiC:

S13 (MPa)

12

17.74

DASA-C/SiC test
values

52.3.5.6

Specific heat capacity of C/SiC LPI material

Figure52.3.3showsthemeasurementsofspecificheatcapacityoftheEADSSTC/SiCLPImaterialfor
thetemperaturerange100Cto1500C.

specific heat capacity [J/(kg K)]

1800

1600

1400

specific heat capacity


1200

1000

800
100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

temperature [C]

Figure52.33C/SiCLPI(EADSST):Specificheatcapacity

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52.3.5.7

Thermal conductivity of C/SiC LPI material

Figure52.3.4showsthemeasurementsofthermalconductivityoftheEADSSTC/SiCLPImaterialfor
the temperature range 100C to 1500C. Values for both inplane and perpendicular to the fibre are
given.

10
9,5
thermal conductivity [W/(m K)]

9
8,5
8

thermal conductivity in-plane [W/(m K)]

7,5

thermal conductivity perpendicular to fiber [W/(m K)]

7
6,5
6
5,5
5
100

200

300

400

500

600

700

800

900 1000 1100 1200 1300 1400 1500

temperature [C]

Figure52.34C/SiCLPI(EADSST):Thermalconductivity
52.3.5.8

Catalycity, plasma erosion and oxidation protection

To avoid plasma erosion and oxidation of the carbon fibres, the C/SiCpanels are covered with an
oxidation protection layer system designed for the appropriate temperature regime. Since the outer
surface of the C/SiC panels is in contact with the hot boundary layer and since its temperature
depends approximately on the difference between convective heat loads and emitted radiation, the
characteristicpropertiesofinterestarethethermoopticalpropertiesandcatalycity.

52.3.5.9

Emissivity

The surface coating is produced by one or more SiC layers applied by CVD chemical vapour
deposition. If a multilayer OPS oxidation protection system is applied, the surface emittance is the
samebecausethetoplayeroftheOPSisthesameastheCVDSiClayer.Themeasuredtemperature
dependentvaluesofthesurfaceemittanceoftheantioxidationcoatingsystemusedbyEADSSTare
showninFigure52.3.5forthetemperaturerange0Cto1200C.Fortemperaturesabovethemeasured
range,theemittancevaluefor1200Chasbeenassumed.

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0,85

surface emittance [-]

0,8

0,75

emittance [-]
0,7

0,65

0,6
0

200

400

600

800

1000

1200

temperature [C]

Figure52.35C/SiCLPI(EADSST):Surfaceemittance,withantioxidation
coating
52.3.5.10 OPS oxidation protection system development for reusable
applications
ThefirstquestioniswhyuseanOPSoxidationprotectionsystemforCMCmaterialsdestinedforTPSand
thermostructuralapplications,ratherthannonoxidisingCMCmaterials,suchasSiC/SiCorNextel/Mullite?
The main reason is that investigations into CMC over the past ten years have shown that C/SiC
components with high strength carbon fibres, e.g. T800, offer the best strength and stiffness at high
temperaturesupto2000C.
ForfuturereusablesystemslikeRLVorCTV,theC/SiCTPSandthermostructuralcomponentsneed
anOPStopreventthecarbonfibrereinforcementoxidising.Oxidationoccurswithexposuretooxygen
atalltemperaturesabove450C,sotheOPSfunctionsinallappliedtemperatureregimesforreusable
C/SiCstructuresupto1600C.
A selfhealing, multilayer OPS, previously developed by EADS, was tested successfully in several
investigations, i.e. TPS shingle and panel plasma tests; thermomechanical cycles. The main
drawbacksofthemultilayerfunctionalcoatingwere:

highly complex and expensive manufacturing route. Each single OPS layer is pyrolysed
separately.

thermalgradientsbetweenthemultilayercoatings,whichcausethermalstresses

TheOPShasacomplexcoatingarchitecture.Thesimplestofwhichconsistsof3to5CVDSiClayers
withaSiO2glasssealingontop.However,itprovedunreliableduringlongtermexposureinairand
notresistantthroughoutthewholetemperaturerangefrom500Cto1600C.Complexsystemshave
bond layers to adjust the thermal expansion coefficient or the chemical compatibility between the
substrateandthecoating.Evenmorecomplexsystemsconsistofmorethanthreelayerswithdifferent
functionssothatthesystemworksfrom500Cto1600C.SelfhealingOPSconsistsofvariouslayers
with different functions: a bonding layer, an intermediate functional layer system with selfhealing
capability and an erosion protection layer. Multilayer oxidation protection coatings are applied to
C/SiCcompositeseitherbyaslurrytechniqueorbyCVD.

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Figure52.3.6summarisesacurrentarchitectureforamultilayer,multifunctional,selfhealingcoating
fromEADSST.
2 CVD Erosion Protection Layers
1 to 3 different functional layers with self-healing properties through
thermo-viscous flow processes for different temperature regions for
each layer
2 CVD Bonding Layers

C/SiC substrate

Figure52.36C/SiCLPI(EADSST):Architectureofmultilayer,selfhealingOPS

ThefunctionofthedifferentlayerssummarisedinFigure52.3.7canbedescribedas:

Erosionprotectionlayer,whichpreventsoxygendiffusiontothefunctionallayerandreduces
the evaporation of the second viscous layer as well as minimising erosion of the coating.
ErosionprotectionlayerslikeSiCreactwithoxygentoformsilicaasanoxygenbarrierduetoits
verylowoxygendiffusioncoefficient.

Functional layer with selfhealing capability, which is an intermediate layer that seals cracks
and prevents oxygen diffusion into the substrate. Best results have been achieved by using
combinations of several boron and silicon phases. The boron containing systems are able to
reactwithdiffusingoxygenandformlowermeltingpointboronglasseswhichcansealcracks
withintherigidlayersbyviscousflowprocesses.

Bondinglayer,whichhasthemaintaskofaccomodatingthedifferencesinthermalcoefficients
betweenthefibrereinforcedSiCmatrixandthesecondlayer.Thebondinglayeralsoprevents
carbonfromdiffusingoutofthesubstrate.NormallythislayerconsistsofSiCappliedbyCVD.

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Crack

Top layers

Functional layer with


self-healing capability

Formation of B2O3 -SiO2 -Glasses


which act as self-healing systems

Figure52.37C/SiCLPI(EADSST):FunctionoflayersinOPS

52.3.5.11 WEPROT and OLCHOS studies on OPS systems


Recent experience in testing of different OPS systems have been gained within the ESA studies
WEPROT, Ref. [5267], [5268], [5276], and OLCHOS, Ref. [5269]. Both studies investigated
differentOPSinanextensivelifecycletestprogramme.TheWEPROTprogramalsoinvestigatedthe
lifetimebehaviouroftheOPSwithrespecttoimpactsanderosioncausedbylowspeedimpact,rain
droperosionandhailimpacts.WithintheOLCHOSprogramme,theOPSsystemsappliedbyEADS
STaregiveninTable52.3.4.

Table52.34C/SiCLPI(EADSST):OPSusedinOLCHOSprogramme
OPS
Reference

E 1.2
E 2.2
E 3.2

Architecture

2 CVD layers, one multifunctional layer, 2 CVD layers


2 CVD layers, two different multifunctional layers, 2 CVD
layers
2 CVD layers, three different multifunctional layers, 2
CVD layers

Total
layers

5
6
7

All three systems survived up to 100 reentry cycles during the test program. The best result of the
threesystemswasobtainedfromtheOPSwiththelowestcomplexity(E1.2),withthecombinedself
healinglayer.
Within the WEPROT study, the system E2.2 has been applied with excellent results even with OPS
samplespredamagedbylowspeedimpactorrainerosion.
The test results from OLCHOS and WEPROT revealed that at the lower temperature range (about
800C to 900C), the selfhealing capacity of the OPS could be improved, whereas at higher
temperatures(1200Cto1500C)theOPSfunctionallayerperformancewasoptimal.

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52.3.6

C/C-SiC LSI liquid silicon infiltration process

52.3.6.1

Material characteristics

There are 3 main types of C/CSiC materials produced by DLR. All of which comprise carbon fibre
bundles in surrounding SiClayers. The manufacturing process parameters and fibre conditioning
definethemechanicalproperties.TheLSI(liquidsiliconinfiltration)processinvolvesmakingaCFRP
part using a special resin with a high carbon content. After pyrolysis at 900C, the resulting porous
C/Cpreformisinfiltratedbyliquidsiliconatabout1600C.Thesiliconpartiallyreactswiththecarbon
toformSiC.

52.3.6.2

Mechanical properties

Table52.3.5summarisesthemechanicalpropertiesoftwogradesofDLRC/CSiCLSImaterial.These
are used for manufacturing TPS and hot structures, e.g. X38 Nose Cap assembly under the TETRA
programme,[Seealso:70.24].
DLRLSImaterialshavealsobeeninvestigatedaspartofanESAfundedstudyonfailurecriteria,Ref.
[5270],[Seealso:64.5]

Table52.35C/CSiCLSI(DLR):Mechanicalpropertiesfordifferentgrades
Materialgrade

Ex=Ey
(MPa)

C/C-SiC XB
60000
C/C-SiC XT
60000
(1)
C/C-SiC XT
60000
Key:

Gxy

xy

(MPa)

15000 0.05
15000 0.05
15000 0.05

(g/cm )

(1/K)

1.9
1.9
1.9

110-6
110-6
110-6

Sx,t=Sy,t

Sx,c=Sy,c

Sxy

72
150
150

225
205
250

54
60
60

(1)inplanebending

Figure 52.3.8 shows mechanical properties for tests on XB and XT grades of DLR C/CSiC LSI
materials.Theaveragevaluesarefor5samplescutfromoneplate,Ref.[5270].

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4 Pkt Biegung

Shear

300

70

60

250

50
200

Schubspannung [MPa]

I 258
I 498-1

MPa

I 498-2
I-498-3
ph609

150

Ph 597
Ph 596
100

40

I258
I498- 1
Ph 596

30

20

10

50

0
0

I 258
I 258

I 498-1

I 498-2

I-498-3

ph609

Ph 597

I 498-1

Ph 596

Ph 596

Platte

Average shear strength

Average bending strength


Zug

Druck
0

180

I 498-1

I 498-2

I-498-3

ph609

Ph 597

Ph 596

160
-50
140
-100
120
I 498-1

I 498-1

I 498-2

100

-150

ph609
80

Ph 597

I 498-2
I-498-3

MPa

MPa

I-498-3

Ph 596

ph609
Ph 597

-200

Ph 596

60
-250
40

-300

20

0
I 498-1

I 498-2

I-498-3

ph609

Ph 597

Ph 596

-350

Average compressive strength

Average tensile strength

Key:
XT grade
XB grade
XT grade (in-plane shear)
XT grade (in-plane bending)

Figure52.38C/CSiCLSI(DLR):MechanicalpropertiesforXTandXBgrades

52.4 Silicon carbide fibre reinforced silicon carbide


52.4.1

Technology status

SiCSiCisbyfarthemostdevelopedoftheoxidationresistantceramicmatrixcomposites.CVIisthe
preferredmanufacturingroute.
Thekeyparticipantsare:

Socit Europene de Propulsion (SEP), France; in collaboration with the French government
andauthoritativeuniversities.AlicencefortheirSiCSiCCVIproductiontechnologyhasbeen
sold to DuPont with the production capability in the USA (1989/1990). SEPs trade name is
CERASEP.

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Oak Ridge National Laboratory, USA; in collaboration with Babcock and Wilcox (USA). The
latter is aiming to use the technology of the former for commercial products. The work is
supportedbytheUSDepartmentofEnergy.

NipponCarbonCo;themanufactureofNicalonfibreisofferingSiCSiCproducedbypolymer
pyrolysis.Thismaterialhasinsulativecharacteristicsbutindifferentmechanicalstrength.

RefractoryCompositesInc.,USA.

ThermoElectronCorp.,USA.

52.4.2

Applications

TheintendedcommercialusesforSiCSiCcompositesinclude:

Rocketandpropulsionunits,Ref.[5236].

Gasturbineenginecomponents,Ref.[5237].

Heatexchangers,Ref.[5238].

Thermalprotectionsystems,Ref.[5239].

Refractoryfurnacelinings,Ref.[5240].

52.4.3

Characteristics

52.4.3.1

Fibres

ThemostnoticeabledisadvantageofSiCSiCcompositesisthelackofafibrewhichisthermallystable
above 1300C, where progressive degradation occurs to present fibres. Nicalon and Tyranno are, at
present,theonlypracticableoptions.

52.4.4

Manufacturing of SiC-SiC

Themainchemicalreactionusedisthatwithmethyltrichlorosilane(MTS):

CH3SiCl3+xH2SiC+3HCl+xH2,@1200C

Excess hydrogen is used as a carrier gas. Deposition times can vary between 30 hrs and 150 hrs,
typically.Workhasmainlyconcentratedonproducingcompositesfromplainandsatinweavefabrics.
ThereisnolimitationonthesizeofSiCSiCcomponentsthatcanbeproduced,butveryfewfacilities
existfordimensionsbetween1mand3m.
All deposition occurs within a closed vessel under controlled gas flow conditions and at an evenly
distributedtemperature.PriortodepositingtheSiCmatrix,theSiCfibresareprecoatedusuallywith
carbonorpyrolyticgraphitetoathicknessof<1m.

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52.5 SiC-SiC composite: Properties


52.5.1

General

SiCSiCcompositesarethemostdevelopedoftheCMCs,sopublishedinformationincludesthe:

Stressstrainprofileofthecomposites,withrespecttoprogressivefailure.

Attainableflexuralandtensilestrengthsatroomtemperature.

Degreesofstrengthretentionathightemperaturesunderextremeenvironments.

Measuredfracturetoughness.

52.5.2

Mechanical properties

52.5.2.1

General

ThemechanicalpropertiesofSiCSiCcompositesaredependenton:

fibreorientations,and

volumefraction.

Figure52.5.1givesstrengthsforsomeoftheSiCcompositionsreported.Itisnoticeablethatthehigher
valuesarefortheSiCfilamentreinforcedSiCandunreinforcedhotpressedceramic.
Filamentreinforcedmaterialsarenotappropriateforstructuraluses,neitherareunreinforcedbrittle
materials.Toughenedcompositeswithfibreshave600MPaasverymuchtheupperlimit.

Figure52.51SiCSiCcomposites:Hightemperatureflexuralstrengthofvarious
compositions

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52.5.2.2

Effect of environment

Testingattemperatureunderinertatmospheresgivesgreaterstrengthvaluesthansimilarcomposites
testedinoxidativeorcorrosiveenvironments,orafterthermalcycling.

52.5.2.3

Effect of fibre coating

Thefibrecoatinganditsfunctionastheinterfacebetweenfibreandmatrixdeterminesthecomposite
behaviour and properties. The insitu fibre strength dictates the ultimate strength of the composite
andthefracturecharacteristics.
The fibre size is removed by either solvent or pyrolysis. The coating is then applied, often by the
organisationundertakingthematrixCVI.Asyetthereisnooneacceptedcoating.Usuallyacarbonor
pyrolyticgraphitecoatingisused;thicknessesbetween0.01mand0.1m.Pyrolyticboronnitridehas
alsobeenpromotedasthecoating,butwithlessprominence.

52.5.2.4

Stress-strain response

Figure 52.5.2shows a representative stressstrain profile for a bidirectional fabric SiCSiC composite
withNicalonreinforcement,Ref.[527].

Figure52.52SiCSiCcomposite(bidirectional):Typicaltensilestressstraincurve

Threezonescanbeseeninthestressstraincurve:

Zone 1: The behaviour of the composite is elastic to a strain of 0.035%, with fibre and matrix
actinginunison.

Zone 2: The matrix is microcracking and there is a gradual transfer of load to the fibres. This
explainsthefallinmodulusfromtheoriginal210GPa.

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Zone 3: The load is entirely sustained by the fibres to 0.6% strain. The 190MPa failure stress
should be viewed in the light of the composite being based on bidirectional fabric. This
strengthlevelisindicative,andhasbeenimprovedupon.

In using SiCSiC composites which possess a very restricted linear elastic response, the mechanical
stressing caused by either direct load or thermal shock should not reach such levels as to promote
progressive microcracking. The design limits, therefore, are more modest than the maximum
attainablestrengths,suggestingvaluesof100MPaforabidirectionalfabriccomposite.

52.5.2.5

Effects of temperature

ThemainadvantageofSiCSiCisthestrengthretentionto1200C,asshowninFigure52.5.3,Ref.[52
2].Thesestrengthswereattainedinanatmosphereofargonandhydrogen.Thehigherinsitustrength
ofcarbonfibrewithrespecttothatofNicalonisalsoevident.

Figure52.53SiCSiCcomposites:Typicalbendingstrengthversustemperature
profilescomparedwithCSiCcomposite
The results shown in Figure 52.5.4 and Table 52.5.1 show SiCSiC capable of sustaining its strength
andfracturetoughnessdespitethermalshockandrepeatedthermalcycling,Ref.[522].Hence,theuse
ofSiCSiCcanbeconsideredforthermalprotectionsystemswherethemodestmechanicalstrengths
canbeaccommodated.

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Figure52.54SiCSiCcomposites:Representativethroughthicknessfracture
toughnessversustemperaturecomparedwithCSiC
Table52.51SiCSiCcomposites:Indicativeproperties,asmeasuredbySEP
(France)
Temperature(C)

Property

RT
-1

Thermal conductivity (Wm C ):


Parallel to fibres
Perpendicular
Thermal diffusivity (10-6m2s-1):
Parallel
Perpendicular
CTE (10-6C-1)
Bending strength (MPa)
Key:

1000 1200 1400 1600 2000

-1

25
6

18
5

18
5

12
4.5
5
300

4.5
2.2
350

2.2
390

3.5
2.2
200

150

50

Material:2DlaminateswithNicalonfabric&10%porosity.
Nostrengthloss@1000Cinairupto500hours.
Thermocycling&ThermalShockto1200Ccausedlittleornochangetostrength
characteristics.
FractureToughnessof25MPamconstantto1300C.
Nocatastrophicfailurecharacteristics.

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52.5.3

Environment

52.5.3.1

Oxidation

Whilst silicon carbide is an oxidationresistant material, SiCSiC composites degrade significantly


underprolongeduse,e.g.ingasturbineapplications.
To combat oxygen attack, SEP provide a grade of SiCSiC which has an applied glaze (glass) to the
outersurfacetoprovideadditionalprotection.

52.6 Whisker reinforced composites


52.6.1

Development

52.6.1.1

Reinforcements

Theadvantagesthatwhiskershaveoverfibresare:

highpurity,and

hightensilestrength.

Table 52.6.1 indicates very high strengths and moduli. The purity provides a high level of thermal
stability.

Table52.61Ceramicmatrixcomposites:Ceramicwhiskers
Whisker

Tradename

type

[Source]

-SiC
-SiC
-SiC
-SiC
-SiC
-Si3N4
Al2O3
Al2O3

Silar SC-9
[Arco, USA]
Silar SC-10
[Arco, USA]
Tokamax
[Tokai Carbon, Japan]
Tateho SCW
[Tateho, Japan]
XPW2
[JM Huber, USA]
VLS
[Los Alamos]
Tateho
[Japan]
Emcor 66
[Engelhard, USA]
[Thermokinetics, USA]

Properties
Density

Size

UTS

Modulus

(kg/m )

(m)

(GPa)

(GPa)

3200

0.6

6.9

689

3200

3190

0.1-1

3-14

400-700

3180

0.1-0.5

20.6

483

3-10

15.9

580

3180

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52.6.1.2

Composites

Whiskersaddedtoceramicsdonotretaintheirveryhighmechanicalpropertiesbecauseitisdifficult
to:

achievebondingbetweenwhiskerandmatrix(tousethewhiskerstrength),

minimisewhiskerdegradationbychemicalinteraction.

Table52.6.2showswhiskerandmatrixcombinationswhichhavebeenassessed.Themainmotivation
forstudyingthesematerialsisforuseininternalcombustionengines.

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Table52.62Ceramicmatrixcomposites:Developmentwhiskerandmatrixcombinations
Whisker
Reinforcement

Matrix

SiC (ARCO)

Si3N4 with Y2O3 & CeO2


sintering aids. Al2O3

-SiC

Si3N4 with Y2O3 & La2O3


sintering aids.

SiC (Tokamax)

Si3N4 with Y2O3 & Al2O3


sintering aids.

SiC (VLS grade)


SiC (Silar SC-9,
ARCO)

Si3N4 with MgO


sintering aid.
Si3N4 with Y2O3 & Al2O3
sintering aids.

SiC (SC-9, ARCO)

Al2O3
Mullite

SiC (SC-9, ARCO)

Al2O3

SiC (SC-9, ARCO)

Al2O3

SiC (SC-9, ARCO)

Al2O3

SiC

Al2O3 (WG300)

SiC (Silar SC-9,


SCW-1)
SiC (SCW-1,
Tateho):
Also Al2O3 & Si3N4
SiC whiskers (VLS
grade)

Mullite
(3Al2O3 :2SiO2)
Al2O3 Corderite
Mullite
ZrO2
Molybdenum disilicide
(MoSi2)

Source
[Reference]
GTE Laboratories, USA.
Ref. [52-41]

Comments

20 wt% whisker content. Powder route. Al2O3 hot pressed @ 1850C & Si3N4 @
1725C.
Hot pressing @ 1800C. Up to 50% whisker content. Whiskers modified strength
Japanese Government Industrial
of monolithic ceramic by very small amount to 650 MPa, fracture toughness
Research Institute. Ref. [52-42]
improved slightly.
Cold isostatically pressed. Nitrided @ 1350C and then Pressureless Sintered @
Swedish Institute for Silicate
1850C. Neither the flexural strength or the fracture toughness of Si3N4
Research. Ref. [52-43], [52-44]
improved. The whisker:matrix bond judged to be too good, causing brittle failure.
Los Alamos National Laboratory, Whisker volume fractions of 40%. Hot pressing @ 1850C. Toughness increased by
USA. Ref. [52-45]
50% to 10.5 MPa m-1/2.
Hot pressed @ 1800C. For 30 vol.% whiskers, fracture toughness increased by
GTE Laboratories, USA.
Ref. [52-46]
40% to 6.4 MPa m-1/2 & flexural strength by 25% to 950 MPa.
Hot pressed @ 1850C for alumina matrix. Fracture toughness of both matrices
ORNL, USA.
improved two-fold. Al2O3 with 20 vol.% whiskers, flexural strength of 805 MPa @
Ref. [52-47], [52-48], [52-49]
RT & 520 MPa @1200C obtained.
30
vol.%
whiskers.
Hot
pressed to 1950C. Flexural strength of 650 MPa;
University of Illinois, USA.
Ref. [52-50]
Fracture toughness 9.5 MPa m-1/2.
15 wt.% whiskers. Hot pressed to 1500C. Flexural strength of 650 MPa; Fracture
Rockwell Corp., USA.
Ref. [52-51]
toughness 4.6 MPa m-1/2.
15 wt.% whiskers. Composite supplied by ARCO. Creep data acquired in air @
University of Southern
1500C, where creep is appreciable even at stresses of 48 MPa.
California, USA. Ref. [52-52]
Fracture
Toughness & Fatigue Crack Growth study. 60% increase in toughness,
Brown University, USA.
K1C values increase by 70 to 150%.
Ref. [52-53]
Up to 40 wt.% whiskers. Hot pressed @ 1700C. Flexural strength: 386 MPa;
General Electric Co., USA.
Ref. [52-54]
Fracture Toughness 3.52 MPa m-1/2. Failure strain: <0.15%.
University of Hamburg/MaxHot pressing of various matrix:whisker combinations. Thermal expansion
Plank Institute, G.
mismatch between whiskers & matrix strongly influence strength levels.
Ref. [52-55], [52-56]
Fracture Toughness of all ceramics increased.
Los Alamos National Laboratory,
20 vol.% whiskers. Hot pressed @ 1640C. 100% increase in flexural strength;
USA. Ref. [52-57], [52-58]
50% increase in Fracture Toughness.

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52.6.1.3

Material processing

Apowderprocessingrouteisusedwithwhiskeradditionsbetween20%and50%byvolume.
Consolidationbyhotpressingoccursatpressuresof~25MPa(3500psi).Thetemperaturesarehigher
than for CVD/CVI; between 1600C and 1950C, depending on the matrix. The composites obtained
showlowporosity.

52.6.2

Properties

52.6.2.1

Composites

Publishedinformation indicates that the strength and fracture toughness of the composites are only
marginally better than those of the base monolithic ceramics. The base ceramics have flexural
strengthsbetween500MPaand900MPa,withfailurestrainsto0.3%.

52.6.3

Applications

For spaceplane structures, continuous fibre composites are likely to be more appropriate than
whiskerbasedsystemsonthegroundsofpseudoplasticorbenignfailurecharacteristics.

52.7 Potential applications


52.7.1

Resum

CMCmaterialsweredevelopedforhightemperatureapplicationswheretheirlowdensity,compared
withmetals,andfracturecharacteristics,comparedwithmonolithicceramics,madethemofinterest
forreusableandhypervelocityvehicleprojects.Variousinternationalandnationalbasedprogrammes
have progressed CMC technology such that some materials have been fully characterised for use in
specificthermostructuralapplications.
The demands for improved data rates and lower power consumption in satellite communications
systemsmeansthatopticalbasedsystemshaveadvantagesoverthoseusingradiowaves.CMCsare
of interest for such applications which need materials with a longterm, very high dimensional
stabilityinthespaceenvironment.

52.7.2

High temperature applications

52.7.2.1

General

CMCsweredevelopedforuseattemperatures>1000C.Withtheonsetofdegradationat1200C,their
application is largely dictated by the timedependent retention of residual properties. At higher
temperatures,e.g.1650C,oxidationprotectionofthecarbonfibrereinforcementisnecessarybecause
potentialapplicationsaregenerallyinoxidisingenvironments.ThemainfeaturesofCMCsaretheir
thermalcharacteristics,includingtheabilitytowithstandthermalshockandthermalcycling,coupled
withadequatemechanicalperformance.

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52.7.2.2

Thermo-structural systems

VariousRLVconceptvehiclesperceivedtheuseofCMCsfortheprotective,aerodynamicsurfacesof
spaceplanes, [See: Chapter 70]. Some examples include, Ref. [5262], [5263], [5265], [5266], [5271],
[5273],[5274],[5275]:

X38bodyflaps,nosecapassembly,[Seealso:70.XX]

X33elevon,Ref.[5273].

Hopperelevon,Ref.[5273].

OPSX37elevon,Ref.[5273].

52.7.2.3

TPS thermal protection systems

VariousRLVconceptvehiclesperceivedtheuseoftilesandshinglesinfortheTPS,[See:Chapter71].

52.7.2.4

Deployable hot structures

FOLDHOSTisaconceptforadeployabledecelerator;asshowninFigure52.7.1,Ref.[5273],[5277].
ThisisbasedontherequirementsfortheMarsMissionISRUinsituresourceunit.Thedeceleratoris
completely folded inside the payload container for launch. During ejection the decelerator deploys
automaticallybyaspringloadeddeploymentmechanism,[Seealso:70.25].
ThebenefitsofconsideringCMC(C/SiC)forthisapplicationcanbesummarisedas,Ref.[5273]:

Allotherhotstructuresmadeofmetallicmaterials,e.g.InconelorhightemperatureODS,are
limitedintemperaturecomparedwithC/SiCandarealsomuchheavier.

C/SiC material is a suitable hot structural material because of its strength (about 200 MPa),
stiffnesscomparabletoaluminumbutwithalowerdensitythanaluminium.

C/SiC can support higher loads at about 1600C compared with room temperature
performance.

Inotherconcepts,adeployabledeceleratorwithcoldstructuralpanelsandadditionalTPS,e.g.
ablator,amounttoaboutdoublethemasscomparedwithaC/SiCdecelerator.

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Figure52.71Ceramicmatrixcomposites:FOLDHOSTconceptfordeployable
decelerator
52.7.2.5

Propulsion systems

Withinenginesandpropulsionsystems,CMCsareconsideredforsomestaticcomponentsinorderto
avoiddynamicmechanicalloads.

52.7.2.6

Heat exchangers

CMCsareconsideredforextremehightemperatureheatexchangers.

52.7.2.7

X-38 body flaps

TheX38testvehicledesignincludestwopairsofmoveableflightcontrolsurfaces(ruddersandbody
flaps)fortheintendedautonomous,controlledreentryandparafoilassistedlanding.
Each body flap can be moved independently for roll and pitch manoeuvres. For the NASA X38
experimentalvehicleV201,thedimensionsofeachflapwere1.6mlong;1.6mwide,Ref.[5263].
AnumberofcomprehensivestudieswereundertakenontheapplicationofCMCforthebodyflapsin
ordertomeettheexactingconditionsexperiencedduringreentry(V201flightconditions;combined
thermal, pressure, mechanical loading; 4 reentry cycles). The studies have resulted in the design,
manufacture, testing and flight qualification of CSiC composite body flaps by MAN Technologie.
TheseareshowninFigure52.7.2,whichalsohighlightstheassociateddesigndevelopmentsnecessary
tomakeafullyfunctional,complexallCMCstructure,Ref.[5263].
Each flap contains about 100 different parts. These are made from a 2D C/SiC composite. A
modification to the basic processing method (carbon fibre fabric preforms infiltrated with SiC) was
applieddependingonthesizeandshapeofthecomponentparttobeprocessing.Thisresultedintwo
materialTypeshavingslightlydifferentdensities,tensilestrengthandstraintofailure,Ref.[5265].

[Seealso:70.23]

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Figure52.72Ceramicmatrixcomposites:ApplicationsX38bodyflaps

52.7.3

High precision optical structures

The development of spacebased laser communication optical systems need lightweight materials
with longterm thermal and dimensional stability. In addition to material selection, design and
manufacturing aspects, such as number of components, production costs for a series of parts,
machining and preparation of highprecision optical surfaces and assembly (with provision for
accuratealignment)arealsokeydemands,Ref.[5264].
Foropticalsystems,e.g.CassegrainorOffaxisTelescopeconcepts,C/CSiCCMCswereinvestigated
fortheTelescopeTubeandUpperSpidercomponents,asshowninFigure52.7.3,Ref.[5264].
To achieve the dimensional stability, the thermal behaviour of the component parts needs to be
known and controlled, i.e. mismatch in thermal expansion between different materials, such as the
supportstructureandthemirror.Inthiscase,withaZerodurmirror,anearzeroCTEwasnecessary
forthecompositeparts.

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Figure52.73Ceramicmatrixcomposites:ApplicationsOpticalcommunications
systems
ThecharacterisationofthethermalbehaviourofC/CSiCcompositesshowedthat,Ref.[5264]:

Inplane(fibreaxis)compositethermalexpansionisaffectedbythe:

veCTEC/C:(35C)=0.7x106K1;(+50C)=0.5x106K1.

larger,+veCTEoftheSiCmatrix:CTESiC:=<4x106K1.

Varyingthephasecontentofthecomposite,byadjustingtheSiCcontentbetween30wt.%and
50wt.%,affectedthecompositeCTE,e.g.measuredinplaneCTEsatRT:

lowSiC0.2x106K1

highSiC+0.8x106K1

OthermeansofcontrollingtheCTEofthesematerialsincludedthechoiceofreinforcementfibre
(HT,HM,IM)andthefibrearchitecture.

The standard LSI C/CSiC compositeuses HT carbon fibres in a woven fabric, an XP60 highyield
carbonaceous precursor, resulting in a composite containing ~75%C/C, ~25% SiC, with ~5 wt.%
unreactedsilicon.

[See:Table52.3.1fortypicalstandardLSImaterialproperties]

Prototypes components have been manufactured using the LSI (Liquid Silicon Infiltration) process,
developedbyDLRforspacecraftthermalprotection,Ref.[5264].

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52.8 References
52.8.1

General
[521]

M.Gominaetal
ApplicabilityofFractureMechanicstoFibreReinforcedCVD
CeramicComposites
FractureMechanicsofCeramics,Vol.7,p1732

[522]

M.Daucheretal
PropertiesofSiliconCarbidebasedCeramicMatrixComposites
Proceedingsof30thNationalSAMPESymposium
1921March,1985

[523]

P.J.Lamicqetal
SiCSiCCompositeCeramics
Am.Ceram.Soc.Bull65[2],p336338(1986)

[524]

R.Naslainetal
AnAnalysisofthePropertiesofsomeCeramicCeramicComposite
MaterialsobtainedbyCVIdensificationof2DCCPreforms
ProceedingsofICCMV,August1985,p.499514

[525]

J.Y.Rossignoletal
MechanicalBehaviourinCompressionloadingof2DComposite
MaterialsmadeofCarbonfabricsandaCeramicMatrix
Proceedingsof30thNationalSAMPESymposium
1921March1985,p.15191525

[526]

J.L.Chermantetal
MorphologicalandMechanicalCharacterisationofCeramic
CompositeMaterials
TailoringMultiphaseandCeramicComposites
Vol.20p615629,1985

[527]

R.Naslain&F.Langlais
CVDProcessingofCeramicCeramicCompositeMaterials
TailoringMultiphaseandCeramicComposites
Vol.20,p145163,1985

[528]

P.Donguy&J.Broca
HighTemperatureCompositeMaterialsforRocketPropulsion
AGARDCP449:ApplicationofAdvancedMaterialfor
Turbomachinery&RocketPropulsion.35October1988
Paper23.

[529]

A.Melchoiretal
ThermostructuralCompositeMaterialsforLiquidPropellantRocket
Engines
AIAA872119,AIAA/SAE/ASME/ASEE23rdJointPropulsion
Conference,June29July2,1987,SanDiego,California

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[5210]

A.Lancombe
CeramicMatrixCompositesMaterialsforAerospacePlaneThermal
Structures
ESAWPP004October1988

[5211]

D.P.Stintonetal
ImprovedFibrereinforcedSiCCompositesFabricatedbyChemical
Deposition
Ceram.Eng.SciProc.Vol.7,part78,1986,p.983989

[5212]

A.J.Caputoetal
FibrereinforcedSiCCompositeswithImprovedMechanical
Properties
Am.Ceram.Soc.Bull.66[2],p.368372,1987

[5213]

A.J.Caputoetal:OakRidgeNationalLaboratory,USA
ImprovementsintheFabricationofCeramicFibreCeramicMatrix
CompositesbyChemicalVapourInfiltration
ORNL/TM9651;DE85015971;June1985

[5214]

D.P.Stintonetal
SynthesisofFibrereinforcedSiCCompositesbyCVI
Am.Ceram.Soc.Bull65[2],p.347350,1986

[5215]

A.J.Caputo&W.J.Lackey
FabricationofFibrereinforcedCeramicCompositesbyCVI
Proceedingsof8thAnnualConferenceonComposites&Advanced
CeramicMaterials,p.654667.1984

[5216]

H.H.Moelleretal
SiCFibrereinforcedSiCCompositesusingCVI
SAMPEQuarterly,Vol.17,No.3,p.14.April1986

[5217]

A.J.Caputoetal
Developmentofanew,fasterProcessfortheFabricationofCeramic
FibrereinforcedCeramicCompositesbyCVI
Proceedingsof9thAnnualConferenceonCompositesandAdvanced
CeramicMaterials,p.694705,1985.ACSPublication

[5218]

H.H.Moelleretal
FibrereinforcedCeramicComposites
Ceram.Eng.Sci.Proc.8[78],p.979984,1987

[5219]

D.P.Stintonetal
AdvancedCeramicbyCVITechniques
CeramicBulletin,Vol.67,No.2,p.350355,1988

[5220]

R.A.Lowden&D.P.Stinton
InterfaceModificationsinNicalonSiCComposites
Ceram.Eng.Sci.Proc.9[78],p.708722.1988

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[5221]

J.W.Warren
FibreandGrainreinforcedCVISiliconCarbideMatrixComposites
Proceedingsof9thAnnualConferenceofComposites&Advanced
CeramicMaterials,p.806820,1985.ACSPublication

[5222]

Y.M.Panetal
ToughnessAnisotropyofaSiCSiC/LaminarComposite
TailoringMultiphaseandCompositeCeramics
Vol.20,p.615629.1985

[5223]

P.Reaganetal
CVDSiliconCarbideComponents
Ceram.Eng.Sci.Proc.8[78],p.958967,1987

[5224]

P.Reaganetal
SiliconCarbideCompositeComponents
Ceram.Eng.Sci.Proc.9[78],p.881890,1988

[5225]

J.S.Copes&R.G.Smith
MicrostructuralCharacterisationofThermallyagedSiconexOxide
FibreSiCCompositeMaterials
NASATechnicalMemorandum87085,USAAVSCOM85C1421st
UniversityConferenceonCeramicScience,PennsylvaniaJuly1985

[5226]

R.T.Bhatt
MechanicalPropertiesofSiCFibrereinforcedReactionBondedSi3N4
TailoringMultiphaseandCeramicComposites
Vol.20,p.675686,1985

[5227]

N.D.Corbinetal
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D.K.Shettyetal
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R.Coulmetetal
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LongfibreReinforcedSolGelderivedAl2O3Composites
ProceedingsofMat.Res.SocietySymposium
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A.C.Pierreetal
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B.Benderetal
EffectofFibreCoatingsandCompositeProcessingonPropertiesof
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CeramicsBulletinVol.65,No.2,p.363369,1986

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H.Hannacheetal
CompositeMaterialsmadefromPorous2DCarbonCarbonPreform
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J.Y.Rossignoletal
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Composites.Vol.18,No.2,p135144,April1987

[5236]

R.Kochendorfer
MonolithicandFibreCeramicComponentsforTurboenginesand
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AGARDCP449.ApplicationofAdvancedMaterialfor
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D.E.Tripp
ContinuousFibreCeramicMatrixCompositesforHeatEngines
NASALewisResearchCenter,LewisStructureTechnology
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[5238]

W.E.Coleetal
CeramicCompositeHeatExchanger
Ceram.Eng.Sci.Proc.8[78],p968975.1987

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R.E.Fischeretal
CeramicCompositeThermalProtectionSystems
Proceedingsof9thAnnualConferenceonCompositesandAdvanced
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[5240]

W.W.Liang&M.E.Schreiner
AdvancedMaterialsDevelopmentforRadiantTubeApplications
IndustrialCombustionTechnologies,Chicago,USA
p305311,1986.ASMPublication

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V.K.Sarin&M.Ruhle
MicrostructuralStudiesofCeramicMatrixComposites
Composites,Vol.18,No.2,April1987

[5242]

R.Hayamietal
Si3N4:SiCWhiskerCompositeMaterials
TailoringMultiphaseandCompositeMaterials
Vol.20,p663674,1985

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ECSSEHB3220Part5A
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[5243]

R.Lundbergetal
SiCWhiskerreinforcedSi3N4Composites
Am.Ceram.Soc.Bull66[2],p330333,1987

[5244]

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Composites,Vol.18,No.2,April1987

[5245]

P.D.Shaleketal
HotPressedSiCwhisker/Si3N4MatrixComposites
Am.Ceram.Soc.Bull65[2],p351356.1986

[5246]

S.T.Buljanetal
Si3N4:SiCComposites
Am.Ceram.Soc.Bull66[2],p347352.1987

[5247]

P.F.Becheretal
TougheningofCeramicsbyWhiskerReinforcement
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G.Wei&P.G.Becher
DevelopmentofSiCwhiskerreinforcedCeramics
Am.Ceram.Soc.Bull64[2],p298305.1985

[5249]

T.N.Teigs&P.G.Becher
WhiskerReinforcedCeramicComposites
TailoringMultiphaseandCeramicComposites
Vol.20,p639647.1985

[5250]

J.Homenyetal
ProcessingandMechanicalPropertiesofSiCwhisker:Al2O3matrix
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Am.CeramSoc.Bull.67[2]p343347.1987

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J.R.Porteretal
Processing&CreepPerformanceofSiCwhiskerreinforcedAl2O3
Am.Ceram.Soc.Bull66[2],p343347.1987

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A.H.Chokshi&J.R.Porter
CreepdeformationofanAluminaMatrixCompositeReinforcedwith
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[5253]

A.A.Morroneetal
FractureToughnessandFatiguecrackGrowthbehaviourofan
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JournalofMaterialScience23,p32063213.1988

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S.C.Samanta&S.Musikant
SiCwhiskerreinforcedCeramicMatrixComposites
Proceedingsof9thAnnualConferenceonCompositeAndAdvanced
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N.Claussen&G.Petzow
WhiskerreinforcedOxideCeramics
JournaldePhysique,ColloqueCISupplementauNo.2,Tome47,
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WhiskerreinforcedZirconiatoughenedCeramics
TailoringMultiphaseandCeramicComposites
Vol.20,p647662.1985

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F.D.Gacs&J.J.Petrovic
FeasibilityofaCompositeofSiCwhiskerinaMoSi2Matrix
JournalAm.Ceram.Soc.68[8]C200201.1985

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W.S.Gibbsetal
SiCWhisker:MoSi2MatrixComposites
Ceram.Eng.Sci.Proc.8[78],p643648,1987

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Dr.A.Rittwegeretal:DaimlerAerospace/DASA,Bremen(D)
ThermoelasticAnalysisofaCeramicCompositeElevon
ProceedingsoftheEuropeanConferenceonSpacecraftStructures,
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November,1998.ESASP428,p351358

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M.Dogiglietal:MANTechnologie,Karlsfeld(D)
HypersonicAirIntakeRampaComplexHotCMCStructure
ProceedingsoftheEuropeanConferenceonSpacecraftStructures,
Materials&MechanicalTesting,Noordwijk,NL.2729thMarch,
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H.Kringsetal:MANTechnologie,(D)
FESTIPTechnologyDevelopmentsinMaterials
ProceedingsoftheEuropeanConferenceonSpacecraftStructures,
Materials&MechanicalTesting,Noordwijk,NL.2729thMarch,
1996.ESASP386,p10851096

[5262]

D.Sygullaetal:MANTechnologie/DLR(D)
TheUSEuropeanCooperationintheX38andCRVprograms
Abstractfromwebsite:www.iafastro.com(April2003)

[5263]

M.Dogiglietal:MANTechnologie(D)
AdvancedKeyTechnologiesForHotControlSurfacesInSpaceRe
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Proceedingsof53rdInternationalAstronauticalCongress,10th19th
October,2002.Houston,Texas,USA.PaperNo.IAC02I.3.02.
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[5264]

A.Schppachetal:CarlZeiss/DLR(D)
UseofCeramicMatrixCompositeinHighPrecisionLaser
CommunicationOptics

334

ECSSEHB3220Part5A
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Materials&MechanicalTesting,Noordwijk,NL.29thNovember1st
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SAMPEJournalVol.38,No.4(July/August2002),p2229

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U.Trabandt&W.P.P.Fischer:AstriumSIBremen
X38NoseSkirtPanelsResultsofQualificationTesting
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U.Trabandtetal:EADSST(Bremen)/DLRCologne/Universityof
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CeramicMatrixCompositesLifeCycleTestingUnderReusable
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Int.J.Appl.Ceram.Technol.,2[2]150161(2005)

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U.Trabandtetal:EADSST(Bremen)/DLRCologne/Universityof
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RLVTPSandHotStructuresOperationalCostEvaluationafterLife
CycleTestingwithRain,HailandLowSpeedImpacts
4thInternationalReentrySymposium,Archachon2005

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V.Liedke,U.Trabandt&M.Dogigli:
OxidationLifetimeImprovementofCMCbasedHotStructures
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ESAContractReportNo.6713/02/NL/CP;DocumentNumber:OLC
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U.Trabandtetal:Astrium,Bremen
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U.Trabandt&E.Monreal:EADSST(Bremen)/EADSDC
LiquidPolymerC/SiCandPotentialApplicationsinSpace
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ProceedingsofHTCMC5:5thInternationalConferenceonHigh
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335

ECSSEHB3220Part5A
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ProceedingsofHTCMC4:4thInternationalConferenceonHigh
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U.Trabandtetal:Astrium(Bremen&Friedrichshafen,D)
DeployableCMCHotStructureDeceleratorforAerobrake
Proceedingsof17thADSConference,May2003

336

ECSSEHB3220Part5A
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53 Glass and glass-ceramic matrix


composites
53.1 Introduction
The chemical stability and environmental resistance of glassbased materials made them a possible
matrix material for temperatures in the range 600C to 1300C. Interest has focused on carbon and
silicon carbide continuous reinforcements. The matrix can be chemically tailored to be more
compatiblewiththefibre.ThemostdevelopedmaterialsaredescribedinthisChapter.
Compositesaremanufacturedwiththeglassinaviscousphase,hencelimitingthehightemperature
fibredegradation.
For structural use, the mechanical properties determined from development materials are
encouraging,butasyetappeartobedifficulttoreproduce.Themechanicalcharacteristicsofthemost
advancedcompositesaregiven.
For aggressive environments, where metals and polymer composites degrade, the glass and glass
ceramiccompositescanbeattractive.

53.2 Continuous fibre composites


53.2.1

Characteristics

Glassesandglassceramicsoffer:

thermalstability,intherange600Cto1300C,

oxidationresistance,

erosionresistance,

chemicalstability.

Without modification by reinforcement, they lack combined strength and fracture toughness for
structuraluse.

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53.2.2

Composite development

53.2.2.1

Matrix

Work began with glasses such as borosilicates, having thermal capabilities around 600C. With
modifications to the glass constituents, by gradually introducing a higher ceramic content, thermal
stabilitybeyond1000Cispossible.
Importantattributesare:

Glasses can be created with a broad range of chemistry to control fibrematrix chemical
interaction.

Glassescanbeproducedwithawiderangeofthermalexpansioncharacteristicswhichcanbe
tailoredtonearlymatchthoseofreinforcingfibres.

Themodestelasticmoduliofglasses(50GPato90GPa),andglassceramics(80GPato110GPa)
enablehighmodulusfibrestoprovidetruereinforcement.

Theabilitytocontroltheviscosityofglassesandthenflowthemeasilyunderpressureenables
thephysicaldensificationofcompositeswithoutmechanicaldamagetothefibres.

Thecompositedensificationprocesscanberapid,sinceglassmatrixflowisallthatisneeded.In
thisrespect,thematrixcanbetreatedasathermoformablematerialwhichcanbemelted.

Table 53.2.1 shows the progression of the matrices used. Whilst these are mainly related to
developments at United Technology Research Center (UTRC) and Corning Glass (USA), the
informationisindicativeofthegroupofcompositesasawhole,Ref.[532],[533].

Table53.21Glassandglassceramicmatrices
Matrix

Major

Minor

Type

Constituents

Constituents

Max.Use
Temp
(C)

Glasses

7740 Boro-silicate
1723 Aluminosilicate
7930 High Silica

B2O3, SiO2

Na2O, Al2O3

600

Al2O3, MgO, CaO, SiO2

B2O3, BaO

700

SiO2

B2O3

1150

Glassceramics

LAS-I

Li2O, Al2O3, MgO, SiO2

LAS-II

Li2O, Al2O3, MgO, SiO2

LAS-III
MAS
BMAS
CAS
Ternary Mullite
Hexacelsian

Li2O, Al2O3, MgO, SiO2


Al2O3, MgO, SiO2
BaO, Al2O3, MgO, SiO2
CaO, Al2O3, SiO2
BaO, Al2O3, SiO2
BaO, Al2O3

Key:

ZnO, ZrO2,
BaO
ZnO, ZrO2,
BaO
ZrO2
BaO
-

100
1100
1200
1200
1250
~1500
~1700

:Incompositeform.

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53.2.2.2

Reinforcements

AnumberofreinforcementshavebeenconsideredforGMCs,including:

Continuousfibresandfilaments:

SiliconCarbide(SiC)

Boron

Carbon

Alumina

Glass

Whiskers.

By far the greatest effort has centred on fibre yarns of carbon, alumina, and SiC. Composites with
carbon fibres came first and exhibited significant strength and stiffness coupled with good fracture
toughness and low density (~2000kg/m3). For potential space use, there is the added benefit of
dimensional stability conferred to the composite by the carbon fibres. This can be exploited in
applicationsnotrequiringhightemperatureperformance.Themajordisadvantageofcarbonfibresas
areinforcementathightemperaturesisthattheyreadilyoxidiseinair.
Thealuminafibresystemshaveundergonemodestdevelopment.Whilstthesehavebeenshowntobe
unaffected by exposure to temperatures up to 1000C, the overall levels of toughness and strength
werelowerthanforcarbonandSiCreinforcements,Ref.[531].
SiCyarnreinforcedcompositesarenowthemainfocalpointfordevelopmentsinmatrixcomposition
togiveimprovedcomposites.

53.2.3

Manufacture

53.2.3.1

General

In comparison with other ceramic candidates, the glassy matrix composites offer considerable
potentialbecauseoftheir:

easeofcompositedensification,

lowcost,and

performancecharacteristics.

Whilst process technology was originally developed with glasses, they can be used with glass
ceramics. The key is that composite densification takes place whilst the matrix is in a substantially
glassy and viscous form. After full densification, the glassceramic can be heat treated to achieve a
matrixwithsuperiortoughnessandhightemperaturestrength.
Twofabricationtechniquesdominateforthesecomposites:

HotPressing,and

MatrixTransferMoulding.

Both methods exploit the good flow characteristics of glasses at high temperatures and are
appropriateforcontinuousfibrereinforcements.

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53.2.3.2

Hot pressing

Unidirectionalmonolayertapesaremadebywindingslurryimpregnatedyarnsontoamandrel.The
slurryconsistsofwater,awatersolubleresinbinderandaglasspowder.Thesetapesarecuttomake
plies,whicharedensifiedbyhotpressing.Forproperdensificationtooccur,pressingiscarriedoutat
atemperaturewheretheglassviscosityislowenoughtopermittheglasstoflowintotheinterstices
betweenindividualfibresoftheyarnbundles.Pressureisappliedonlyafterthemouldtemperature
reaches the softening point of the matrix. The resulting composites are generally >98% theoretical
density. Multidirectional composites made from tapes are possible, as are variants using fabric
reinforcements.

53.2.3.3

Matrix transfer moulding

Hot pressing of tapes and woven fabric layups is less suitable for complex external and internal
geometrycomponents.Inthesesituationscarefullyengineeredfabricpreformscanbeused.Theseare
arrangedinsideamouldcavity,thenafluidglassmatrixistransferredathightemperatureintothe
mouldcavitytofullyimpregnatethepreform.Whilstthinwallandcomplexshapescanbeproduced,
the desired fluidity of the glasses can only be achieved by using a substantially higher processing
temperature than for hot pressing. This, in turn, can result in excessive fibrematrix interaction and
consequentembrittlementofthecomposite.

53.3 Carbon fibre reinforced composites


53.3.1

Material

Developments in these materials have centred on borosilicate glass for the matrix. UTRC have used
T300,GY70,P100andHMUfibresandAerospatialeXASandIM6,Ref.[534].

53.3.2

Mechanical properties

53.3.2.1

Tension

Table53.3.1andTable53.3.2summarisemechanicalpropertiesachievedbythecomposites,Ref.[53
8].Themechanicalpropertiesarerespectableforthisclassofmaterial.Manyoftheglassmatricesare
PYREXfromCorningGlassWorks(USA),Ref.[538].

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Table53.31Carbonfibre/borosilicateunidirectionalcomposites:Mechanical
properties
CarbonFibre

Fibre(Vol%)

T300

39

GY-70

58

P-100

54

Properties

UTS
E
UTS
E
UTS
E
flex

XAS

65

E
ILSS
flex

IM6

68

E
ILSS

Key:

Unidirectionalcomposite

RT
RT
RT
RT
500C
RT
500C
RT
500C
RT
500C
RT
500C
RT
500C

(MPa)
(GPa)
(MPa)
(GPa)
(MPa)
(GPa)
(MPa)
(MPa)
(GPa)
(GPa)
(MPa)
(MPa)
(MPa)
(MPa)
(GPa)
(GPa)
(MPa)
(MPa)

710
127
680
322
680
322
1240
1237
158
154
38
36
1030
970
160
160
30
30

InertArgonenvironment

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Table53.32UnidirectionalandangleplytensiledataforHerculesHMUcarbon
fibrereinforced7740borosilicateglasscomposite
UnidirectionalTensileData
Composite

0
Mean value
10
Mean value
30
Mean value
60
Mean value

PL

(GPa)
165
170
173
169
120
146
144
140
72
70
68
70
35
38
33
35

(MPa)
299
266
304
290
139
128
153
140
29
41
39
37
11
16
19
15

UTS(MPa)

787
856
711
785
170
175
168
171
50
50
41
47
18
18
24
23

0.170
0.195
0.183
0.183
0.184
0.198
0.179
0.187
0.169
0.197
0.187
0.184
0.112
0.134
0.086
0.111

UTS(MPa)

429
469
424
441
179
193
189
187
44
40
48
44
25
25
22
24
252
317
331
300

0.286
0.269
0.295
0.283
0.887
0.834
0.972
0.898
0.696
0.687
0.633
0.672
0.287
0.313
0.248
0.283
0.022
0.005
0.025
0.017

f
(%)
0.618
0.657
0.531
0.602
0.123
0.121
0.111
0.118
0.078
0.073
0.060
0.070
0.054
0.075
0.077
0.069

AnglePlyTestData
Composite

[10]s
Mean value
[30]s
Mean value
[45]s
Mean value
[60]s
Mean value
[0/90]
Mean value
Key

PL

(GPa)
158
161
163
161
81
70
77
76
42
35
36
38
24
24
20
23
81
80
86
82

(MPa)
170
160
224
185
12
19
14
15
5.6
5.6
6.6
5.9
3.0
2.8
4.5
3.4
39
52
39
43

f
(%)
0.420
0.418
0.319
0.410
0.399
0.524
0.594
0.506
0.384
0.249
0.512
0.382
0.655
0.408
0.459
0.507
0.403
0.500
0.527
0.477

PLindicatesproportionallimit,astheinitialdeviationfromlinearityof/curve.
FibreVolumeFraction:40to43.6%,exceptfor60UDwhereVf=30%.

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53.3.2.2

Notched

ThenotchsensitivityofHMUcarbonfibrereinforcedCode7740borosilicateglassisshowninTable
53.3.3,Ref.[536].The0/90compositesarereasonablynotchinsensitive,Ref.[536].

Table53.33Mechanicaltestdatafornotched0/90reinforcedHMU/7740
composites
HoleDia.
(mm)

Unnotch
ed
1.6
3.1
6.4

d/b

Fibre
Vol.%

0
0
0
0.110
0.113
0.112
0.202
0.431
0.429

39
38
40
39
38
40
39
38
40

Actual
UTS

Normalised
ActualUTS

(MPa)

(MPa)

309
320
341
324
334
330
296
297
306

1.0
1.0
1.0
1.05
1.04
0.97
0.96
0.93
0.90

Key

:Ratioofnotched/unnotchedtensilestrength.

d/b:Ratioofholediametertospecimenwidth.

(MPa)

Ultimate
Extensometer
Strain(%)

43
81
76
121
37
77
16
20
31

0.48
0.56
0.57
0.92
1.05
0.97
1.08
1.42
1.52

PL

This is in agreement with fracture theory which predicts this response from composites with low
values of interfacial (fibre to matrix) shear resistance and high values of insitu fibre strength. The
desirablebenignandfibrepulloutcharacteristicsofthisglassmatrixceramicarethesameasforall
brittlematrixcomposites.

53.3.2.3

Environment

Owingtotheinertnessofglassmatrixcompositeswithrespecttovacuum,thereisinterestintheUSA
forthesematerialsinstructuralapplications.Materialcharacterisationisproceeding,Ref.[536].

53.3.2.4

Thermal expansion

Ascarbonfibreshaveahighlynegativeaxialcoefficientofthermalexpansion(CTE),itispossibleto
achieveacompositewithaCTEclosetozero.

53.3.3

Applications

The incorporation of highmodulus carbon fibres, e.g. GY70 and P100, into glasses has been
exploitedinspacerelatedmirrorsandreflectors.
OnesuchapplicationisinthermallystableinfraredmirrorsusingUTRCThermallyStableComposites
(TSC). A 300mm diameter frit bonded composite mirror in the form of an eggcrate sandwich
constructionhasbeendeveloped,Ref.[537].Anaddedadvantageofusingthesematerialsisintheir
abilitytobemachined,replicatedandfiguredusingconventionalpolishingtechniques.

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53.4 Silicon carbide fibre reinforced composites


53.4.1

Composite development

53.4.1.1

Matrix

In moving from carbon to SiCfibre reinforcementsin search of oxidation resistance, it became clear
thatborosilicateglassescouldnotexploitthefullpotentialofSiCfibres,suchasNicalon,Ref.[539].
It was therefore necessary to move to glassceramics, such as lithium aluminosilicate (LAS) with
various modifications. There is a further group of matrices, such as magnesium aluminosilicate
(MAS),Ref.[5310],andBariummagnesiumaluminosilicate(BMAS),Ref.[5311],whichofferhigher
thermalstabilitythanLAS.Thesecouldbeexploitedinthefuture.Thematrixcompositionsnotonly
contributetosuchcompositepropertiesaselasticmodulusandcoefficientofthermalexpansion,but
moreimportantly,matrixcompositionsprovideameansofcontrollingfibrematrixreactionsduring
composite densification. This reactivity, or lack thereof, determines the nature of the fibrematrix
interface.

53.4.1.2

Fracture

Animportantfeatureofthesecompositesistheirfracturecharacteristics,whicharefibrousinnature,
providing high crack growth resistance and hence toughness. The term fibrous implies significant
fibrepulloutratherthanacleanfracturethroughfibreandmatrix.InthesuccessfulLASmatrix/SiC
yarnsystems,thefibrematrixinterfacehascharacteristicswhichprovideexcellentfracturetoughness,
Ref.[5310].Amongthesearetheformationofniobiumcarbide(NbC)particlesaroundthefibresand
averythincarbonrichlayerbetweenthefibreandNbCparticle.TheNbCresultsfromthereaction
betweenNb2O5fromtheLASmatrixandtheSiCfibres.

53.4.1.3

Thermal stability and toughness

The thermal stability and toughness of glassceramics are achieved through microstructural
modifications obtained by heat treatments. For the LASII/SiC system, the aspressed matrix is
primarilyglassywithsmallamountsofMullite(3Al2O3.2SiO2)andquartzsilicasolidsolutionLAS
crystals, which form on cooling from the fabrication temperature. By heattreatment, a matrix is
achieved which is highly crystalline, primarily spodumene with a small amount (<10 vol. %) of
residualglassyphaseatthegrainboundaries.
Table53.4.1givesthepropertiesofvariousaspressedandceramicSiC/LAScomposites.

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Table53.41SiCreinforcedglassceramiccomposites:ComparisonofRT
unidirectional(0)propertieswithSiCfibrereinforcedepoxy
Matrix

Property

Matrix state
Fibre Vol.%

Epoxy

LASI

LASI

LASII

LASII

P
46

C
46

P
44

C
44

Tension

Strength (MPa)
Elastic modulus
(GPa)
Failure strain (%)

875

455

670

680

106

133

128

136

0.84

0.33

0.90

1.03

Flexural

Strength (MPa)
Ratio flexural to
tensile strengths
ILSS (MPa)
Key

1240

755

758

1380

1050

1042

1.67

2.06

1.54

87

34.4

P:Aspressed;C:Ceramed

53.4.1.4

Stress-strain and fracture

The stressstrain and fracture characteristics of glassceramic matrix composites are different from
thoseofthermosettingresincomposites.Thishasimportantconsequenceswhendesigningwiththese
newmaterials.

Thestressstrainresponseofunidirectional(0)LASII/SiCcompositesisnotlinear(Hookean)
tofailure.

At fairly modest strains of around 0.4%, the matrix starts to crack locally as this reflects the
straincapacityofthematrix.Theprogressofthecracksisinhibitedatthefibrematrixinterface,
duetodecouplingbetweenthetwo.

Anetworkofmicrocracksdevelopsasthestrainincreases.Thismicrocrackinghastheeffectof
loweringtheelasticmodulus,uptothemaximumstresswhichoccursataround1%strain.

Unlikepolymermatrices,theglassceramicmatricesmakeasignificantcontributiontostiffness
astheirmoduliareintherange60GPato100GPa,whereasthoseofpolymersare2GPato3GPa.
Progressivematrixcrackingthereforedeprivesthecompositeofsomeofitsstiffness.

When the highest stress is reached, catastrophic failure is not inevitable because progressive
fibrepulloutcanoccur.

The maximum stress achieved by the composite is very much determined by the retained in
situstrengthoftheSiCfibres.

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53.4.2

Effect of in-situ fibre strength

Theimportanceofinsitufibrestrengthappliestoallhightemperaturecompositesbecausethereisa
riskoffibredegradationbythermallyinducedchemicalandmicrostructuralmodifications.
As an indication of the strength degradation which can occur solely through high temperature
processing,SiCfibreshavebeenextractedfromcompositeswheretheirstrengthhasfallenfromthe
original2070MPato1450MPa,i.e.a30%loss.

53.4.3

Effect of fibre-matrix bonding

Modest fibretomatrix bonding ensures the desired strength and toughness characteristics. This has
implicationsfortheoffaxiscompositeresponse,suchas90plystraintofailure.

For 0/90 constructions, the 90 ply strain to failure is low at around 0.05%; a consideration for
designingcomponentswiththesematerials.Thereforefabricsandmultidirectionalfibrepreformsare
preferable to unidirectional composites by providing increased fibre integration and avoiding weak
matrixdominatedplanes.

53.5 Silicon carbide reinforced composites: properties


53.5.1

LAS matrix composites

53.5.1.1

General

TheLASmatrixversionshaveundergonethegreatestdevelopmentandarethemostappropriateto
concentrate on. The progression from LASI to LASIII improved the overall strength and thermal
stabilityofcomposites.

53.5.1.2

Stress-strain response

Unidirectional LASI composites exhibit Hookean (linear) stressstrain response without


significantlevelsofmicrocrackingpriortotheultimatestrength.

ForLASIIandLASIII,asignificantextensiontothestressstrainresponseoccursbeyondthe
onsetofmatrixmicrocracking.ThiseffectivelygivesaProportionalLimit;seeFigure53.5.1.

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Figure53.51Glassceramiccomposites:Tensilestressstraincurvefor
unidirectional(0)SiC/LASIIatroomtemperature
Theproportionallimitprovidesatenuouscomparisonwiththeresponseofmetalsandisanindicator
of the true strength of the composite in terms of elastic response. All tensile and flexural strength
figures stated relate to the ultimate strength of the composite, i.e. the insitu strength of the fibres,
beyondtheonsetofmicrocracking.
Figure53.5.2providesabetterinsightintothetruestresstostrainresponseofaglassceramicmatrix
composite,Ref.[5311].

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Key: Temperature: 25C, Strain Rate 5 x 10-5 sec-1

Figure53.52Glassceramiccomposites:Flexuralstressstraincurvefor
SiC/BMASIII

53.5.2

Mechanical properties

53.5.2.1

General

Published literature shows that problems have been encountered in achieving reproducible results
with the development materials; not least in relation to insitu fibre strength. No definitive
explanationhasbeenidentified.

53.5.2.2

Tensile and flexural

Both the tensile and flexural strengths of SiC/LAS composites have been measured and indicative
valuesaregiveninFigure53.5.3,[Seealso:Table53.4.1],Ref.[5313].

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Conditions: Three-point bend in Argon

Figure53.53SiCreinforcedglassceramiccomposite:Flexuralstrengthversus
temperatureforunidirectionalSiC/LAS

Whilst the tensile mode of failure is fairly well understood, the flexural response is slightly more
complex due to the presence of compressive forces within the specimens. This gives rise to a
phenomenonwheretheflexuralstrengthscanactuallyincreaseatintermediatetemperatures(800Cto
1000C) just below temperatures where excessive matrix softening leads to a loss in strength, [See:
Figure53.5.3].
Theincreaseinflexuralstrengthat800Cto1000Cisthoughttoresultfrompartialmatrixsoftening
enablinglocalisedloadredistributionduringthreepointbending.
Flexuralstrengthsarealwayshigherthantensilestrengthforacorrespondinglysimilarmaterial.The
hightemperaturebendstrengthsinFigure53.5.3wereobtainedinaninertatmosphere.

53.5.2.3

Effect of environment

The effect of oxidation is shown in Figure 53.5.4. The bend strengths above 600C show a dramatic
dropandfluctuationindicatingoxidativepenetrationofthecomposite.

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Conditions: Three-point bend, in Argon and Air

Figure53.54SiCreinforcedglassceramiccomposite:Flexuralstrengthversus
temperatureforunidirectionalSiC/LASIII
53.5.2.4

Compression

ThecompressiveresponseofSiC/LAScompositesprovidesafurthercontrastonfailurecharacteristics,
Ref.[5314].Matrixmicrocrackingisagainpresentbeyondcertainstrainlevels,butfibrebucklingand
fibre (bundle or yarn) kinking determines ultimate strain levels. Figure 53.5.5 shows compressive
strengthversusstrainresponsesforLASII/SiCcomposites.
Offaxisplies,suchas45and90,incompositeshavelowfailurestrains.Thisisobservedfortensile
loading, and coupled with matrix microcracking (proportional limit) makes clear that maximum
permissibleoperatingstrains,hencestresses,aremodestforthesecomposites.

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Figure53.55SiCreinforcedglassceramiccomposite:Compressivestressstrain
responseof0,0/90,and45SiC/LASIII,at23C
Figure53.5.6showstheflexuralstressstrainresponseofa0/45/90LASII/SiCcompositeatvarious
temperatures. The response of this multidirectional composite has a proportional limit of around
100MPaforalltesttemperatures.

Figure53.56SiCreinforcedglassceramiccomposite:Flexuralstressstraindata
for0/45/90SiC/LASforawidetemperaturerange
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Figure 53.5.7 and Figure 53.5.8 provide indicative strength data for SiC/LAS composite against the
unreinforcedmonolithicglassceramic,Ref.[5317].

KEY:
c Ultimate Compression Strength
y Yield Strength in Compression
AE Acoustic Emission Threshold in
Compression

Figure53.57SiCreinforcedglassceramiccomposite:Strengthsversus
temperatureformonolithicLAS(Pyroceram)andunidirectionalLAS/SiC
(Compglas)

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Key:

TUltimatetensilestrength

flexUltimateflexuralstrength

Figure53.58SiCreinforcedglassceramiccomposite:Dependenceoffailure
strengthswithtemperatureandloadingmodefor0Compglasandmonolithic
Pyroceram
53.5.2.5

Fatigue

The formation of microcracking at modest stress levels, often well below ultimate strength, has
important implications for repetitive loading, as in fatigue, Ref. [5315], [5316]. Flexural fatigue
testing indicates that the use of peak fatigue stresses greater than the proportional limit have the
effect of inducing further microcracking. This implies a larger network of microcracks providing
greater access for the environment to enter the composite and increase the fibre degradation. The
repetitive increase in microcracking effectively lowers the proportional limit. As a result of high
tensilestressfatiguetheproportionallimitstresscanbereducedbyasmuchas60%.
SomepreliminaryflexuralfatiguedatahasbeenacquiredforUD(0)LASII/SiCcomposite,seeFigure
53.5.9,Figure53.5.10andFigure53.5.11.Themainpointscanbesummarisedas:

At22C(RT)theultimateflexuralstrengthswerebetween700MPaand850MPawithaspread
inproportionallimitof300MPato600MPa.

Peak flexural stresses less than 650MPa were required to ensure that 105 fatigue cycles are
enduredandallowrunout.

The residual strengths of specimens surviving 105 cycles were similar to those of asmade
specimens.

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When the test temperature was raised to 600C, the ultimate bend strength of the asmade
composite increased reaching 1000MPa to 1100 MPa. The proportional limit was however
muchlowerataround380MPa.

Subsequent fatigue tests at this temperature showed that peak fatigue stresses had to be less
than380MPatoachieve105cyclerunout.

Theresidualstrengthofthecompositeexperiencing105cycleswascorrespondinglylow.

Fibre volume fraction: 45 to 50%

Figure53.59SiCreinforcedglassceramiccomposite:Comparisonofflexural
strengthundervariousloadingconditionsfor0SiC/LASat22C

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Fibre volume fraction: 45 to 50%

Figure53.510SiCreinforcedglassceramiccomposite:Comparisonofflexural
strengthundervariousloadingconditionsfor0SiC/LASat600C

Fibre volume fraction: 45 to 50%

Figure53.511SiCreinforcedglassceramiccomposite:Comparisonofflexural
strengthundervariousloadingconditionsfor0SiC/LASat900C

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At the same time stress rupture tests lasting 50 hours were conducted to quantify the continuous
stresslevelthatthecompositecouldwithstandwithoutfailure:

For50hours,thiswasaround380MPa.

At900C,stressesbelow300MPawereneededtoachieve105cyclesrunout;seeFigure53.5.12,
Figure53.5.13andFigure53.5.14,Ref.[5316].

Figure53.512SiCreinforcedglassceramiccomposite:Roomtemperaturefour
pointflexuralfatigueof0SiC/LASII

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Figure53.513SiCreinforcedglassceramiccomposite:Roomtemperaturetensile
fatigueof0SiC/LASIII

Figure53.514SiCreinforcedglassceramiccomposite:Roomtemperature
uniaxialtensilefatigueof0/90SiC/LASIIand0/90SiC/LASIII

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53.5.2.6

Summary of strength data

The conclusion to be drawn from the strength data presented is that the ultimate strengths of these
compositesatroomtemperaturearerespectableataround800MPaforaunidirectionalcompositein
bending.However,theusablestrengthfordesignpurposesisloweredby:

Offaxisplies,

Tensileandcompressiveloadings

Hightemperatures,upto1000C

Fatigueloading

Theinitiationofmicrocracking.

Itissuggestedthat200MPaisarealisticdesignstrengthfigurefor0unidirectionalcompositeand
100MPaforbidirectional.Thetermstrengthisusedloosely,butisapplicabletotensile,compressive
andflexuralmodes.

53.5.2.7

Fracture toughness

The fracture toughness data on glassceramic matrix composites show that LASII and LASIII
composites possess attractive properties compared with monolithic glasses, glassceramics and
ceramics.
The throughthickness fracture toughness of a unidirectional or bidirectional composite are around
30MPam,comparedwith2MPamformonolithicglassceramicmatrix.Thehighestvaluesarefor
throughthicknessandfracturetoughnessbetweenplanesisdistinctlylower.
Bothnotchedthreepointbendtestsandcantileverbeamspecimenshavebeenusedtoderivefracture
toughnessvalues.
Whilst these values are termed K1C by some sources, they are only for comparative purposes. The
knowledgeonfracturemechanicsofthesematerialsisincomplete.
For2Dfabricbasedcomposites,poorinterlaminarandthroughthicknessstrengthsposeproblemsin
some applications. Like many composites the option is available to use 3D fibre preforms (fibre
architecture) to improve these strengths. 3D braided SiC/LASIII have been successfully prepared,
whichgivemoreevenfracturetoughnessvaluesinthroughthicknessorientations,Ref.[5318].

53.6 Potential applications


53.6.1

Technology status

53.6.1.1

USA

ThemosthighlydevelopedcompositesarethoseofUTRCunderthetradenameCOMPGLAS.These
include the LAS systems. These materials are being evaluated for the gas turbine engine and
aerospaceapplicationsintheUSA.However,theyarenotofferedascommercialmaterialsonaworld
widebasis.

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53.6.1.2

Europe

Developments in borosilicate matrix composites at Aerospatiale (France) and Harwell Laboratory


(UK)forengineapplicationsattemperaturesof~600Carereported,Ref.[534],[5319].

53.6.1.3

Summary of composite development

Fibre,matrixandinterfacearealltailoredtoachievestrong,toughcomposites.

Lowfibrematrixinterfacialstrengthimplieslowoffaxisstrength.

Nonlinear stressstrain curves and an elastic modulus that decreases with increasing strain
shouldbetakenintoaccountinsuccessfuldesigns.

Flexural tests by themselves are an inadequate means of defining composite stressstrain


behaviourorstrength.

Environmentalstabilityandcompositestructurallifepredictionarethekeyissuesforsuccessful
compositeapplication.

Nonstructural applications, such as tribology and dimensional stability, can provide the first
usageofthesecomposites.

Microindentationtesttechniquesarebeingusedtoassesstheinterfacialshearstrengthbetween
fibreandmatrices,Ref.[5320].

53.6.1.4

Applications resum

There are two main advantages of glass and glassceramic composites over their ceramic matrix
counterparts:

Thematricesarethermoformable,likemetals,givinggreaterfreedomonprocessingandbetter
controlofcomposition.

The consolidation temperatures of 800C to 1300C stay within the stability range of the
inorganic,ceramicandcarbonfibres.

For intermediate temperatures of 500C to 1000C, these composites have weightsaving attractions
overmetals,e.g.titaniumandnickelalloys.Forlongtermapplications,theircreepperformancehas
yettobedetermined.
Inmanyrespects,theirabilitytoachievespecificphysicalratherthanmechanicalpropertiescanbea
drivingforcefortheiruse,e.g.lowCTEmaterials(withcarbonfibres)canbeusefulinapplicationsof
longterm exposure to space environments, such as LEO, where plastics and metals can show
progressivedegradation.
Thesecompositescanalsobeusedforelectronicsubstratesandcarriers.

53.7 References
53.7.1

General
[531]

T.A.Michalske&J.R.Hellman
StrengthandToughnessofContinuousAluminaFiberReinforced
GlassMatrixComposites

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J.Am.Ceram.Soc.71[9],p725731.1988
[532]

K.M.Prewoetal
FibrereinforcedGlassesandGlassCeramicsforHighPerformance
Applications
CeramBulletinVol.65,No.2,p305314.1985

[533]

K.M.Prewo
TheDevelopmentofFiberreinforcedGlassesandGlassceramics
TailoringMultiphaseandCompositeCeramics
Vol.20,p529547.1985

[534]

A.Moguez
GlassMatrixComposites,ManufactureandPerformanceData
LookingAheadforMaterialsandProcesses.ElsevierScience
Publishers,TheNetherlands.p17.1987

[535]

R.A.Allaireetal
GlassMatrixCompositesforHigherUseTemperatureApplications
SAMPEQuarterly.October1987.p2530

[536]

W.K.Tredway&K.M.Prewo
CarbonFibrereinforcedGlassMatrixCompositesforSpacebased
Applications
ONRReportR879174701
ContractN0001485C0332.ADA184355.August1987

[537]

J.H.Bluegeetal
ThermalStabilityofLightweightGraphiteGlassSandwichReflectors
forInfraredAstronomy
SPIEVol571LargeOpticsTechnology.p254258.1985

[538]

[8]
V.C.Nardone&K.M.Prewo
TensilePerformanceofCarbonFibrereinforcedGlass
JournalofMaterialScience23.p.168180.1988

[539]

K.M.Prewo&J.J.Brennen
SiliconCarbideYarnReinforcedGlassMatrixComposites
JournalofMaterialsScience17,p12011206,1982

[5310]

V.JPowers&C.H.DrummondIII
SiCFiberreinforcedGlassceramicCompositesinthe
Zirconia/MagnesiumAluminosilicateSystem
Proceedingsofthe10thConferenceonCompositesandAdvanced
CeramicMaterials,p969977,1986

[5311]

R.L.Stewartetal
FractureofSiCFiber/GlassceramicCompositesasafunctionof
Temperature
FractureMechanicsofCeramics,Vol.7,p3351

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[5312]

J.J.Brennen
InterfacialCharacteristicsofGlassandGlassceramicMatrix/Nicalon
SiCFiberComposites
TailoringMultiphaseandCompositeCeramics
Vol.20,p549560.1985

[5313]

K.M.Prewo
TensionandFlexuralStrengthofSiCFibrereinforcedGlassceramics
JournalofMaterialsScience21,p35903600.1986

[5314]

JLankford
Temperaturestrainrate&FibreorientationEffectsinthe
CompressiveFractureofSiCfibrereinforcedGlassmatrix
Composites
Composites,Vol.18,No.2,p145152.April1987

[5315]

K.M.Prewo
FatigueandStressRuptureofSiliconCarbideFibreReinforcedGlass
ceramics
JournalofMaterialsScience22,p26952701.1987

[5316]

E.Minford&K.M.Prewo
FatigueBehaviourofSiCfiberreinforcedLithiumAluminoSilicate
Glassceramics
TailoringMultiphaseandCompositeCeramics,
Vol.20,p561570.1985

[5317]

J.Lankford
StrengthofMonolithicandFibrereinforcedGlassceramicsatHigh
RatesofLoadingandElevatedTemperature
Ceram.Eng.Sci.Proc.9[78],p843852.1988

[5318]

F.Koetal
StructuralTougheningofGlassMatrixCompositesby3DFibre
Architecture
Ceram.Eng.Sci.Proc.8[78],p822831.1987

[5319]

D.M.Dawsonetal
FabricationandMaterialsEvaluationofHighPerformanceAligned
CeramicFiberreinforcedGlassMatrixComposite
Ceram.Eng.Sci.Proc.8[78]p815821.1987

[5320]

D.H.Grandeetal
Fibre/matrixBondStrengthStudiesofGlass,CeramicandMetal
MatrixComposites
JournalofMaterialScience23,p311328,1988

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54 Carbon-Carbon matrix composites


54.1 Introduction
54.1.1

Applications

TheapplicationsforCarbonCarboncompositescanbebroadlygroupedasthoseaimingto:

exploithightemperaturecapability,or

capitaliseondimensionalstabilitycharacteristics.

54.1.2

High temperature

BasedontheexperienceofusingCCmaterialforshortduration,singleusespaceapplications,their
characteristics appropriate for use in reusable, longlife structures were investigated. The work was
largely conducted in programmes considering space planetype vehicles. The applications included
thermalprotectionthermalshieldsforregionsofthevehicleduringreentry,[Seealso:Chapter71].
Despite their advanced commercial status, mechanical property data is limited. This is a direct
reflectionoftheinfluencematerialprocessinghasonthefinalmaterial.Assuch,anydatastatedare
consideredasindicativeonlyofwhatispossible,[See:54.2].
AnimportantconsiderationistheoxidationofCarbonCarbonattemperaturesabove500C.Various
protectionmethodsaredescribed,[See:54.4].

54.1.3

Dimensional stability

The low thermal expansion characteristics of CC composites make them of interest for applications
demanding very high dimensional stability. The knowledge of materials and processing, developed
initiallyforhightemperatureapplications,hasenabledaCCcompositetoreachqualifiedstatusfor
somestructuralpartsforspacetelescopesorscientificinstruments,[See:54.6].

54.2 Material description


54.2.1

Characteristics

54.2.1.1

General

Interest in carbon matrix composites has centred on materials which combine a carbon fibre
reinforcement with a carbon matrix. These materials are known as carboncarbon (CC) composites.
Therearemanyvariants,asshowninFigure54.2.1,arisingfromthe:

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specificfibreused,

forminwhichthefibreisused,and

methodofcreatingthecarbonmatrixphase.

Theselectionofmaterialsandprocessingrouteuseddeterminethespecificmechanicalpropertiesof
the finished component. A major advantage of multidirectional carboncarbon composites is the
freedomtoorientateselectedfibretypesandamountstoaccommodatethedesignloadsofstructural
components.

54.2.1.2

Fibre architecture

Thearchitectureofthecarbonfibrereinforcementcantakemanyformsincluding,[Seealso:6.31]:

randomshortfibres,

unidirectionalfibres,

braidedstructures,

laminatedfabrics,

orthogonal3Dweaves,ineitherCartesianorcylindricalcoordinates,

multidirectionalstructures,suchas4Dstructures.

54.2.1.3

Properties

GeneralpropertiesofCCcompositesare:

lightweight.

abilitytooperateathightemperaturesowingtotheirrefractorynature.

goodmechanicalpropertiesincludingfractureresistance.

lowthermalexpansion.

Mechanical properties are usually satisfactory in the two dimensions containing the reinforcement,
butthecarbonmatrixisweaksotheperformanceinthethirddirectionisverylow,[See:54.3].

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Figure54.21Carboncarboncomposites:Schematicdiagramofmaterialselection
andprocessingroutes
54.2.1.4

Oxidation

The major hindrance is that the oxidation resistance of CC is poor. Exposure to oxygencontaining
atmospheresattemperaturesabove500Cresultsinsignificantweightlossandpropertydegradation.
To improve oxidation resistance it is necessary to create a barrier to the aggressive environment;
usuallybycoatingthecomposite.

54.2.2

Manufacturing techniques

54.2.2.1

Reinforcement forms

The carbon fibrereinforcement is generally woven into a preform to produce unidirectional or


multidirectional (2D, 3D or 4D) fibre arrangements. Figure 54.2.2 shows the fibre arrangement in
SEPCARB4Dpreform.

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Figure54.22Carboncarboncomposites:4DfibrearchitectureinSEPCARB4D

Figure54.2.3showsexamplesof3Dfibrepreforms.

3-D preform

3-D polar preform

Figure54.23Carboncarboncomposites:3Dfibrepreforms
Theweavingprocessesusedtocreatemultidirectionalnearnetshapepreformshavebeenthetopicof
extensiveoptimisationandautomation,Ref.[541].Producingthefibrepreformremainsasignificant
costcontributor.Thechoiceofwovenpreformislinkedtotheapplication,e.g.throatnozzlesuse3D
and4Dpreforms,someexitconesuse3Dpolarweavepreforms(cylindricalcoordinates)tosustain
the severe thermal stresses. Polar weave preforms are used for cylinders and other shapes of
revolution,e.g.cylindersandcones,convergentordivergentsections,Ref.[5423].3Dcarboncarbon
isalsousedtomanufacturehightemperaturefasteners,e.g.screws,nutsandbolts,Ref.[5422].
Someexamplesofcomplexshaped,multidirectionalfibrepreformsareshowninFigure54.2.4.

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Figure54.24Carboncarboncomposites:Examplesofmultidirectionalfibre
preforms
54.2.2.2

Matrix

Thematrixphaseisintroducedintothepreformbyeither:

Liquid Impregnation: using resins or pitches, which are subsequently carbonised. The use of
pitchneedsatwostageprocess:

partialimpregnationorrigidisationofthefibrepreformandpyrolysis,then

densification.

Chemical Vapour Infiltration (CVI): under the controlled temperatures and pressures of a
reactionvessel,methaneorethaneareconvertedanddepositedaspyrolyticcarbon.

Theliquidresinroutealsoneedsrepetitionoftheimpregnationandpyrolysistreatmentstoachieve
densification of the composite. Repetition of the densification stage is undertaken to achieve the
desireddensityandproperties.
TheCVImethodreliesonthedepositionofthecarbonmatrixonandbetweenfibres.Theprocessing
timescanexceed100hours.
CVIisnormallyusedforthinwalledparts.Liquidinfiltrationmethodsareusedforthickersections.A
combinationofbothtechniqueshasalsobeenused,Ref.[542].

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54.3 C-C composite: Properties


54.3.1

Mechanical properties

54.3.1.1

General

AlthoughCCcompositesareinadvancedstagesofdevelopmentandapplication,comparedwiththe
othermaterialoptions,verylittledataonmechanicalpropertieshavebeenpublishedopenly.Thisis
primarily due to the significant resources put into their development and evaluation and the
commercial demands of those companies in capitalising on the expertisegained. There arehowever
somegeneralcommentsonthemechanicalpropertiesofCCmaterialswhichcanbepresented.
Table 54.3.1 gives mechanical properties which are indicative of those attainable by different CC
composites,butcautionisneededintheirinterpretation,Ref.[544],[545].

Table54.31Carboncarboncomposites:Indicativemechanicalproperties
CCCompositeType

PropertiesatRT

Density
Tensile Strength
Tensile Modulus
Compressive
Strength
Compressive
Modulus
54.3.1.2

3D

2D

(GPa)
(GPa)

1750 1950
200 - 260
90 - 100

1820 1950
127 - 172
68 - 101

(MPa)

140

214

88 - 170

(GPa)

68

3.2

61 - 73

(kg/m3)

CCwithSiCCoat

1700 - 1800
100 - 140
63 - 67

Multidirectional reinforced composites

Thereinforcementfibrearchitectureinfluencesthecompositeperformance,[See:54.2].Themechanical
propertiesaregenerallysatisfactoryinthetwodirectionscontainingthereinforcement,butthecarbon
matrixisweaksotheperformanceoftheotherdirectionisverylow.Thisproblemiscrucialduring
manufacturing when high internal stresses provoke delamination of the constituent plies or in
applications involving high thermomechanical loading, such as reentry and rocket motors
components,Ref.[5423].
Multidirectional carboncarbon composites provide the freedom to orientate fibres of various types
andamountstoreactthedesignloadsofthestructuralcomponents.Theycanalsobemachinedandto
create small radii. The cost of producing the fibre preforms, even using fullyautomated weaving
machines,isstillsignificant.This,alongwithlowmechanicalperformanceinnonreinforceddirection,
arethemaindisadvantages,Ref.[5423].
Whilst the nose cone and leading edges of the Space Shuttle Orbitor are formed from 2D carbon
fabric,multidirectional(3Dand4D)areusedforstructuresexperiencingseverethermalstresses,e.g.
throatnozzels,exitcones,[See:54.2].Mechanicalfasteners,using3Dreinforcements,shownolossin
strength at high temperatures and demonstrates the superiority of CC compared with metals, Ref.
[5422].

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54.3.1.3

Stiffness

ThemodulusofCCcompositesisdictatedbythemoduliof:

fibre,and

matrix.

Usuallythestiffnessofthematrixinpolymericmatrixcompositesisignored,butforCCmaterialsthe
stiffnesscontributionissignificant.
Figure 54.3.1 shows the stiffness of three CC materials created from different carbon matrix
precursorsthathavereceiveddifferentheattreatmentsat1000Cand2600C.Theresultantstiffnessis
determinedbycalculationofthetheoreticalmoduluswithoutthematrixstiffnesscontribution,hence
valuesgreaterthan1.0arequoted.

Conditions:

Materials produced from different matrix precursors, with two different final heat treatment
temperatures (HTT).

Figure54.31Carboncarboncomposites:Predictedmodulusvaluesfrom
conventionaltheorywithoutamatrixcontribution
54.3.1.4

Strength

Theoretically, three parameters control the strength of a composite consisting of brittle fibres in a
brittlematrix:

modulusoffibres.

straintofractureratioofmatrixtofibre.

fibrevolumefraction.

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In practice, CC composites have exceeded theoretically predicted limiting values of strength and
strain.Thishasbeenattributedto:

compressiveprestressingofthematrix,and

energyconsumingfractureprocessesinthematrixandatthefibrematrixinterface.

Compressive prestressing of the matrix occurs by shrinkage of the matrix phase during processing
and is influenced mainly by the carbon residue of the matrix precursor and fibre surface reactivity,
Ref. [543]. Excessive shrinkage can result in matrix cracking which is deleterious in the extreme to
compositeproperties.
Figure 54.3.2 illustrates the tensile behaviour of 3D carboncarbon composite at RT and at high
temperatures under an inert atmosphere, Ref. [5420], [5421]. The tensile response of 4D carbon
carboncompositeunderthesameconditionsisshowninFigure54.3.3,Ref.[5418],[5419].

A: Room temperature tensile behaviour

Tensile behaviour at 45 which


corresponds to a rotation around
z-direction.

B: High-temperature tensile behaviour (inert atmosphere)

Directions: x, y and z

Figure54.32Carboncarboncomposites:Tensileresponseof3Dcomposite

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A: Room temperature tensile behaviour

X corresponds to a 45 rotation around


z-direction

B: High-temperature tensile behaviour (inert atmosphere)

x-direction

Figure54.33Carboncarboncomposites:Tensileresponseof4Dcomposite
54.3.1.5

Fracture

The internal cracks and porosity are responsible for the apparent pseudoplasticity phenomenon
exhibitedbyCCcomposites.Sealingoftheseimperfectionsimpairspseudoplasticityandpromotesa
brittlefracturemode.
The energy absorption capacity of the composites is linked to the fibrematrix bonding and crack
propagationmechanisms,i.e.:

Weak bonding enables diversion and blunting of the propagating matrix crack at the fibre
matrixinterface,permittingfibrepullout.

Strongbondingreducesthepossibilityofcrackdeviationandenablesthecracktopassthrough
thefibre;limitingbothstrengthandenergyabsorptioncapacity.

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54.4 Oxidation protection systems


54.4.1

Requirements

To be successful, the coating should retain its mechanical and physical integrity throughout all
temperature excursions. This can be in the range of 160C to +1700C during one mission of a
reusablespacecraft.Consequentlythecoatingshouldremainadheredtothecompositeandnotcrack,
whichwouldotherwiseenableoxidativeingress.

54.4.2

Coating development

54.4.2.1

General

Significantefforthasbeenplacedontheinvestigationofcoatings,aswithoutthemtheutilisationofC
Cmaterialsisseverelylimited.
Theparticularcoatinguseddependsonthethermalregimeencountered,e.g.:

SiliconNitride:Si3N4hasdemonstratedprotectionupto1250C.

SiliconCarbide:SiC(mostcommonlyreported)whichcanbeenhancedbyaSiO2basedsurface
layer(TEOS)toprovideprotectiontotemperaturesof1700C,Ref.[546].

54.4.2.2

Coating systems

Protectionsystemscanbeverycomplex(multiplex)andadifferentonespecifieddependingonthelife
expectancyrequiredinathermocyclicoxidationenvironment,Ref.[546]to[5413].
Tosummarise,theprotectionconstituentscaninclude:

inhibitors,intheformofparticulatesaddedtoaresinpyrolysedmatrix.

infiltration of oxidation resistant ceramics into a porous CC substrate. Infiltration can be


achievedbyCVI/CVDandincludeSiC,Si3N4,BN,AlN,TiCandB4C.

conversionofsurfacecarbontosiliconcarbide,togiveadiffusioncoating.

anoverlaycoating,e.g.SiC.

glassyinterlayersandcoatingswhichactasasealingmedium.

Operationabove1700Crequiresmorecomplexcoatingscomposedof,Ref.[542]:

hafniumdiboride,

hafniumoxide,and

iridium.

54.4.3

Matrix modification

Themodificationofthecarbonmatrixbytheincorporationofapreferentiallyoxidisingfillermaterial
(boron carbide)and organometallic materials(which convert to B, Siand Ti during pyrolysis) have
shownsomeincreasedoxidationprotectionattemperaturesbelow1000C,Ref.[547].Thisapproach
differsfromtheprotectivecoatingmethodinthatitprovidesdirectoxidationresistancethroughout

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the composite thickness, whereas coatings rely on surface protection and indirect protection of the
compositethroughthickness.
The modified matrix route avoids problems of nonuniformity of coatings and potential thermal
expansionmismatchwhichcanresultincrackingofthecoatingandasubsequentlossofprotection.
Theeffectofamodifiedcarbonmatrixonmechanicalperformanceofthecompositeisunknown,or
whetherithasanybenefitattemperaturesabove1000C.

54.4.4

Design factors

The design of an oxidation protection system should be closely tailored to the intended application
andenvironment.OneofthebasicproblemsisensuringthatcompletecoverageoftheCCispresent
at all oxidising temperatures in the intended thermal cycle. This is hindered by the low to negative
coefficientofthermalexpansionfortheCCcomparedwiththepositiveexpansionofselectedcoating
materials.Thisusuallyresultsincrackingoftheprimaryprotectivecoatingoncoolingandtheneedto
sealthecracksduringsubsequentheatingcycles.
Eachapplicationimposesitstemperaturespectrumandlifeexpectancyincludingthermalcycles.Two
applications for protected CC are Thermal Protection Systems for spaceplanes, [See also: Chapter
71],andgasturbineenginesforaircraft.Thesehavecontrastingexpectations,assummarisedinTable
54.4.1.

Table54.41Carboncarboncomposites:Requirementsforoxidationprotection
systemsfortwoapplications
Requirement

Max. temperature
(C)
Life expectancy
(hours)
Thermal cycles

SpaceplaneTPS

Gasturbineengine

Nosecone

Exhaustpetals

1700

800 + excursions to
1300

30

300 - 2000

60

2000+

In general, protection systems increase further the complexity and cost of the component. Coating
systems can consist of between five and ten applied layers. In selecting protective materials, the
oxidationresistanceandcoatingimpermeabilitytooxygenshouldbeconsidered.Optionsinclude:

Anouteroxideimpermeablebarrier,e.g.Al2O3,HfO2,ZrO2,withbetterpermeationresistance
thanthesilicaformedonsiliconcarbide.

Anintermediatelayerbetweentheoxideandsiliconcarbidelayer,tobridgethedifferencesin
CTE,e.g.aluminiumnitridewiththealuminaouterlayer,Ref.[5414].

A primary silicon carbide coating deposited in thin layers with a progressive reduction in
depositiontemperaturetofillinthecracksofthepreviouslayer,Ref.[5415].

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54.5 Potential applications


54.5.1

Resum

54.5.1.1

Single use components

CarbonCarbon composites have a long history of use in space programmes, particularly for single
cycle,shortdurationthermalexposuresinanonreusableapplication.Theseinclude:

reentryshields.

motorcomponents,enginesandnozzles.

Lookingatthewideruseinaerospaceapplications,CCcompositesareappropriatefor:

highenergybrakingsystems,

hightemperatureseals,and

dimensionallystablestructures.

Inallprobability,CCisthenaturalselectionforhightemperatureapplications(between1200Cand
2000+C)ofshortduration.

54.5.1.2

Reusable components

Forreusablecomponents,suchasthermalprotectionsystems,thecostofoxidationprotectioncanbe
prohibitive and preference can be given to ceramic matrix composites. The reliability of oxidation
protectionsystemsafterrepetitivethermalcyclingcanproveadecidingfactor.
Duringreentry,extremetemperaturesof~1700Careexperiencedbythenoseconeandleadingedges
of a space vehicle. It is to those areas that CC composites have been applied on Space Shuttle as
thermal protection systems, Ref. [5416]. Other applications include nozzles on Pershing II missiles
andotherrocketcomponents.
Adevelopmentprogrammeforaturbinewheelinturbojetenginesdestinedforhypersonicaircraftis
alsoadvanced,Ref.[5417].
The most noticeable attributes of CC composites are thermal stability to 2000C and beyond, plus
goodfracturecharacteristics.

54.5.2

Commercial availability

54.5.2.1

General

OneprimarybenefitofthewidescaleuseofCCcompositesisthattheyaresignificantlyadvancedin
both performance and process characterisation. Those companies active in the application,
manufactureandtestofCCcompositesare:

Aerospatiale(France):materialmarketedasNOVELTEX.

SEP(France),

Dunlop(U.K.),

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Sigri(Germany),and

LTVAerospaceandDefense(USA).

It is the knowledge, expertise and facilities held within these companies that enables a widerscale
exploitationofCCmaterialsinfutureprojects.

54.5.2.2

Further developments

ThereareareaswhichneedevaluationtoimproveconfidenceinCCfurther;suchasestablishingthe
inspectionproceduresandqualificationofCCformorestructuralusage.
Atpresentthemainapplicationareasareinthermalprotectionbarriers.However,theevaluationof
rotating engine components can provide information on material performance under dynamic
loadings.
ConceptualdesignsforthermalprotectionsystemswithintheEuropeanreusablevehicleprogrammes
includedCCcompositesasacandidatefortheHermesnosecone.

[SeealsoChapter71forTPS]

54.6 Dimensionally stable structures


54.6.1

Introduction

Carboncarboncompositespossesnearzerocoefficientsofthermalexpansionanddonotsufferfrom
moistureinduceddistortion.ThesecharacteristicsmakeCCmaterialsofinterestinthemanufacture
ofhighlydimensionallystablestructuresforspacetelescopesorscientificinstruments.
ComponentsmadefromtheCCmaterialbythemanufacturingprocessesdescribedhavebeenspace
qualifiedfor:

GOCEgravityfieldandsteadystatecceancirculationexplorerprogramme.

Pleiadesprogramme.

Thecompositecomprisescontinuoushighstrengthcarbonfibres,intheformofafabric,inacarbon
matrix.Theconsolidatedcompositehasafibrevolumefractionofabout60%.
ThesummaryofthemainfeaturesoftheCCtechnologyincludes:

Veryhighthermoelasticstability:CTEof1.107/Cforaquasiisotropiclayupconfiguration.

Low density with good mechanical properties enabling simple and reliable analyses; as for
conventionalCFRPmaterials.

Moistureinsensitivity.

Notbrittle.

Withstandsveryhightemperature.

Various architectural possibilities, e.g. thin and large size cylinders, plates and honeycomb
sandwiches,whichcanbeadaptedintoefficientstructuralconcepts.

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Manufacturingfacilitiesavailablewithlargesizecapabilities,e.g.upto2.5m.

Industrialmaturity,withfurtherpotentialgrowth.

54.6.2

Material characterisation

Thematerialisqualifiedfordifferentconfigurations,i.e.:

monolithic,e.g.forcylindersorspiderblades.

structuralsandwichpanels.

ThebasicpropertiesaregiveninTable54.6.1foraquasiisotropiclayup,atroomtemperature.

Table54.61Carboncarboncomposites:Basicproperties
Property

Density (kg/m3)
CTE( 10-6 /K)
Tensile strength (MPa)
Short beam shear strength (MPa)
Tensile modulus (GPa)

Typicalvalue

1600
0.1
> 160
> 12
> 60

Intheadditiontothebasicmaterialmanufacturing,anumberofadditionalprocessesweredeveloped
forCCcompositesindimensionallystablestructures,i.e.:

Bondingprocesses,forbothstructuralbondingandforheaterbonding.

PaintingprocessontoCCsubstrate.

Nondestructive inspection procedures, using infrared thermography were also developed and
appliedtoensureintegrity.

54.6.3

Manufacturing process

54.6.3.1

General

The CC manufacturing process described has been qualified by Alcatel Alenia Space at Snecma
Propulsion Solide (Safran group) and Hitco (SGL group) to produce components demanding high
stabilityinspaceapplications.
The overall manufacturing sequence includes the usual steps used for CFRP parts, e.g. layup of
prepreg and cure, plus hightemperature steps needing special furnaces, e.g. for carbonisation and
densification.
Figure54.61showstheequipmentusedduringsomestepsofthemanufacturingprocess.

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Figure54.61Carboncarboncomposites:Manufacturingprocessequipment
54.6.3.2

Process steps

Themanufacturingprocesshasanumberofsequentialsteps:

Heat setting of the fabric, which is a heattreatment that is essential in order to stabilise the
carbonfabricbeforeitissubmittedtoveryhightemperatureslaterintheprocessing.Thefinal
CTEpropertiesalsodependonthetemperatureofthisheattreatment.

Prepregging, which is the same process used for conventional CFRP materials. The carbon
fabricisimpregnatedwitheitheranepoxynovolacorphenolicresin,i.e.highcharresins.The
resin content is chosen with respect to the desired final fibre volume content; taking into
accountanyresinlossbybleedingduringthecure.

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Layup, which is a stateof the art step of the process that has no particular constraints. As
withanyCFRPpart,layupangles,stipulatedinthedesign,needtoberespected.

Curing,aswithanyconventionalprepregCFRPpart.

Carbonisation, which uses hightemperature furnace facilties to convert the organic resin into
carbon. The resulting material is relatively fragile, so special care is taken during handling.
Since no special processes are undertaken after carbonisation, except weighing, the risk of
damagingthepartislimited.

CVIdensification,thefinalprocessstep,iswheretheporousmaterialisdensifiedusingahigh
temperature chemical vapour infiltration (CVI) process. At the end of this step, the part is no
longerfragilebecausethepyrocarbonhaspenetratedthemicrostructure,butthisisalsopresent
onthesurfaces,producingasealcoatafewmicronsthick.

Densifiedpartscanbemachinedeasilywithtoolingsuitedtocarbonbasedmaterials.

54.6.4

Sandwich structures

54.6.4.1

GOCE programme

CCsandwichstructureshavebeenspacequalifiedthroughtheGOCEGravityFieldandSteadyState
Ocean Circulation Explorer programme. GOCE is an ESA programme, which uses a threeaxis
gravitygradiometertodetermineforthefirsttimethestationarygravityfieldwithhighaccuracy.
CC technology has been selected for the construction of the highly stable sandwich panels that
support the accelerometers and electronics, as well as the thermal control unit of the Electrostatic
GravityGradiometerofGOCE;asshowninFigure54.6.2.

Figure54.62Carboncarboncomposites:GOCEgradiometer
54.6.4.2

Qualification programme

ThequalificationprogrammefortheCCtechnologyincluded:

Dimensionalverifications,e.g.masstovolume,panelflatnessandthickness.

Tensileandcompressivetests.

Bendingtest.

Outofplaneandinplanepulltests.

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Inserttests.

Stabilitymeasurements.

Microyieldtest.

Thermoopticalandthermaltests.

54.6.4.3

Sandwich panels

TheCCsandwichconfigurationcomprises:

facesheets:1.5mmand3mmthick,quasiisotropic.

honeycombcore:3/1610pcf,20mmto80mmthick.

Small prototypes and fullscale panels were developed and tested during the qualification phase at
AlcatelAleniaSpace.
ProcedureshavebeenimplementedatHITCO(SGLgroup)forthemanufacturingofCCflightparts.
The CC sandwich structure has been completely qualified to subsystem level, e.g. vibration and
stabilitytesting.Twoflightstructureshavebeensuccessfullymanufactured.
Owingtothehightemperatureconstraints,aspecialprocesswasdevelopedandqualifiedtolocally
strengthenunbondednodesintheCChoneycomb.

54.6.5

Cylinder structures

54.6.5.1

Pleiades programme

CCcylinderstructureshavebeenspacequalifiedthroughthePleiadesprogramme.
PleiadesisaCNES(Frenchspaceagency)Earthobservationprogramme,whichisthesuccessortothe
Spot series. The optical instrument is currently manufactured under the industrial responsibility of
AlcatelAleniaSpace.
The structure is made of a CC cylinder with a carbon/cyanate M2 spider and a Carbon/cyanate
reinforcementringconnectedbytitaniuminserts.
Prior to the Pleiades programme, developments of CC cylinders were conducted at Alcatel Alenia
Space,withadditionalfinancialsupportfromCNESandtheFrenchMinistryofDefense.

54.6.5.2

C-C cylinders

ThefeaturesofallthemanufacturedCCcylindersare:

Monolithic,i.enotasandwichstructure.

Thickness1.6mmto4.8mm.

Length:300mmto2.5m.

Diameter:300mmto800mm;mandrelavailableupto2.5m.

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54.6.5.3

Qualification programme

Thequalificationprogramforcylindersincluded:

Dimensionalverifications,e.g.masstovolume,circularity.

Tensiletests.

Inserttests.

Stabilitymeasurements.

Microyieldtest.

Thermoopticalandthermaltests,e.g.conductivity,emissivity.

The qualification program was performed anddemonstrated on both small and large test cylinders.
Figure54.6.3illustratestherangeoftestcylindersizes.

Figure54.63Carboncarboncomposites:Testcylinders
54.6.5.4

Flight cylinders

Figure54.6.4showsthePleiadesflightcylinder,whichis780mmdiameterand2mlong.
TwoflightcylindersweresuccessfullymanufacturedbySnecmaPropulsionSolide(Safrangroup),a
partnerofAlcatelAleniaSpace.Asof2005,theseareundergoinginstrumentintegration.

Figure54.64Carboncarboncomposites:Pleiadesflightcylinder

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54.7 References
54.7.1

General
[541]

Y.Grenie
CarbonCarbonCompositesandAerospatiale:StateoftheArtand
Prospects
LookingAheadforMaterialsandProcesses.PublishedbyElsevier
Science,TheNetherlands.1987.p377386

[542]

A.J.Klein
CarbonCarbonComposites
AdvancedMaterialsandProcessesincludingMetalProcessing11/86,
p6468

[543]

W.Huttner
CarbonCarbon:AninverseCompositeStructure
Z.Werkstofftech16,p430435,1985

[544]

APradier
AdvancedCompositeMaterials:TheEmergingStructuralMaterials
forHighTemperatureApplications
ESA/ESTECInternalNoteYME/AP/0151,July1987

[545]

J.L.Macret&A.Hordonnead
VeryHighTemperatureMaterialsforMechanicalApplications
ESAWPP004.October1988

[546]

A.Kepling
EvaluationofSiliconCarbideConvertedCarbonComponentsfor
LiquidRocketApplications
AIAA/ASME/SAE/ASEC22ndJointPropulsionConference
June1618,1986.PaperAIAA861429

[547]

I.Jaured&D.C.Nagel
OxidationProtectioninCarbonCarbonComposites
Mat.Res.BullVol.21,p13911395,1986

[548]

S.M.Simetal
SolGelCoatingsonCarbonCarbonComposites
Mat.Res.Soc.SympProceedings,Vol.73,p647652,1986

[549]

Q.D.Quinn&J.J.Stolglich
MechanicalTestingofaCoatedCarbonCarbonCompositeat
ElevatedTemperaturesinAir
U.S.ArmyMaterialsTechnologyLaboratory
Report:MTLTR8615;ADA169355,May1986

[5410]

E.V.Gellhornetal
SiliconCarbideCoatedCarbonCarbon:AnAdvancedMaterialfor
RocketSystems

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AGARDCP449.ApplicationofAdvancedMaterialfor
Turbomachinery&RocketPropulsion,35October1988
Paper19
[5411]

J.R.Style&J.E.Sheeham
CeramicCoatingsforCarbonCarbonComposites
CeramicsBulletinVol.67,No.2,1988,p369374

[5412]

OxidationInhibitingCarbonCarbonComposites
U.S.Patent4.795.677.January1989

[5413]

K.H.Hanetal
RateofOxidationofCarbonFiber/CarbonMatrixCompositeswith
AntioxidationTreatmentatHighTemperature
J.Electrochem.Soc.:SolidstateScienceandTechnology,April1987,
Vol.134,No.4,p10031009

[5414]

O.Franc&J.L.Machet
OxidationResistantCarbonCarbonMaterials
ESASP303,June1990.p8790

[5415]

W.Huettneretal
OxidationInhibitedCarbonCarbon:ACandidateMaterialforHot
Structures
ESASP303,June1990,p9195

[5416]

E.W.Johnsonetal
SpaceShuttleOrbitor;LeadingEdgeStructuralDesign/Analysisand
MaterialAllowables
ProceedingsofAIAAStructuresandStructuralDynamicsand
MaterialsConference.Paper860949,p382393,1986

[5417]

AlcatelAleniaSpace(France)

[5418]

XAubardetal
ModelingofTheMechanicalBehaviorof4DC/CComposite
Materials
JNC12,ENSCachan15thto17November2000

[5419]

XAubardetal
DamageModellingof4Dcarbon/carboncompositeforhigh
temperatureapplication
CeramicsInternational26(2000),p631637

[5420]

CTallaron
Mechanicalbehaviourandmicrostructuralstudyof3DC/C
compositeatveryhightemperature
JNC12,ENSCachan15to17November2000,Vol1,p511

[5421]

J.PDumontetal
DamageMechanicsfor3DComposites
CompositesStructures8(1987)p119141

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[5422]

GSavage
CarbonCarbonComposites
PublishedbyChapman&Hall,UK.

[5423]

AstriumST,formerlyEADSST,Bordeaux(France)

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55 Material availability
55.1 Introduction
This chapter considers available material forms, with emphasis on differentiating between standard
product forms and those in which material and component are created simultaneously; known as
Netshape.
As with all development materials or those with smallvolume specialist uses, the amount of data
availableislimitedandveryapplicationdependent.
Product support and sources of European expertise in material processing of advanced metal and
ceramicbasedmaterialsaregiven.
The factors contributing to the cost of finished components are described, as are indications of the
complexityforeachmaterialgroup.

55.2 Material forms


55.2.1

General

Advancedmetallicandceramicmaterialscanbepreparedorcreatedinmanyforms,inanattemptto
enhance properties. However, this creates a complex picture for designers and engineers seeking
verified design data and manufacturing routes. It is appropriate to differentiate between materials
whichcanbeobtainedas:

Standardproductforms,and

Netshapeprocesses.

55.2.2

Procurement

Procuring new materials can be an evolutionary process, with continual improvements and
modifications being introduced. There are few standard product forms equivalent to, for example,
CFRPprepregsorwroughtmetalsections.

55.2.3

Processing

Manyoftheadvancedmetalandceramiccompositesarefairlydifficultmaterialstoprocesshencethe
preferencefornearnetshapeornetshapemethods.Thisindicatesspecialisedprocessfacilities,which
arenotalwayswidelyavailable.

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55.3 Standard product forms


55.3.1

General

It is assumed that basic raw materials have been converted to a form which can be worked to a
finishedcomponent.Inthisrespect,thematerialisessentiallyfullyformedbut,ifnecessary,canbe:

mechanicallyworked,

machined,or

heattreated.

Suchmaterialscanbeeasilycharacterisedbysupplierandenduseralike.

55.3.2

Wrought metal products

Theseinclude:

Conventionalmetalalloys(includingplateandextrusionproductforms),e.g.:

Mg,

Al,

Ti,and

Cu.

ODSandmechanicallyalloyed(MA)metals:madefromconsolidatedpowders,notably:

Al,and

Cu.

Particulatereinforcedmetalmatrixcomposites(MMC),notablyaluminiumbased..

Machinablecarboncarboncompositesections:CCcompositesarerelativelysoftmaterialsthat
canbemachinedwiththecorrecttooling.2Dcompositescanbeconsideredastandardproduct
whereas complex multidirectional reinforcement (3D, 4D, 5D, 6D, nD) are netshape
components.

55.3.3

Standard materials for net-shape processing

There is a range of standard materials and products which are suitable for applying to netshape
processes,including:

fibres,eitherfor:

winding,

fabrics,or

preforms.

continuousfibreprepregsorfoils,notablyTiorAlMMCs.

ingotsofalloysorparticulatereinforcedMMCs.

castingcompositions.

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powdercompositions,forconsolidation.

55.4 Net-shape components


As materials become more difficult to process, there is a greater desire to achieve netshape
processing; not least to avoid machining of hard brittle materials. Equally, those ceramic materials
which cannot be melted are usually synthesised by vapour deposition or by pyrolysis, whereby the
final material and product forms are created simultaneously. In these cases, the final material
propertiesaretheresponsibilityofthoseconductingthefinalprocessing.
Theenduserhaseithertocharacterisethematerialasmadeorrelyonaspecialistsubcontractor(s)
forbothprocessingandcharacterisation.
Materialsfornearnetshapeornetshapeprocessesinclude:

Metalmatrixcomposites(MMC):

Continuousfibrepreformsinfiltratedwithliquidmetal,usuallyaluminium.

Consolidated foils and prepregs with continuous fibres orfilaments, e.g. Ti/SiC, Al/B,
Al/SiC,andAl/C.

Forgingsandcastingsofparticulatereinforcedmetals,usuallyaluminium.

Hotisostaticallypressed(HIP)powders,includingintermetallics.

Ceramicmatrixcomposites(CMC):

Continuous fibre reinforced ceramics, e.g. SiCSiC and CSiC prepared by vapour
infiltration(CVI)ordeposition(CVD).

CompositeswithfibresorwhiskerspreparedbyresinpyrolysisorSolGeltechniques.

Hot pressed ceramic compositions with powders, whiskers or fibres, usually silicon
nitride(Si3N4)based.

GlassandGlassceramicmatrixcomposites.

CarbonCarboncomposites(CC):

PreparedbyresinpyrolysisorCVIdensificationtogiveeitherablockornearnetshape
component,havingmultidirectionalreinforcement,e.g.3D;nD.

55.5 Data and product support


55.5.1

Material supply

New materials prepared in low volumes always present problems in establishing a supply of
consistentmaterial.Thereasonscaninclude:

Materialsarebeingoptimisedandimproved.

Supplyisinitiallyfrompilotplantproductionfacilities.

Insufficientproductioncapacityexists.

Customerdemandisinitiallyinsufficienttoexpandproductionfacilities.

Singlesourcesupply.

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Commercialorstrategicrestrictionsonsalesordatadissemination.

55.5.2

Property data

55.5.2.1

General

This ECSS handbook contains indicative data on material capabilities for new metallic and ceramic
compositions.
It is impracticable to describe in depth the properties of all materials and grades. An end user or
designer should establish a knowledge base on selected materials with specific end applications in
mind.
In some cases the technology can prove too expensive to warrant inhouse facilities, so specialist
contractorsprovidethenecessaryexpertise.

55.5.2.2

Standard product forms

Wherestandardproductsareused,thereisalargerpoolofknowledgebasedontheexperienceofthe
materialsuppliersandendusers.

55.5.2.3

Net-shape components

Where netshape components also dictate material properties, greater reliance is placed on the
expertiseofthematerialprocessors.

55.6 Data sources


55.6.1

European expertise

Table55.6.1presentsaresumofrecognisedEuropeanexpertiseonthenewermaterials.

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Table55.61Advancedmetalsandceramics:SignificantEuropeansourcesof
expertise
Material
grouping

Developing
technology

Enduser

Magnesium
compositions

Aluminium
compositions

AMS Ltd., UK. (MMC)


Raufoss A/S, Norway
(ODS)

Aerospatiale, F. (All)
MBB, G. (All)
British Aerospace, UK
(All)
Rolls Royce, UK
SNECMA, F.
MTU, G.
British Aerospace, UK
(SPF/DB)
Dornier Luftfahrt, G
(SPF/DB)
Rolls Royce, UK. (All)
SNECMA, F. (All)
MTU, G. (All)

Material/product
supplier
Magnesium
Electron, UK
(MMC)
BP MMC Ltd.,
UK (MMC)
Alcan, UK
(MMC, Al/Li)
Pechiney, F.
(Al/Li)

Titanium
compositions

BP Ltd., UK. (Ti/SiC)

Superalloy
compositions

Intermetallics
(IM)
Beryllium(Be)

Max-Plank Institute,
G. (IM)
ONERA, F. (IM)

Brush Wellman
(Be)
Interatom, G.
(Be)

GEC Alsthom, UK
Rolls Royce, UK

SEP, F.
Dornier, G.

SEP, F.

SEP, F.

Aerospatiale, F.

Dunlop Aviation,
UK
Le Carbone, F.
Aerospatiale, F.

Glass matrix
and Glassceramic
composites
Ceramic matrix
composites
Carbon-Carbon
composites

MBB, G.

IMI,UK

INCO Alloys, UK

Theseareclassedas:

Suppliersofmaterial.

Collaborators.

Specialisedcontractors.

Majorendusers.

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55.7 Costs
55.7.1

Relative comparisons of materials

55.7.1.1

General

Presenting a full breakdown of the costs of using advanced metallic and ceramic materials is very
difficult. Materials in development or produced in low volumes usually have high initial costs
indicativeofimmaturecommercialproducts.SomematerialsrepresentEnablingTechnologies,such
thatprojectsaretotallydependentonthemforsuccess,e.g.veryhightemperaturecomposites.Other
materials can be in a competitive position with each other, e.g. for use at 300C, aluminium MMCs
versusSPF/DBtitaniumalloysversusaluminiumODSalloysversuspolyimidematrixcomposites.

55.7.1.2

Direct material costs

The direct material costs of selected precursor materials and composites are summarised in Table
55.7.1.

55.7.1.3

Production cost control

As the newer materials have significant direct purchase costs, the main means of controlling total
productioncostsareby:

minimumpartcounts.

minimummachining.

netshapeprocessing.

Themaincontributingfactorstohighcostsinclude:

expensivefibresorfilaments.

prolonged processing, such as powder attrition (mechanical alloying); chemical vapour


infiltration(CVI);repeatedresinpyrolysis;complexfibrepreforms.

hightemperaturetooling.

machining,particularlydiamondmachiningofhardmaterials.

inspectionandqualitycontrol.

Someofthesecostsareunavoidableifasolutionisrequiredtomeetaprojectneed.

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Table55.71Advancedmetalsandceramics:Directmaterialcosts
Precursormaterial

perkg

Fibres

Carbon
Silicon carbide fibres
Silicon carbide monofilaments
Alumina fibres

15-300
500-750
400-1500
500

Metals

7XXX series Al alloys (Wrought)


8090 Al/Li alloy (Wrought)
Titanium 6Al-4V alloy (Wrought)
Aluminide powder

6-8
15-18
30
150-1500

Composites

(Flatsheetfortestspecimens)

Silicon carbide fibre reinforced aluminium


SiC-SiC ceramic matrix composite
Carbon-Carbon composite
Date:1992

>750 <1500
>2200 <5000
750-1500

55.7.1.4

Finished product cost comparison

Table 55.7.2 is a comparison of the relative cost of finished products in selected materials. They are
indicative,butreflectthebasictrend.

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Table55.72Advancedmetalsandceramics:Relativecostsofcomponents
Relativecost
offinished
product

Complexity
scale

Multidirectional CFRP

Modest

1 to 2

Wrought Magnesium
Alloys
7XXX series Wrought
Aluminium Alloys

Low to
Modest

1 to 2

Materials

8090 AluminiumLithium Alloy

Low

Modest to
Medium

1 to 3

Aluminium ODS Alloy

Medium

2 to 3

Carbon Fibre
Reinforced Aluminium
Alloy

Medium to
High

2 to 4

Medium

1 to 2

Wrought Titanium
Alloy
Silicon Carbide Monofilament Reinforced
Titanium
Conventional Nickel
Superalloy
Consolidated Titanium
Aluminide
Machined Beryllium

Ceramic Matrix
Composite:
SiC-SiC by CVI
Hot Pressed Glassceramic Matrix
Composite: LAS/SiC
Carbon-Carbon
Composite

High

3 to 5

Medium

Medium to
High

3 to 5

Medium to
High

2 to 3

Very High to
Extremely
High
Very High
High to Very
High

6 to 9

5 to 7

4 to 5

Comments
Well understood technology. Costs
reducing through automation &
lower part counts over aluminium.
Well understood technology. Fewer
applications than aluminium.
Well understood technology applied
to ambient temperature structures.
Technology established for 5 years.
Requires more usage to increase
confidence.
Improves high temperature
capabilities of 7XXX series, but
lacks applications.
Lacks applications. Some
fundamental issues still to be
resolved, e.g. poor transverse
strength & corrosion.
Well established technology for
intermediate temperature (200 to
600C) applications.
Still under development. Seeking
applications principally in gas
turbine engines.
Well established technology
particularly for gas turbine engines.
Still under development. Competing
for gas turbine use.
Specialised high modulus material,
but has established history. Lack in
confidence on low ductility/toxicity
has hindered use.
Recent development for very high
temperature applications.
Processing is specialised & capital
intensive. Lower processing costs
sought.
Easier to achieve than CMC's, but
are restrained to 1000C
Well established technology,
although cost and poor oxidation
performance can limit application.

Key:

Basedoncosttoweight.However,variationsindensityareenormousfrom1740kg/m3
(Magnesium)to9500kg/m3(Superalloys).

Rankingtoreflect:

Technicaldifficulty

Availabilityofknowledge&facilities,and

Materialcost

1=Easilyachieved;10=Extremelydifficult.

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56 General design rules


56.1 Introduction
This chapter describes the different mechanical and fracture characteristics of each material group,
andconsiderationsforthedesignofstructuralcomponents.
Metal and ceramicbasedcompositesare complex,multiphasematerials,inwhich each phase hasa
significantinfluenceonboththepropertiesandstabilityathightemperatures.Defectswhichaffectthe
requiredcharacteristicsarediscussed.
Composites consisting of hard, brittle phases present problems for machining. The use of netshape
processing aims to minimise the need for machining. However, the factors to be considered along
withappropriatetechniquesarepresentedwhenmachiningisnecessary.

56.2 Mechanical response


56.2.1

General

Thenumberofmaterialsystemsnowavailableorunderdevelopmentislarge.Eachisbeingoptimised
with certain operating environments in mind. This can mean enhancing certain properties at the
expenseofothers.Notallmaterialscanbeadequatelycharacterisedbytheirresponsetomechanical
loading,e.g.stressstrain.

56.2.2

Composite development

56.2.2.1

General

Theevolutionofcompositematerialsbasedonmatrixandreinforcementhasincreasedthecomplexity
not least by introducing anisotropy which renders comparisons with isotropic materials largely
superfluous.

56.2.2.2

High temperatures

A general trend is that as higher temperature capabilities are sought from metals and ceramics, the
ambient modulus increases but strength and strain to failure gradually diminish. This should be
consideredbydesigners,andexpectationsofmaterialductilitylowered.

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56.2.3

Material characteristics

56.2.3.1

Fibre reinforced plastics (CFRP)

Anisotropic.

Essentiallyelasticmaterialstofailure.

Lowstraintofailure(<2%),otherthanfordamagetolerant45configurations.

Forlaminates:

Tensilepropertiesarefibredominated.

Compression and shear properties are significantly influenced by matrix support to


fibres.

Weaknesses, principally low interlaminar and transverse strengths; designs need to avoid
delaminationsandinterlaminarfractures.

Goodfatigueperformanceinfibredominateddirections,principallyintension.

56.2.3.2

Metals alloys

Isotropic.

Essentiallyelasticplasticmaterials.

Designsbasedonproofstresses,e.g.0.2%PS.

UTSandelongationtofailure(ductility)areinplasticdeformationzone.

Goodductilityprovidesconfidencefordamagetolerance.

Conformtofracturemechanicspredictions,e.g.fracturetoughness.

Heattreatmentandmechanicalworkedconditionimportant.

56.2.3.3

Particulate reinforced metals

Nearisotropic.

Elasticplasticmaterials,withshortenedelasticregion.

Designmodulusdifficulttoestablishduetosmallelasticregion,buthigherthanunreinforced
metal.

Elongationtofailureusuallyin2%to8%range.

Smallparticles(1mto3m)preferabletolargerparticles(above15m)inretainingmetallic
characteristicsofductilityandfracturetoughness.

Heattreatmentandmechanicallyworkedconditionimportant.

Tensilestrengthsequaltoormarginallybetterthanunreinforcedmetal.

Hardnessandcreepresistanceimproved.

CTElowered.

56.2.3.4

Continuous fibre reinforced metals

Anisotropic.

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Essentiallyelasticmaterialstofailureandfibredominated.

Highermodulusthanunreinforcedmetalalloysinfibredirections.

Longitudinaltensilestrengthdictatedbyinsitufibrestrength.

Transverse and interlaminar strengths should be better than CFRP, but often limited.
Controlled by fibrematrix interface and transverse fibre strength, it can contribute to poor
performance, i.e. low utilisation of matrix capability due to strain incompatibilities and
embrittlement.

Reducedthermalexpansion.

Highinternalstresses,duetoCTEmismatchbetweenmatrixandfibre.

Bettercreepresistancethanmatrixalloy.

56.2.3.5

Advanced metallic systems

(IncludesODS,MA,RSPalloysandintermetallics).

Isotropic.

Refined microstructures usually from powder processing which give improvements in


modulus,creepresistance,hardnessandthermalstability.

56.2.3.6

Monolithic ceramics

Isotropic.

Highmodulusandthermalstability.

Goodstrengths(bestincompression).

Lowstraintofailure,<1%.

Verydefectsensitive,pronetocatastrophicfailure.

56.2.3.7

Ceramic matrix composites

(IncludesGMC,GCMC&CMCwithcontinuousfibres).

Complexanisotropic.

Microstructureinfluencedbymatrix,fibres,matrixtofibreinterface,voidageandpopulationof
microcracks.

Principallythermostructuralmaterials.

Elasticmaterials,butwithtwostraincomponents:

matrix,=0.1%to0.3%,and

fibres,=~1%.

Ultimatetensilestrengthsandstraintofailuredeterminedbyinsitufibrestrength.

Modest strength, but benign fracture characteristics, compared with those of monolithic
ceramics.

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56.2.3.8

Carbon-carbon composites

Complexanisotropic.

SimilarcharacteristicstoCMCs,butlowermodulusandtougher.

Tensile strength gradually increases in temperature range 1000C to 2000C, which is a rare
featureofanymaterial.

56.3 Stress-strain response


56.3.1

Isotropic and anisotropic materials

56.3.1.1

General

Thereisalwaysadesiretocomparematerialseveniftheirmicrostructuresareradicallydifferent.The
greatestcomplicationsariseincomparingisotropicandanisotropicmaterials.Allmaterialshavetheir
attributesanddisadvantages.
Figure56.3.1andFigure56.3.2providerepresentativestressstrainprofilesforadvancedmetallicand
ceramic systems. These curves do not reflect the lower density of the composites over their heavier
metal alloy counterparts. The strain axis in Figure 56.03.2 is modified to reflect the lower strain
capabilityofceramicsystems.

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Figure56.31MetalsandMMCs:StressstrainresponsecomparedwithCFRP

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Figure56.32Metalsandceramicbasedmaterials:Stressstrainresponse

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56.3.1.2

Strain to failure

Asabroadstatement,allanisotropicmaterials(composite)possesslowerstraintofailure(elongation)
than isotropic metals (ceramics excluded). This can be perceived as a weakness or in some cases
unacceptable.
Experiencehas,however,shownthatmassefficientstructurescanbeproducedinlowstraintofailure
(1%to1.5%)composites.

56.3.1.3

High temperatures

Forhighertemperatureapplications,increasingemphasisisplacedoncompositesforsomestructures
seekingmassefficiencyorextendedlifeexpectancy.

56.4 Fracture characteristics


56.4.1

General

Isotropicalloysofmagnesium,aluminium,titanium,nickelandcopperbehavebroadlyinaccordance
withconventionalfracturemechanics.
As materials become progressively more anisotropic, their fracture behaviour becomes less
predictablebytheoreticalmodels.Comparisonsareprovidedforguidance.

56.4.2

Near-isotropic materials with modest ductility

Thisgroupcoversmaterialswith~2%to6%ductilityandincludes:

lowvolumefraction(<20vol.%)particulateMMCs,

pressedpowderderivatives,e.g.ODS,MA,RSPalloys,and

intermetallics,e.g.aluminides.

Theycanbetreatedassimilartoisotropicalloysinthebasicmodesoffracture.

56.4.3

Anisotropic, fibre reinforced MMCs

56.4.3.1

General

Thesematerialscannotbecomparedwithisotropicalloys.Theirbehaviourismorecloselylinkedto
thatoffibrereinforcedplastics.

56.4.3.2

Effect of matrix

The difference between MMCs and FRPs centres on the matrices, which for metals have inherently
highermoduliandstrengthsthanplastics,e.g.epoxy.
TypicallyforMMCs,thematrixmodulusisafactorof20to40timeshigherandthematrixstrength
some6to20timesgreatercomparedwithFRPs.Themetalmatrixcanalsodeformplastically,whereas
epoxiesrarelyexceed1.5%to2%failurestrain.

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56.4.3.3

Tension

For tensile characteristics, a fracture model similar to that of CFRP can be used. However, overall
strength is dictated by the insitu fibre strength. There is no loss in strength through fibre
degradationinCFRP,whichisnotnecessarilytrueforMMCs.

56.4.3.4

Compression and shear

ForcompressiveandshearperformanceofMMCs,theinterfacebetweenfibreandmatrixissignificant
indeterminingpermissiblestrains.
TransversestrengthsofMMCsareconsiderablylowerthanthoseforthemetal(matrix)alone.Thisis
becausethefibreinthetransversedirectionandinterfacecannotsustaintheload.

56.4.4

Anisotropic, fibre reinforced CMCs

56.4.4.1

General

Theceramicmatrixcomposites,suchasSiCSiC,cannotbecomparedwithmonolithicceramics.CMCs
modifythemicrostructureofmonolithicceramicstoimprovethetolerancetomechanicalloadingand
thermalshock.
Standardfracturemechanicprinciplesareinappropriate,asthematerialsarenotsensitivetoasingle,
smallcrackpropagatingtoacriticalsize.

56.4.4.2

Effect of matrix

Byincorporatinghighmodulusfibreswithstraintofailuresof1%to1.5%,thislevelofstraincapacity
isthenconferredtothecomposite,eventhoughthatofthematrixaloneisonlyabout0.2%.Thisgives
afarfromidealengineeringmaterial,whereelasticityisexhibitedto0.2%andthereaftermicroscopic
crackdamagepropagatesandmultiplieswhilstthefibresholdthecompositetogether.

56.4.4.3

Strength

The ultimatecomposite strength is determined by the insitufibre strength. This relies onthe fibre
and matrix being decoupled by an interface material such that the matrix cracks are stopped and
deflected, whilst providing opportunities for fibre pullout. Such a composite possesses excellent
thermalshockresistance;asisalsoseenwithcarboncarboncomposites.However,overallstrengthis
modest compared with other engineering materials. Hence, their use for thermostructural
applications,wherethermalandheatmanagementrequirementsprevail.
Compared with nickelbased superalloys, CMC strengths are low, however their density is
approximately 35% less than these alloys, providing opportunities for using greater sectional
thicknesseswithoutincurringaweight(mass)penalty.

56.4.4.4

Permissible stress

When designing with CMCs, the maximum permissible design stress has to be less than the yield
stress,i.e.onsetofsignificantmicrocracking.
Theremainingstraincapacityisthenthemarginofdamagetoleranceofthecomposite.Thiscouldbe
equatedwiththeductilityshownbymetals.

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56.5 Residual stresses


56.5.1

Isotropic materials

For metals, residual stresses can be reduced by heat treatment processes. Also, the range of
temperaturesseenbytheapplicationisusuallywellwithinthestablerangeofthematerialandfew
microstructuralchangesoccurovertheworkinglifeofthestructure.

56.5.2

Anisotropic materials

56.5.2.1

General

Residualstressesaremorepronouncedinanisotropicmaterialsorwhenjoiningdissimilarmaterials.

56.5.2.2

Effect of temperatures

Iftheintendedrangeofapplicationtemperaturesiswide,thenresidualstressescanalsodeterminethe
integrity of both the material and the structure. Designs should evaluate the effects of residual
stresses.
Where materials are used at high temperatures or for a short duration (life), there is a tendency to
operate a material close to its limits. Often a slow degradation occurs which gradually changes the
characteristicsofthematerial,e.g.microcracking,oxidation,creep,diffusion(chemical)reactions.

56.5.3

Influence on microstructure

Residual stresses can be tensile or compressive and occur when adjacent material phases, e.g. fibre
and matrix, have different moduli (stiffness) and CTE. These can be sustained in material systems
with ductility or significant strain capacity. More susceptible are high modulus, low strain phases
whichcanfracturetorelievestress.
Residualstressesareimportantwithrespectto:

Fibrecoatings:Ifaprotectivecoatingisappliedtoafibreathightemperatures,thenoncooling
toambientthecoatingbecomesstressed.Asmostfibreshavelowaxialexpansivityandarehigh
modulusmaterials,thecoatingexperiencestensilestresses.

Brittlematrices:Whenpreparingceramicmatrixcomposites,thematrixisstressedforthesame
reasons as for fibre coatings. A significant population of matrix microcracks can result from
stressrelieving mechanisms. Whilst this is tolerated, the cracks provide an entry point for
oxidation.Minimisingtheinitialmicrocrackingbylowprocesstemperatureshasadvantages.

Protective coatings: Coatings applied to components should contain low residual stresses to
avoidspalling.Residualstressesdeterminethemaximumpermissiblecoatingthickness.

Reductionintransverse properties: In either MMCsor CMCs, residual stresses are influenced


byprocesstemperaturesusedtoformthecomposite.Ifamatrixisstressedthenitscapacityto
sustain further applied load is limited. This is a contributing factor to the modest transverse
(matrixdominated)strengthsofhightemperaturecomposites.

As with CFRP, the fibre orientations in adjacent lamina can determine the viability of a composite
construction.

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56.5.4

Influence on structures

56.5.4.1

Temperature

Changesinapplicationtemperaturescanhavesignificantimplicationsifresidualstressesexist,some
examplesinclude:

Distortion:Thiscanoccurinunbalancedconstructions,e.g.thinsectionswithasinglesurface
protective coating or joints between dissimilar materials. Outofplane distortion, such as
bendingortwisting,isastressreliefmechanism.

Reducedsectionalstrength:Amaterialcanhaveanacceptablestrengthatambienttemperature,
butcoolingtocryogeniclevelscancompoundresidualstressestounacceptablelevels.

Thermal gradients which can producing throughthickness variations or compound residual


stresses.

56.6 Defects
56.6.1

General

Withawiderangeofmaterialsavailableitisdifficulttostatethesignificanceofdefectsandflawson
theintegrityofthematerial.

56.6.2

Defect sources

Defectscanarisedueto:

manufacturingrouteused.

impactdamage.

mechanicalorthermalfatigue

corrosionorotherenvironmentaldegradation.

56.6.3

Isotropic materials

56.6.3.1

General

Broadly, a single crack or flaw ultimately determines the fracture of isotropic or nearisotropic
materials.

56.6.3.2

Alloys

Fracturemechanicscanbeusedformetalalloystodeterminethesignificanceofacrackatanystage
withinstructurallife.

56.6.3.3

Particulate MMCs

These materials can be treated like alloys, although full densification does not guarantee material
integritywhenloadisapplied.

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Beforeconsideringtheuseofparticulatereinforcedcomposites,evidenceissoughtthatbondingexists
betweenparticlesandmatrix.Withoutaninterfaceforloadtransfer,theparticlecanbeconsideredas
tobeaninclusion,withthematrixrequiredtosustaintheload.
Intheeventofpoorbondingordebonding,theinterfacebetweentheparticleandmatrixbecomesa
sourceforcrackinitiationandpropagation.

56.6.4

Anisotropic materials

56.6.4.1

General

Foranisotropiccomposites,thefinalfractureislargelyaresultofmanycracksaccumulatingtoreacha
criticalpopulationdensity.
Withinlaminarcomposites,thereareplaneswithdifferentfracturecharacteristics:

Interlaminarplanes(2Dcomposite)areusuallytheweakest(matrixdominated),and

Throughlaminaplanesshowgreaterresistancetocrackpropagation(fibreassisted).

The use of 3D or multidirectional reinforcement assists by increasing interlaminar strength but


loweringstrengthsintheothermajoraxialplanesthroughadilutioneffect.

56.6.4.2

Continuous fibre MMCs

Thephasespresentarefibres,matrixandinterface.LikeCFRP,voidagelevelsshouldbelow,<2vol.%.
Anythinggreaterthanthiscanbeviewedasunacceptableandthemanufacturingrouteatfault.
Excessive fibrematrix interaction, with fibre degradation, is also a concern. The insitu strength of
fibresissometimeslessthanpredictedandajudgementisthenmadeastowhethersatisfactorylevels
havebeenattained.Prolongedcontactwithmoltenmetal(matrix)orlackofaprotectivecoatingare
usuallythecauseoffibredegradation.
Evidenceoffibrebreakageasaresultofcompositemanufacture,oftenfrompressformingtechniques,
isagaincauseforconcern.Largediametermonofilamentscanprovesusceptibletobreakageifover
formed.Smalldiameterfibresaremoretolerantofmechanicalhandlingandformingtoradii.

With continuous fibres, there is the possibility of fibre contact without matrix wetting between the
fibres. These are sometimes called neckless defects. High levels indicate a poor manufacturing
technique,e.g.lackofpressureortimeformeltinfiltration.Occasionalinstancesshouldbetolerable.
The presence of reinforcement phases can modify the solidification and the microstructure of the
metalsalloysusedasmatrices.Itcannotbepresumedthatcharacteristicsseeninunreinforcedalloys
are automatically conferred to the matrix; especially as alloys can be controlled with heat treatment
andmechanicalworking.

56.6.4.3

Continuous fibre CMCs

Thesearecomplexmaterialsconsistingoffibre,matrix,interface,voidsandmicrocracks.
As with MMCs, insitu fibre strengths are generally lower than anticipated by a simple Law of
Mixtures. Greater opportunities exist for thermal degradation of fibres and corrosive attack, even
assumingafibrecoating(interface)isused.

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Thematrixisthemorecomplexphaseduetoitsinhomogeneity.Mostceramicmatricesaremadeby
lowpressure infiltration techniques, although hot pressing has some attractions. Low pressure
synthesisreliesonagradualbuildupofmatrix,possiblywithpyrolysisstages,andthisgivesriseto
discontinuitiessuchasentrappedvoidsandlocalcracking.Voidageupto10%canbetolerated,andis
unavoidableinsomeprocesses.
In view of their use as thermostructural materials, modest strengths should be accepted. It can be
argued that some voidage makes a constructive contribution to the benign fracture characteristics.
Excessivevoidagehinderstheintegrityofthecompositebyreducinginterlaminarintegrity.Voidage
in excess of 10% is generally unacceptable, unless for thermal insulation purposes rather than for
structuralengineering.
The significance of microcracks is a more difficult issue to resolve. It is recommended that an
acceptable composite be established which fulfils the requirements. That composite is then
characterisedbymetallographyandNDTtodetermineitsstateofintegrity.NDTtechniquessuchas
Xray and backscattering are used for imaging the bulk of the material. The validity of NDT
techniques which can detect individual microscopic features is less appropriate in view of the large
populationofmicrofeatures.

56.7 Machining
56.7.1

General

Withthepossibilityofusingmaterialswhicharehardandbrittleorcontainreinforcingphases,their
machiningcharacteristicscanbesummarisedasadvisorystatements.

56.7.2

Isotropic metal alloys

Conventional machining techniques are used, with accepted practices for each alloy group. Whilst
aluminiumisreadilymachinable,thereisanincreasingreluctancetoremovelargeamountsofmetal
fortitaniumandsuperalloys.A90%metalremovalisnotuncommonforaluminium,butasmaterial
costsincreasethereisreluctancetocreateunnecessaryscrap.Segregationofscrapisalsonecessaryfor
somealloys,especiallythosecontaininglithium.

56.7.3

Particulate MMC

Machiningispossible,butatacost.Thesematerialstendtorelyonsiliconcarbideoraluminaparticles
forthereinforcingphases.Thesearehardandextremelyabrasive.Conventionalhighspeedsteeland
carbide tooling wear out very fast. Diamond tipped or coated tooling provides the only realistic
optionforprolongedtoollifeandanacceptablesurfacefinish.

56.7.4

Continuous fibre MMC

Otherthantrimming,thesematerialsarenormallyconsolidatedvianetshapeprocessroutes;forthe
same reasons as particulate MMCs. The fibres or filaments are not amenable to clean cutting, other
thanperpendicularlythroughthefibre.

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56.7.5

Carbon-Carbon composites

These are machinable, as the matrix is relatively soft. Carbide tooling is appropriate for the harder
carbonfibres.Thisistrueprovidedthatnoglassyorceramicoxidationinhibitingphasesarepresent.

56.7.6

Ceramic matrix composites

All the phases present are very hard and abrasive. Diamond tipped tooling is the only mechanical
machining option available. That said, all machining is kept to an absolute minimum and ideally
restrictedtoslittingortrimming.Thisplacesafirmemphasisonnetshapeprocesstechniques.

56.7.7

Techniques

Inadditiontothosehighlightedforeachmaterial,MMCandCMCcomponentscanbelasermachined,
althoughconsiderableexpertiseisrequired.

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57 Environmental aspects of design


57.1 Introduction
Thischapterdescribestheenvironmentalfactorsassociatedwithspacewhichhaveadirectinfluence
on material selection. Such factors form part of the material development process, where an
applicationdictatestheuseofaparticularmaterialtype.
Wherethematerialsavailablecannotmeettherequirementsalone,protectionsystemsareused.These
canbeintheformofacoatingoramoresubstantialstructure,suchasashield.Inbothcases,therole
andlifeofthesystemneedsevaluationwithrespecttothewholestructure.

57.2 Space parameters


57.2.1

Material selection

Material selection is biased towards the specific needs of space programmes. Some of the issues
associated with the acceptance of fibrereinforced plastics are of less concern if metals and ceramics
areconsidered.
Equally, metals and ceramics are applied within environments where it is inconceivable to use
plastics,particularlyathightemperatures.
Table57.2.1summarisesthematerialsenvironmentalresponse.

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Table57.21Advancedmetalandceramicbasedmaterials:Relevanceofspace
parameterstomaterialselection
MaterialGroup

Parameter
Outgassing/Offgassing
UV or Radiation
Stability

Plastics(CFRP)

Metallics

Ceramics

Atomic Oxygen (LEO)

Toxicity
Flammability
Moisture Absorption

Low CTE but some


instability
NA

Bulk material stable


Thin films may
degrade

Controlled CTE
possible
e.g. SCC

Thermal Cycling

Will accept -170C


to +200C

Thermal conductivity

Low, Anisotropic

Will go close to 1000C


as maximum

Good to High

Will go to high
temperatures

Low to Medium

Modest CTE,
temperature
range important

Engines & TPS

For engines

Dimensional Stability
Aqueous Corrosion
Embrittlement at
Cryogenic
Temperatures

Thermal expansion
Oxidation Resistance
Hydrogen
Embrittlement
Emissivity
Flux Capacity
Hot Gas Corrosion

Low axial CTE.


High transverse
CTE
NA
other than LEO

For fuel tanks


NA
NA
NA

Wide variations
possible

Engines, (Ni).

For propulsion systems

Key

:Issueformaterialselection.

:Unimportant,duetogoodmaterialstability.

NA:Notappropriate.

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57.3 Application specifics


57.3.1

Material selection

From the specific requirements of space programmes, it is possible to identify key issues which
influence material selection. These are instances where compromises should be made in materials
development to ensure that a particular parameter is addressed to reach an acceptable performance
level.
Suchissuesinclude:

Thermalexpansion:controlledandconstant,despitepersistentthermalcycling.

Hydrogen effects: avoidance of hydrogen embrittlement in the handling of hydrogen fuel,


throughouttherangeoftemperatures.

Oxidation and hotgas corrosion: sufficient resistance to survive 30 missions for a reusable
thermalprotectionsystem(TPS).

Thermalconductivity:veryhigh.

Creep:resistanceforshort,singlecyclelifeexpectancyat550C.

57.4 Protection systems


57.4.1

Requirements

Protectionsystemsareusedinenvironmentswhichcanseverelydamageamaterialorstructurewere
it directly exposed. The more obvious occurrences are linked to high temperatures or high energy
situations.
Withtheadventofreusablestructures,otherissuesthataffecttheintegrityofmaterialsorstructures
include:

AtomicoxygenattackinLowEarthOrbit(LEO),

Micrometeoritesandhighvelocitydebrisimpact,

Oxidationbyheatedairorcombustiongases,

Hotexhaustgascorrosion,

Aqueouscorrosion,saltsandacids,

Biofungalattack,

Lighteningstrike,

Thermalflux.

SomeofthesephenomenawereinvestigatedintheESAfundedWEPROTstudy,Ref.[571].

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57.4.2

Types of protection systems

57.4.2.1

General

Protection systems are usually thin coatings (less than 1mm), but they can be more substantial in
termsofshieldsorthermalprotectionpanels.Coatingsareusedonbothmetallicandceramicbased
materials.

57.4.2.2

Function

Traditionally,aprotectionsystemissacrificialinshieldingtheunderlyingsubstrateorstructureandis
not expected to contribute to overall strength, e.g. thermal barrier coatings. Thermostructural
components perform a combined role, but some materials need an additional surface coating, e.g.
oxidationprotectionsystemsforcarbonfibrereinforcedcomposites,suchascarboncarbonandC/SiC
CMCs.

57.4.2.3

Integrity

Theintegrityoftheprotectionsystemshouldbesuchthatitcontinuestofunctionthroughoutthelife
oftheapplication.
Coatingsthatcrackorspallhavelimiteduseifthisoccursearlyinthelifeofthecomponent.Insome
cases,protectivecoatingsarefarfromideal,butaretheonlysolution.
Reproducible and predictable performance are preferable, even if regular repairs or component
replacementsarenecessary.

57.4.3

Evaluation of protection systems

57.4.3.1

WEPROT study

WithintheESAfundedstudyWEPROT,asurveywasconductedofthemajorterrestrialandorbital
environmentsforthermalprotectionsystemsonRVandRLV,Ref.[571].
Thestudycomparedtheperformanceofcandidatemetallicbasedsystems(titaniumaluminideand
PM1000 ODS) with ceramicbased (oxidebased and C/SiC CMCs) against terrestrial and orbital
environmentsidentifiedasappropriateforreusablevehicles.

57.4.3.2

Ceramic-based TPS

For C/SiC TPS, the environmental phenomena which cause damage to the surface coating or the
structuralmaterial,soreducingreusability,canbesummarisedas,Ref.[571]:

A low speed impact, e.g. tool drop during assembly or maintenance, of about 0.5 Joule can
cause damage to the oxidation protection system (OPS) that can reduce the life performance
due to oxidation of carbon fibres during reentry. Repair of the damaged area can probably
restorereusability

Humidityaffecting theinsulation below a C/SiC panel.Useofsuitable coatings orsprayscan


avoidwaterpenetration;buthasnotbeeninvestigatedfurther.

Rain erosion is a key issue for the economical operation of an RLV. The test activities aim to
identifytheeffectthatrepairoftheOPShasonservicelife.

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Hail impingement damages the OPS and probably the underlying structure when it occurs
duringlaunchordescentandlanding.ReplacementoftheTPSisneededifthestructureishail
damaged. During landing, catastrophic failure caused by hail is unlikely; but has not been
investigatedfurther.

LightningstrikeduringdescentorlandingcausesdamagetotheTPS.Precautionsintheformof
properdesignofattachmentscanavoidseriousdamage.

Hypervelocity impact by micrometeoroids or debris is a key issue for the life of the TPS.
Published literature indicated that orbital environmental phenomena affecting the life were
more serious than expected at the beginning of the TPS development for RLV. A weather
proofinginvestigation,includinghypervelocitytests,wasnecessary,Ref.[575].

57.4.3.3

Metallic-based TPS

TPS made from TiAl was identified as the most advanced metallicbased system because of its
strengthtoweight ratio for sandwich panels, along with surface stability against oxidation or
degradationafterthermaltreatments.Themainfindingscanbesummarisedas,Ref.[571]:

Lowspeedimpactprobablycausesdentsinthefacesheetbutnocracking

Although humidity is not a problem for a metallic sandwich panel, the insulation system
beneathhastobeprotectedbyawaterproofcoating.

Rainerosionattypicallandingspeedsprobablycausesseriousdamagebecausemediumenergy
impact causes dents with cracking. Rain erosion tests, with subsequent plasma and thermo
mechanicaltesting,areintendedtoshowtheoccurrenceandextentofdamage,Ref.[573].

AlthoughthelightningstrikebehaviourofTiAlisunknown,catastrophicfailureofODSand
Tialloysdidnotoccur.Itisexpectedtoperforminasimilarmannertohypervelocityimpacts,
i.e. possible holes without cracks. This phenomenon was not considered further during test
programme.

Hypervelocity impact by micrometeorites or debris causes holes without cracking, this was
confirmedbyinitialhypervelocityimpactstestsonTiAl.Thedifferencesindamagecausedby
debrisandmicrometeoritesisforfurtherinvestigation.

An assessment of damage tolerance against tool drop, rain erosion and repeated thermal cycling
formedpartoftheWEPROTtestcampaign,Ref.[572],[573],[575].

57.5 References
57.5.1

General
[571]

U.Trabandtetal:Astrium(Bremen)/Plansee
SurveyofmajorterrestrialandorbitalenvironmentsforRVandRLV
WEPROTWP1100:SurveyReportWEPROTTN001ASTR(January
2003)

[572]

U.Trabandtetal:EADSST(Bremen)/DLRCologne/Universityof
Bremen/ESAHQ(Paris)
CeramicMatrixCompositesLifeCycleTestingUnderReusable
LauncherEnvironmentalConditions
Int.J.Appl.Ceram.Technol.,2[2]150161(2005)

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[573]

U.Trabandtetal:EADSST(Bremen)/DLRCologne/Universityof
Bremen/ESAHQ(Paris)
RLVTPSandHotStructuresOperationalCostEvaluationafterLife
CycleTestingwithRain,HailandLowSpeedImpacts
4thInternationalReentrySymposium,Archachon2005

[574]

V.Liedke,U.Trabandt&M.Dogigli:
OxidationLifetimeImprovementofCMCbasedHotStructures
(OLCHOS)
ESAContractReportNo.6713/02/NL/CP;DocumentNumber:OLC
ARCS2000

[575]

U.Trabandtetal:EADSST(Bremen)
WeatherProofingofReusableTPSagainstTerrestrialandOrbital
EnvironmentsRain,HailandImpactTestingonDifferentTPS
ProceedingsofHTCMC5:5thInternationalConferenceonHigh
temperatureCeramicMatrixComposites,Seattle,2004

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58 Joint selection factors


58.1 Introduction
Thischapterdescribesthefactorstobeconsideredforthedesignandmanufactureofjointsbetween
metals and ceramic materials. As most joints experience high temperatures, the effect of material
selectionandmanufacturingmethodonresidualstressesisconsidered.
Thebenefitsandproblemsassociatedwithusinganinterlayerinafusedjointisdescribed,alongwith
thoseofferedbymechanicaljointsorgradedstructures.

58.2 Basic considerations


58.2.1

Material characteristics

When dissimilar materials, such as metals and ceramics, are joined, there are specific physical
characteristics of the materials which are important. Their importance is closely linked with the
thermalhistoryofthejoint,i.e.:

creatingthejoint,and

theoperatingconditionsthatareappliedtothejoint.

Whereverpossible,thephysicalandmechanicalpropertiesofdissimilarmaterialsshouldbematched
as closely as possible. Stiffness and coefficient of thermal expansion are the most significant
properties.
Withsomematerialpairings,thereisconsiderabledisparityinpropertiesandaviablejointcanneed
aninterfacematerialtobridgethedifference.
Toprovideaninsightintothevariationsinpropertiesofprospectiveconstituentsofjoints,Table58.2.1
providesindicativedataontherangeofmaterialsthatcanrequirejoining.

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Table58.21Dissimilarmaterialsforjoints
Properties
Max. Temp. Melting Temp.
Strength, UTS
(MPa)
(C)
(C)
Metallic alloys
400
110-150
600
890
450
1725
650-865
700
1500
(YS: 310-750)
1276
800
1455
(0.2%PS: 1056)
1310
900
1390
MMC

Conductivity @ RT,
(Wm-1 C-1)

Comments

150
6.0

Standard aerospace alloy.


Most common Ti-alloy.

150

Common stainless steel.

11.2

Well established Ni-alloy.

New material.

600

Anisotropic, Fibre-reinforced,
high modulus, unidirectional.

200

600

Particulate reinforced.

1040 (L)

500

1725

Monofilament reinforced.

TD

TD

900

1455

Monofilament reinforced.

2.1 to 3.5
3.2
4.2 to 5.4
7.7 to 8.1
6.5

310
280-331
345-470
300-372
186

Flex: 400-845
Flex: 845
Flex: 300-540
Flex: 240-400
Flex: 405

10-30
21.3
125-200
39(25)
1-2

Powder based.
Powder based.
Powder based.
Powder based.
Powder based.

C-SiC

1 to 2

200-250

400

~1600

N/A

SiC-SiC: 2-D fabric

210

230

~1600

N/A

25(L)
6(TT)

C-C: 2-D fabric

0 to 1

90-100

127-172

~2000

N/A

Material

CTE,
(x 10-6C-1)

Stiffness, E
(GPa)

Aluminium: 7075
Titanium: Ti-6AI-4V

23.0
11.0

70
120

Steel: SS 316

14.0

196

Nickel: lnconel 718

13.0

200

Aluminide: Ni3AI

12.5

226

~0 to -I

379-414

552-834

200

<23.0

100

610
(0.2%PS: 490)

<11.0

225

Silicon Nitride
Sialon
Silicon Carbide
Alumina
Zirconia (ZrO2)

Aluminium:
DWG-A1/P100(UD)
Aluminium:
2124/18vol.% SiCp
Titanium/SiCf:
Ti-6AI-4V/SCS-6(UD)
Nickel/W Fibre (TFRS)

Monolithic ceramic
1400
1900
1600
1700
2050
2960
CMC

Anisotropic. 2-D carbon fibrereinforced.


Anisotropic. 2-D SiC fibrereinforced.
Anisotropic. 2-D C-C composite.

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Key:

Aluminium

25.3

69

Silver

20.6

71

Copper

18.3

117-132

Nickel

15.2

210

Molybdenum
Niobium
Tungsten

5.1 to 5.7
7.2 to 8.1
4.5

303
98
411

Titanium

7.6

108

Base material or interlayer (Pure)


69
AD
660
(0.2%PS: 25)
140
AD
960
220
AD
1083
(0.2%PS: 50)
323
AD
1452
(0.2%PS: 63)
435
2615
900
240
2467
1000
550
3387
1200
369
AD
1675
(0.2%PS: 246)

238

418

397

79

135
52
130

Refractory metal
Refractory metal
Refractory metal

16

YS:Yieldstress.PS:Proofstress.Flex:Flexural.N/A:Notapplicable.TD:Temperaturedependent.AD:Applicationdependent.

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58.2.2

Joint strength

58.2.2.1

General

Designingandimplementingjointsalwaysrequiresanelementofcompromise,notablywithrespect
tothestrengthattainable.

A suitable joint is one having sufficient strength for the intended application with retained
integrityoveradesiredtimeperiod.

Ajointcannotbestrongerthantheweakestmaterialbeingjoinedandfailureatultimateload
occurssomewhereinthesystem.

Bynecessityandforconfidence,thatfailureisconsistentandreproducible.

58.2.2.2

Residual stress

Infusedjointsbetweendissimilarmaterials,eithermetalsorceramics,themajorlimitingfactortojoint
strengthisresidualstressinoneofthematerials.Thisstressincreaseswithtemperaturechangesaway
fromthatatwhichthejointisfirstformed,especiallyoncooling.
Insomenonoptimisedjoints,theresidualstresscanexceedthebasicstrengthofoneofthematerials
and fracture occurs without external loading. Whereas other nonoptimised joints might withstand
cooling,butonlyverysmallsustainedloadsareneededtocompoundtheresidualstressesandcause
jointfailure.

58.2.2.3

Failure

Inceramictometaljoints,failureismostprevalentintheceramicbecauseofitsbrittleness,lowstrain
tofailure,higherstiffnessandmodeststrengthcharacteristics,[See:Table58.2.1].
In practice, joints between radically dissimilar materials require considerable ingenuity to obtain
reasonablejointstrengths.

58.2.2.4

Effect of fusion temperature

Itiscommontousefusiontemperaturesintherange800Cto1000Cbetweenceramicsandmetals.
The actual amount of expansion at these temperatures is quite considerable, e.g. 0.27% for silicon
nitrideand1.3%forsteel.

At the fusion temperature, residual stresses are assumed to be zero. On cooling, the degree of
contraction of these materials differs and constraints are imposed by the differences in physical
properties.
Forexample:

Si3N4
Steel

E
310
196

3.0
14.0

TheSi3N4isatadisadvantagebecauseitcontractsbyasmallamountandcannotstretchbecauseofits
high modulus. It has limited strength with no capacity for ductileplastic behaviour. On cooling to

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ambient,itisthereforehighlystressedatthedirectpointofconnectiontothesteelbeforeanyexternal
loadisapplied.
It has been calculated that for a supposed direct silicon nitridetosteel joint fused at 1200C, the
residualtensilestressesintheSi3N4approach1000MPa,Ref.[581].Suchastressisbeyondtheability
of Si3N4 to sustain without fracture. Indeed, the fusion temperature has to be lowered dramatically
beforeSi3N4cansustainanysignificantexternaltensileloading.

58.2.2.5

Reproducibility

Given the effect of the fusion temperature, significantly different strengths are reported for what
appeartobejointsbetweenidenticalmaterials(substrates).
Jointstrengthishighlydependentonthepreciseconditionsusedinformingthejoint.Inanoptimised
joint,theresidualstressescanbereducedbyseveralhundredMPaovernonoptimisedvariants.This
differentiates between an acceptable and unacceptable joint purely from consideration of basic
strength,letalonedurability.

58.2.3

Joint design factors

TheclosematchingofstiffnessandCTEofdissimilarmaterialshasbeenhighlighted.Withdissimilar
materialssomeelementofmismatchisinevitable,soafusedjointisdesignedandmadetominimise
theconsequenceofthesemismatches.
Inundertakingthis,carefulconsiderationisgivento:

Thepresence,ornot,ofaninterlayermaterial.

Thetemperatureandpressureofjointconsolidation.

Chemicalcompatibilityofthetwosubstrates.

Loadintroductionintothejoint.

Operatingenvironment,including:

maximumtemperature,and

fatigue.

58.3 Interlayers
58.3.1

Function and effect on fused joints

58.3.1.1

General

Introducing a third material can affect a joint in several ways. The thickness of the interlayer is
important.Theprincipaleffectsinclude:

Residualstresses:Probablyreducedwithinthejoint,andarealleviatedfurtherbytheuseofa
thickinterlayer.

Jointconsolidationtemperature:Determinedbythemeltcharacteristicsoftheinterlayer,orits
abilitytoformadiffusionbondwiththesubstrates.

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Joint strength: Usually determined by the weakest substrate to interlayer bond, or cohesive
strengthoftheinterlayer.

Interlayer material: Selection determines the ultimate service or operating temperature of the
joint.Dependingonthedissimilarmaterialstobejoined,thematerialstriedinclude:

Aluminium

Copper

Niobium

Molybdenum

Titanium

Nickel

Iron

Silver

58.3.1.2

Interlayer materials

Someinterlayermaterialshavelowmeltingpoints,whicheasesproblemswhenfusingjoints.Others
havemuchhighermeltingpointswhichisalsoreflectedinthetemperaturecapabilityofthejoint.
Thecomplicatingfactorsarethesolidstatereactions(diffusion)whichoccurbetweeninterlayerand
substrate. These can occur at varying temperatures, with or without pressure assistance (0MPa to
100MPa).

58.4 Joint consolidation


58.4.1

Temperature and pressure

58.4.1.1

General

These two parameters have a synergistic effect. A low consolidation temperature is desirable to
minimiseresidualstressesoncooling.Thiscanbeaidedbyapplyinghighpressures.However,theuse
ofhighpressures,e.g.withinahotisostaticpressing(HIP)chamber,poseslimitationsonsize,shape
andcomplexityofcomponentsandisnormallyavoided.
Low pressure brazing has always been attractive for fabricating components, such as gas turbine
nozzleguidevanes,becauseofitsrelativesimplicity.
Themajorityofworkonfusionjoiningofdissimilarmaterialshasbeenwithsimplebuttjointsofsmall
crosssectional area. This enables virtually any fabrication process to be used, avoiding the issue of
complexassembly.
Todate,thepressureregimesusedhavebeen:

Lowpressure:

Mediumpressure:

Highpressure: 60MPato207MPa(to30000psi)

0to0.6MPa(to87psi)
0.6MPato15MPa(to2175psi)

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Consolidationtemperatureswithinterlayersrangebetween450Cforaluminiumand1400Cforthe
refractorymetalsNbandMo.

58.4.1.2

Metal substrates

Withouttheinterlayer,joiningisbyeither:

Diffusionbonding,or

Meltingofoneofthesubstrates.Itisonlyfeasibleifoneofthesubstratesismetal,withfusion
occurringat0.5to0.98ofthemetalmeltingtemperature(Tm).

58.4.1.3

Ceramic substrates

For connections between ceramics, either similar or dissimilar, melting of either substrate is neither
practical nor possible in most cases. Therefore, a metallic interlayer is used unless fusion can be
achievedby:

Hightemperatureinorganicrefractorycement

Pyrolysisofpolymeradhesive,e.g.polycarbosilane,toaceramic,suchasSiC.

InfiltrationanddensificationofthebondlineatahightemperaturebyCVD/CVItogiveSiC.

58.5 Material compatibility


58.5.1

Chemical and physical

58.5.1.1

General

Compatibility between dissimilar materials is difficult to define when materials are expected to
functionathightemperatures.

58.5.1.2

Requirements

Aftertheinitialfusion,itisdesirabletohaveastablechemicalandmicrostructuralcompositionwithin
thejointzone.Thisenablesconsistentanddurablejointperformancetobeobtained.
Itisundesirabletohavecontinuingchemicalactivityanddiffusionoccurringduringtheoperational
lifeofthejoint,astheperformancecanbeunpredictable.

58.5.1.3

Potential problems

When a fused joint, with or without a thin interlayer, is created, those occurrences which can be
detrimentalinclude:

Localisedmicrocrackingandflawingofabrittlesubstrate.

Presenceofexcessivequantitiesofbrittlephaseswithinthefusionordiffusionzone.

Inappropriatealloyelementspresentinmetallicsubstrateorinterlayer.

Insomecasesheattreatmentscanbeusedtoreducethermalstressingwithinajoint.
Chemical and physical incompatibilities are of less concern in mechanically interlocking parts, [See:
Chapter61].

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58.5.1.4

Use of alloy interlayers

The majority of interlayer materials studied have been pure metal foils and not alloys. If alloys are
used, then a more complex joint microstructure can be anticipated. This is true of braze materials,
although useful information is presently available from experiences in brazing nickel and titanium
alloys.

58.6 Load introduction


58.6.1

Basic principles

58.6.1.1

General

Thebasicprinciplesforloadintroductionaresimilartothoseforadhesivelybondedorfastenedjoints,
althoughspecialcareistakenifoneoftheadherendsisabrittleceramic.

58.6.1.2

Fused joints

Directtensile,cleavageandpeelloadingsareavoidedbecausejointstrengthsarelowestinthese
modes.

Compressiveandshearloadingsarepreferable.Theformerwhenaceramicispresent.

58.6.1.3

Graded structures

Thesearetolerantofmostlocalisedloadingmodesasagradualtransitionincompositionbetweenthe
twomaterialsisachieved.Ifoneofthematerialsisaceramicthencompressiveloadingispreferable,
butnotessential.Mechanicalinterlocks,pinningandfastening
This class of joints enables disassembly and the inclusion of seals. They also avoid the additional
thermal transient necessary in fusion fabrication. This eliminates thermal distortion on cooling.
However, additional problems arise when assembly is undertaken at ambient temperature and
subsequentheatedinservice.
Positional tolerances take into account thermal expansion and the need to sustain load. Subjects
requiringattentioninclude:

Localisedbearingandcrushingstrength

Notchsensitivityatchangesinsectionandatimmediateloadtransferpoints

Slackeningorovertighteningofjointsbydifferentialexpansion.

[See:Chapter61]

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58.7 Operational environment


58.7.1

Environmental factors

58.7.1.1

General

Forjointsinvolvingmetalsandceramicsappliedinhightemperaturesituations,thereareanumberof
environmental conditions which can invoke instability leading to reduced joint integrity. These
include:

Hotcorrosionbyreactivegases,e.g.O2andH2O.

Thermalshock,introducingdifferentialstressesacrossthejoint.

Thermalcyclinginducesamicrocrackpopulationthatpropagateswithrepetitivecycling.

Mechanicalloading,compounded.

Acousticfatigue.

58.7.1.2

Joint design

Withalloftheenvironmentalconditions,fracturedamageismorelikelytooccurinthemostbrittle
materialspresent,i.e.theceramicinametalceramicconnection.
Theimportantaspectstodeterminearethe:

actualloadstobetransmittedbythejoint.

lifeexpectancy(durability)ofthejoint.

jointstrength,withasufficientmargintoavoidacatastrophicfailureinservice.

58.8 References
58.8.1

General
[581]

A.Frischetal
DiffusionBondingofSi3N4toODSSuperalloyMA6000byHot
IsostaticPressing
PowderMetallurgyConference1990,26July
Paper11,Volume2,p5260

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59 Joints between dissimilar materials


59.1 Introduction
This chapter summarises the requirements for joints between advanced metal and ceramicbased
materials.Theeffectofoperatingenvironmentandtheoptionsavailableformanufacturingthejoint
arealsogiven.

59.2 Requirements
59.2.1

Temperature range

With the advent of spaceplanes and advanced launchers, there are significant thermal management
problemstoberesolvedwithinstructuralconfigurations.
Structuresspanningthetemperaturerangefrom+1600Cdowntobelow250C(20K)canbegrouped
as:

Hot

Warm,or

Cold.

The extreme high temperatures are at the external surfaces of spaceplanes on reentry or in and
aroundpowerplants.Thelowerandambienttemperaturesareinthemainstructuralairframeandin
liquidfuelcontainment.

59.2.2

Structures

59.2.2.1

General

Joints between components of dissimilar materials within a structure largely reflect the points at
whichdifferentoperatingenvironmentsmeet.

59.2.2.2

Materials

Connectionsarelikelytobemadebetween:

metallicandmetallic,

metallicandceramic,and

ceramicandceramic.

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Metallic includes both alloy and metal matrix composite (MMC). Ceramic covers monolithics,
composites(CMC),andcarboncarbon(CC).

RepresentativematerialsaresummarisedinTable59.2.1.

Table59.21Jointsbetweendissimilarmaterials:Representativelistofmaterials
Metallic

Ceramic

Alloys:

Monolithic:

Nickel (Superalloys)
Steel
Copper

Si3N4
Sialon
Al2O3
SiC

MMCs:

CMCs:

Ti-based
Ni-based
Cu-based

SiC-SiC
C-C
Glass-ceramic

59.2.3

Loading

Joints between dissimilar materials are likely to be structural and to some extent loadbearing. The
integrityofsuchjointsinsomecasescanbecriticaltotheintegrityofthespacestructure.
Thejointsneedtowithstand:

directmechanicalloading.

stressescausedby:

thermalgradients.

thermalcycling.

fatigue:

mechanical.

thermal.

Longevityisofhighimportanceinreusablestructures,suchasspaceplanes.

59.2.4

Joining methods

59.2.4.1

General

Theprincipaloptionsforjoiningare:

fusionbondinginallitsforms,[See:Chapter60].

mechanicalinterconnections,includingfastening,

[See:Chapter61]

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59.2.4.2

Fusion bonding

Fusionbondingpracticesinclude:

Diffusionbonding,

Brazing,

Reactionbonding,

Fusionwelding,

Resinpyrolysis.

59.2.5

Joint components

Withinjointstherecanalsobe:

cements,

seals,[See:Chapter75].

interlayers,[See:58.3].

gaskets.

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60 Fusion joining
60.1 Introduction
Jointscanbeachievedinanumberofways,butareprincipallymadebyeitheraliquidphaseorsolid
phase transformation. Broadly, liquid transformations are made at higher temperatures than
comparable solidphase bonding. This is significant as there is usually a preference for lower
temperature processing. However, this is offset by the fact that solidphase transformations usually
requirehigherconsolidationpressuresthanliquidphasebondingtoachieveasoundintegralbond.
Fusion bonding methods are described as is development work aimed at evaluating joint
performance,Ref.[All].

60.2 Joining techniques


60.2.1

General

Table60.2.1comparestherelativemeritsofthedifferenttechniquesdescribed.

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Table60.21Comparisonofjointingandconsolidationtechniques
Jointing/
consolidation

Advantages

Disadvantages

technique

Good for glass to metal


Fusion welding

Good for localised connections


Appropriate to similar
materials
Low pressure technique

Liquid phase
bonding
- Brazing
Diffusion
bonding
- with or
without
interlayer

Graded
structures

Allows use of brazes and frits


to achieve workable joints
Offers means of reducing
jointing temperature
Interlayer gives better
accommodation of CTE
differences
Offers means of
accommodating significant
differences in material CTE
and other properties, e.g.
modulus and conductivity
Appropriate for joining
dissimilar materials

Limited practical
combinations
Inappropriate for large-area
joints
Cannot accommodate
significant CTE differences
Requires wettability
Requires understanding of
chemical capabilities
Cannot accommodate
significant CTE differences
Requires consolidation
pressure
Requires understanding of
diffusion mechanisms

A sophisticated process
technique is to be used to
create a true transition zone

60.2.2

Liquid-phase processing

60.2.2.1

Melt refining

A transition zone is created between the two materials by localised compositional refining of the
molten phase. The materials are usually metals, e.g. steels, and the change occurs in the alloying
constituents,Ref.[All].
Thisincludeszonerefiningandvacuumarcrefining.

60.2.2.2

Fusion welding

One or more component materials are melted and fused with the others. In metaltoceramic
combinations, the metal is usually melted. This process is suited to small localised joints where a
controllableheatsourcecanbeused.

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60.2.2.3

Liquid-phase bonding

Boththematerialstobejoinedremainsolid.Theconnectionismadebyathirdconstituentwhichis
introduced at the faying surfaces and melted, so fusing both materials together as it solidifies. This
third constituent is a lower melting point material and hence the joints thermal capability is
determinedbyitscharacteristics.
Thisincludesbrazing.

60.2.3

Solid-phase processing

60.2.3.1

High-pressure (HIP) bonding

Bothmaterialstobejoinedremainsolid,butsufficienttemperatureandpressureareappliedtocause
bondingbyinterdiffusion.Thiscanbecarriedoutwithorwithoutathininterlayerofathirdmaterial.
Diffusionbondingoccursatatemperaturecloseto,butbelow,themeltingpointoftheleastthermally
stablematerialpresent.

60.3 Joint configuration and performance


60.3.1

Technology status

60.3.1.1

General

Table60.3.1presentsareviewofpublishedpapersonthefusionbondingofdissimilarmaterials.Most
of the work consists of joining trials, with or without interlayers, Ref. [All]. There is rarely any
explanationastowhythematerialsarejoined,i.e.theapplicationsarenotgiven,oranyjustification
fortheselectionofthevariousinterlayers.

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Table60.31Fusedjoints:Technologyreviewofjoints
Material A

Interlayer
material

Material B

Consolidation
technique
Vacuum arc
remelting

Process
conditions
Welding of dissimilar
electrodes

Comments
[Reference]
Graded structure for steam systems in
power stations, Ref. [60-1], [60-2]
Optimisation of interlayer thickness,
single and multiple, Ref. [60-3]
Study to identify efficiencies of interlayers,
Ref. [60-4]

2.25%Cr Mo-steel

316 stainless steel

None

Steel

Alumina (AI2O3)

Nb, Mo, Ti, (1 to 2mm) HIP

1000-1300C at 100 MPa

Type 405 stainless


steel
INVAR
(Fe-32Ni-5Co)

Silicon nitride
Si3N4

Ni,Fe,Ti,Nb (pure) + W HIP

1200-1400C at 100 MPa

Si3N4

Al (pure) (0.5mm)

Hot pressed

700-950C at 0-0.15 MPa

Bond strength optimisation, Ref. [60-5]

AI2O3 & Ti, Pt, Fe,


SS316, Cu

AI, Ag, Cu, & Ni foils

Hot pressed

>450C for Al
>600C for Ag & Cu
>900C for Ni

Evaluation of bond strengths, Ref. [60-6]

ODS nickel superalloy MA 6000

Si3N4

NiCo 36
(Fe-36%Ni)
W-Ni-Cu alloy
Ni & Ti (pure)

HIP

1100C-1300C, 100 MPa

Optimisation of interlayers, both single &


double, Ref. [60-7]

W-6Co alloy

AI2O3 (2% TiC)

Nb plus Ni-based filler

Ni
Steel
Al
Ti
Cr
C
Ti
C
Superalloy

AI2O3
AI2O3
SiC
TiN, TiC
CrN, Cr3C2
SiC, TiC
TiC
SiC
ZrO2

HP bonding
LP brazing
HIP

None
None
None
None

1200C, 60MPa
1255C, 0.2-0.6MPa
1400C, 207MPa
1400C, 207MPa
600C, 207MPa
-

Superalloy
Cu
Ni

ZrO2
TiB2, TiC
TiB2, TiC

None
-

AI2O3

None

PVD
PVD
CVD
PVD-CVD
PVD-CVD
Powder metallurgy,
Wet or dry
sprayed, 1 or 2 gun
-

Comparison of techniques. LP brazing


preferred, Ref. [60-8]
Demonstration of seven zone graded
compositions, Ref. [60-9]

Functionally gradient materials (FGM)


from Japan organised by Science &
Technology Agency, Ref. [60-10]

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Material A

Interlayer
material

Material B

Consolidation
technique

Process
conditions
950C at 3MPa
950C at 3MPa

AI2O3

Al2O3
ZrO2 (PSZ)
Mo.Nb,W, Kovar

AI2O3
AI2O3
AI2O3
AI2O3
AI2O3

Cu
Al
Ta
Fe
Nb

Cu

AI2O3

Ti

Liquid phase bonding Direct wetting sought

AI2O3

Ti alloy, Steel

Al

Solid phase bonding

Si3N4

Si3N4

lm Ti + braze Ag-Cu
or Au-Ni or Au-Ni-Pd

Brazing

AI2O3 or Si3N4

Titanium alloy
(TA6V) or Nb

Cu-40Ag-5Ti braze

Active brazing

SiC fibre/AI2O3
matrix

Stainless steel
304L

Ag/Cu/Ti braze

Active brazing

Stainless steel SS

Cu
Cu

Reaction bonding
None
None
None
None
None
None

Comments
[Reference]
Demonstration of strong joints, Ref. [60-11]

Fusion Welding

Material B melted

Largely impractical, Ref. [60-12]

Diffusion bonding

980C at 8.5MPa
600C at 8.5MPa
1400C at 10MPa
1375C at 1 MPa
1575C at 15MPa

Temperatures between 0.5 to 0.98 Tm


Pressures between 1 & 100MPa

Activity within thin


interlayer
Brazing temperatures:
Ag-Cu: 790C
Au-Ni: 970C
Au-Ni-Pd: 1130C
Under vacuum, 0.1MPa,
applied pressure at 850
to 890C for 2 to 10
minutes
Under vacuum, 1000C
for 20 minutes

Effectively brazing. Direct melting within


joint
Hot pressing required
1m Ti to improve wetting by braze. High
strength joints obtained, Ref. [60-18], [60-21]
Studies on reactions between braze &
substrate, Ref. [60-20]
Initial trials, Ref. [60-24]

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60.3.1.2

Objectives

Theprincipalobjectivesoftheworkaretoobtainstrongbondswhentestedatroomtemperatureand
provideabetterinsightintojoiningmechanisms.Varioustheoriesandmodelsforjointresponseare
alsopresented,Ref.[All].

60.3.2

Joint strength

60.3.2.1

General

Table60.3.2providesaselectionofreportedbondstrengthsforfusionjoints,Ref.[All].Thetestsare
for direct tensile loading normal to the bonded interface, conducted at room temperature. This
represents a fairly exacting stress condition with residual stresses at their maximum, coupled with
undesirabletensileloadingofbrittlematerials.
Consequentlythereportedfiguresarewidelyscattered,varyingfrom5MPato175MPa.Astrengthof
450MPa was achieved when like materials were joined, i.e. Si3N4 to Si3N4 with a Cu interlayer. A
strength of 5MPa is very poor, whereas 175MPa provides a useful strength. The quoted strengths
provideabroadinsightintothatpossible.

Table60.32Fusionjoints:Publishedbondstrengthsforvariousjoints
Material
A

Material
B

Interlayer(s)

Technique

Bondstrength,atRT.
[Reference]

Steel
405 S
Steel
405 S
Steel
Si3N4

Al2O3

HIP (DB)

Mean 63 MPa, Ref. [60-3]

HIP (DB)

Mean 65 MPa, Ref. [60-4]

LP (DB)

Mean 51 MPa, Ref. [60-4]

Si3N4

Mo + Nb
Nickel braze
+ W + Fe
Nickel braze
+ W + Fe
Al

HP (DB)

Si3N4

Si3N4

Ag-Cu

Brazing

INVAR
Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
PSZ
(Zr2O3)

Si3N4
Al2O3
Al2O3
Al2O3
Al2O3
Ti
Fe
SS 316
Cu
Al2O3
S Steel

Al
Al
Ag
Cu
Ni
Al
Al
Al
Al
Cu
Cu

HP (DB)
HP (DB)
HP (DB)
HP (DB)
HP (DB)
HP (DB)
HP (DB)
HP (DB)
HP (DB)
LP (RB)
LP (RB)

Max ~450 MPa, Ref. [60-5]


Max ~32838 MPa, Ref. [6018]
Max ~175 MPa, Ref. [60-5]
Max ~70 MPa, Ref. [60-6]
Max ~40 MPa, Ref. [60-6]
Max ~50 MPa, Ref. [60-6]
Max ~45 MPa, Ref. [60-6]
Max ~50 MPa, Ref. [60-6]
Max ~20 MPa, Ref. [60-6]
Max ~10 MPa , Ref. [60-6]
Max ~5 MPa, Ref. [60-6]
Max ~124 MPa, Ref. [60-11]
Max ~167 MPa, Ref. [60-11]

S Steel

Cu

LP (RB)

Max ~70 MPa, Ref. [60-11]

Si3N4
Si3N4

Key

:70MPaachievedbyannealing

HIPHotisostaticpressing

DBDiffusionbonding

RBReactionbonded

LPLowpressure

HPHighpressure

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Thestrengthsareverymuchdependentonthe:

materialsselected,

specimenconfiguration,and

precisejoiningtechniqueused.

60.3.2.2

Effect of temperature

Jointstrengthsvarywithtemperature.Itcanbeexpectedthatlowerstrengthsareseenatambientor
closetothefusiontemperature,whilstamaximumstrengthoccurssomewhereinbetween.

60.3.2.3

Factors affecting joint strength

Greaterbondstrengthsareseeninthosejointswhich:

minimiseresidualstressesbyuseofmaterialgradation,and

lowfusiontemperatures.

Wheretheserulesarenotfollowed,lowstrengthsorevenfractureoncoolingarepossible.
Theuseofheattreatmentcansignificantlyincreaseambientstrengths,particularlywhereaverylow
strengthisotherwiseindicated.

60.4 References
60.4.1

General
[601]

G.Oakesetal
PropertiesofGradedTransitionJointsProducedbyVacuumArc
Remelting
AdvancesinMaterialTechnologyforFossilFuelPlants.ASM
International,ConferenceProceedings,13September1987
ISBN0871703149,p559572

[602]

I.A.Shiblietal
PropertyValidationofaGradedCompositionTransitionJoint
CreepandFractureofEngineeringMaterialsandStructures
Proceedingsofthe3rdInternationalConference,510April1987
InstituteofMetalspublication,ISBN0904357996,p741759

[603]

K.Suganumaetal
EffectofInterlayersinCeramicMetalJointswithThermalExpansion
Mismatches
CommunicationsoftheAmericanCeramicSociety,December1984,
pC256toC257

[604]

K.Suganumaetal
JoiningSi3N4toType405SteelwithSoftMetalInterlayers

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MaterialScienceandTechnology,Vol2,p11561161.Nov1986
[605]

K.Suganumaetal
JoiningofSiliconNitridetoSiliconNitrideandtoInvarAlloy
usinganAluminiumInterlayer
JournalofMaterialsScience22(1987),p13591364

[606]

M.G.Nicholas
DiffusionBondingCeramicswithDuctileMetalInterlayers
BrazingandSoldering,No.10,Spring1986,p1113

[607]

A.Frischetal
DiffusionBondingofSi3N4toODSSuperalloyMA6000byHot
IsostaticPressing
PowderMetallurgyConference1990,26July,Paper11
Volume2,p5260

[608]

V.Heinzeletal
BondingbetweenTungstenandOxideCeramicsbyBrazing
PowderMetallurgyConference1990,26July,Paper13
Volume2,p6668

[609]

G.P.Yiasemides
SimultaneousSinteringandDiffusionBondingofMetalstoCeramics
usingHIP
PowderMetallurgyConference1990,26July,Paper20
Volume2,p100102

[6010]

A.Yoshitakeetal
FabricationoftheFunctionallyGradientMaterials(FGM)TheState
oftheArt.ESASP303,June1990,p103107

[6011]

W.E.Borbidgeetal
AReviewoftheReactionBondingTechniqueforJoiningCeramicsto
Metals
JournaldePhysique,ColloqueC1,supplmentauNo2,Tome47
fevrier1986,p131137

[6012]

M.G.Nicholas&D.A.Mortimer
CriticalAssessmentCeramic/MetalJoiningforStructural
Applications
MaterialsScienceandTechnology,September1985
Vol1,p657665

[6013]

M.G.Hockingetal
MetallicandCeramicCoatings:Production,HighTemperature
PropertiesandApplications
LongmanScientificandTechnical.ISBN0582033055,1989

[6014]

X.S.Ningetal
BondStrengthandInterfacialStructureofSiliconNitrideJoints
BrazedwithAluminiumSiliconandAluminiumMagnesiumAlloys

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JournalofMaterialsScience26(1991),p20502056
[6015]

.A.DeLucaetal
AnAdvancedCeramictoMetalJoiningProcess
Ceram.Eng.Sci.Proc.,8[78]p602610,1987

[6016]

M.D.Pughetal
TheInteractionofReactionbondedSiliconCarbideandInconel600
withaNickelbasedBrazingAlloy
MetallurgicalTransactions,Volume20ANo.9,September1989
p15711894

[6017]

A.J.Moorhead&P.F.Becher
AdaptationoftheDCBTestfordeterminingFractureToughnessof
BrazedJointsinCeramicMaterials
JournalofMaterialsScience22(1987),p32973303

[6018]

M.L.Santella&L.C.Manley
StrengthandMicrostructureofTitaniumVaporCoatedSilicon
NitrideBrazeJoints
Proceedingsofthe3rdInternationalSymposiumonCeramic
MaterialsandComponentsforEngines.p513527,Nov1988

[6019]

K.Suganumaetal
RelationshipbetweentheStrengthofCeramic/MetalJointsinTensile
andThreepointBending
AmericanCeramicSocietyCommunications,Vol69
Oct1986,pC235toC236

[6020]

C.Peytouretal
CharacterisationofCeramic/TA6VTitaniumAlloyBrazedJoints
J.Mater.Res.,Vol5,No.1,Jan1990,p127135

[6021]

M.L.Santella
BrazingofTitaniumVaporCoatedSiliconNitride
AdvancedCeramicMaterials,Vol3,No.5,1988,p457462

[6022]

G.Hanfleretal
DiffusionBondingofCastandEBWeldingofPMNickelbase
Superalloys
ProceedingsoftheConferenceHighTemperatureAlloysforGas
TurbineandOtherApplications.Liege,Belgium,Oct69,1986p801
810.D.ReidelPublishingCompany

[6023]

S.Kangetal
IssuesinCeramictoMetalJoining:AnInvestigationofBrazinga
SiliconNitridebasedCeramictoaLowexpansionSuperalloy
CeramicBulletin,Vol68,No.9,1989,p16081617

[6024]

S.Karunanithy
MeltInfiltrationandReactionattheFibre/MatrixInterfaceDuringthe
BrazingofaFibrereinforcedCeramictoMetal

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Am.Ceram.Soc.Comm.,Vol73,Jan1990,p178181
[6025]

M.Shimadaetal
DiffusionBondingofAl2O3andSi3N4CeramicsbyHIPping
EmergentProcessMethodsforHighTechnologyCeramicsPlenum
Press,1984,p591596

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61 Mechanical connections
61.1 Introduction
61.1.1

Requirements

61.1.1.1

General

Joints enable a number of components to be assembled into an integrated structure and load to be
transferredbetweenthecomponentsparts.

61.1.1.2

Similar materials

Joiningsimilarmaterialsistheeasiestsituation,achievableby:

mechanicalfastening,

bonding,or

welding(metalsandsomeplastics).

61.1.1.3

Dissimilar materials

Withdissimilarmaterialsthereisgreateruncertaintyonthecompatibilityoftwoconnectingsurfaces,
particularlyifthermalexcursionsareenvisaged.Ifreliabilityandconsistencyofjointperformanceis
paramount,thengreaterrelianceisplacedonmechanicalconnectionsthanthosesolelyusingfusion
orbondingtechniques.

61.1.1.4

In-service

Mechanical connections have the added ability to be disassembled and reassembled. This is
particularly useful in power units containing rotating components such as fan blades and pumps.
Equally,atregularintervals,individualcomponentscanbe:

Monitored,

Removed,

Cleaned,

Inspected,and

Repairedorreplaced.

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61.2 Versatile joints


61.2.1

Applications

61.2.1.1

General

Adistinctionismadebetweenthedemandsof:

Static, cold structures: such as airframes, thin skins and sandwich structures in CFRP and
aluminium,and

Dynamic, hot structures: such as engines and thermalresistant structures using titanium,
superalloys,hightemperaturecompositesorcombinationsthereof.

61.2.1.2

Static cold structures

Predominantmethodsare:

Mechanicalfastening,[See:Chapter22]:

threadedfasteners.

insertsforsandwichpanels,[See:Chapter23].

Adhesivebonding,[See:Chapter21].

[See: ECSSEHB3221 Adhesive bonding handbook, ECSSEHB3222 Insert design handbook,


ECSSEHB3223 Threaded fasteners handbook, ECSSQST7046 Requirements for
manufacturingandprocurementofthreadedfasteners]

61.2.1.3

Dynamic hot structures

Withthelikelihoodofthermalexcursions,allowanceismadefordifferentthermalexpansionsandthe
needforrelativemovement.
Mechanical connections, welding and brazing are common. Whilst fasteners can be used, e.g. bolts,
theirreliabilityunderhot,cyclicandcorrosiveconditionsshouldbeascertained.
The use of fastener systems in joint configurations between dissimilar materials is often the only
optionforapplicationssuchasthermalstructuresandTPSonreusablevehicles.Rivetsareavoided.

61.2.2

Mechanical techniques

Mechanicaljointmethodsinclude:

Retentionrings.

Tapers.

Interlocks.

Collars.

Pins.

Clips.

Compressionjoints.

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Threadedfastenerssystems,e.g.screws/bolts,nuts,washersandbushes,madefrom:

specialisthightemperaturemetals.

ceramicbasedcomposites.

monolithicceramics.

Inselectinganappropriatejointconfiguration,importantfactorsincludethe:

Intendedlifespan,

Reuseofstructuresandcomponents,

Serviceintervals,

Accessforinspectionandreplacement.

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62
(Heading number reserved)
ThisSectionhadoriginallybeenplannedtocoveraparticularsubjectasdirectlymappedtotheESA
PSS03203thatthisdocumentsetsuperseeds,theidentifiedsubjectwasconsiderednolongerrelevant
forthispublication.
To retain the original cross reference structure of the handbooks part 18, this heading has been
reservedasaplaceholderonly

63
(Heading number reserved)
ThisSectionhadoriginallybeenplannedtocoveraparticularsubjectasdirectlymappedtotheESA
PSS03203thatthisdocumentsetsuperseeds,theidentifiedsubjectwasconsiderednolongerrelevant
forthispublication.
To retain the original cross reference structure of the handbooks part 18, this heading has been
reservedasaplaceholderonly

435