Injection Molding Amorphous vs Crystalline Resins

Dan Saunders Sr. Technical Consultant

The information and suggestions provided in this presentation are based on data believed to be reliable, but the DuPont Company makes no warranties express or implied as to their accuracy and assumes no responsibility or liability arising out of its use by others. Further, the information and suggestions are not intended to substitute for any testing you may need to conduct to determine for yourself the suitability of a particular material for a particular purpose. DuPont makes no guarantee of results and assumes no obligation or liability in connection with the use of the information or suggestions provided in this seminar.

October 12, 2006

Copyright 2006 E. I. du Pont de Nemours and Company. All rights reserved. DuPont Engineering Polymers. reserved.

Crystalline vs Amorphous Polymers

What are the broad similarities and differences between crystalline and amorphous polymers? Similarities
Broad range of commercial formulation
Amorphous - ABS, PC, PS, PMMA, etc Crystalline - PA, PE, PP, PET, PBT, etc

Differences
Molecular interactions of the polymer chains
Amorphous low order in solid phase Crystalline high order in solid phase

Multiple processing techniques

Injection molding, blow molding, extrusions

Response to temperature changes

Amorphous Tg only Crystalline Tg and Tm

Environmental sensitivities
Upper and lower use temperatures, weathering, mechanical and electrical properties, etc

Solvent resistance
Crystalline polymers are generally better

10/12/2006 DUPONT CONFIDENTIAL

Crystalline and Amorphous Plastic Properties

Crystalline resin strengths solvent resistance, fatigue resistance, property enhancement by fillers and reinforcing agents, creep, cycle time, flow Amorphous resin strengths clarity, low warpage, acceptance of plasticizers, density, thermoforming

Amorphous resins are defined by their chemistry and Tg. Tg is the upper use limit Crystalline resins are defined by their chemistry, Tg and Tm. Tm is upper use limit

10/12/2006 DUPONT CONFIDENTIAL

Modulus vs. Temperature

Crystalline and Amorphous Polymers
Modulus

High Crystallinity
Rigid

Low Crystallinity

Amorphous

Tg
C

Tg
A

Tm
C

Temperature

The specific chemistry of the polymer (monomers) controls the actual values of Tg and Tm.

10/12/2006 DUPONT CONFIDENTIAL

Polymer Glass Transition Temperatures

Tg -100 C 0 C 100 C

POM PTFE PE POM PP PA 6/6 Sat Nylon 11

PVC PS PA 6/6 DAM

ABS PMMA

PC HTN

Amorphous
"Rigid"

Crystalline
"Rigid" Moderate fatigue resistance High creep resistance Brittle Good fatigue resistance Lower creep resistance Ductile

Below Tg

Low fatigue resistance High creep resistance Brittle "Elastomeric no mechanical properties

Above Tg

The above are generalizations, exceptions due exist.

10/12/2006 DUPONT CONFIDENTIAL

Property Summary Crystalline and Amorphous Polymers

Common Features both amorphous and crystalline resins can be found that meet these requirements
Mechanical Electrical Flammability Useful temperature range strength toughness

Unique Features that differentiate polymer types Unique Features that differentiate polymer types Feature Crystalline Amorphous Feature Crystalline Amorphous
Solvent resistance Solvent resistance Optical properties Optical properties Endurance Endurance Filler enhancement Filler enhancement Dimensional stability Dimensional stability
10/12/2006 DUPONT CONFIDENTIAL

+ + 0 0 + + + + 0 0

0 0 + + 0 0 0 0 + +

Property Summary Crystalline and Amorphous Polymers

There are many parts that can be made using either an

amorphous or a crystalline resin. Polymer modification is a broad and evolving process.

Polymer suppliers are constantly adding new grades that aim to correct deficiencies and improve strengths.

Resin selection for a specific application needs to be

an iterative process that compares the application requirements with various polymer attributes. Processing characteristics are important. Environmental factors are important.

10/12/2006 DUPONT CONFIDENTIAL

Processing Crystalline and Amorphous Polymers

Common Features
Multiple processing techniques Controlled heating and cooling Moisture sensitive

Unique Features Crystalline Unique Features Crystalline Shrinkage High Shrinkage High Flow High Flow High Sharp melting range Yes Sharp melting range Yes

Amorphous Amorphous Low Low Low Low No No

Due to their different thermal characteristics, amorphous Tg and crystalline Tg and Tm, different molding rules are used for amorphous and crystalline polymers
10/12/2006 DUPONT CONFIDENTIAL

Plastic Processing
Why are different processing conditions needed to injection mold crystalline and amorphous polymers?
The density (volume) of amorphous and crystalline polymers change at a different rate under the influence of changing temperatures and pressures. Mold Fill and Pack Parameters Resin viscosity at processing temperatures and pressures Mold Fill The effect of resin modulus vs. temperature are different Ejectability

10/12/2006 DUPONT CONFIDENTIAL

10

Density vs. Temperature at Atmospheric Pressure

Density, g /cc

Amorphous

Crystalline

Tg
C

Tg
A

Tm
C

Temperature

Specific Volume is 1 / Density

10/12/2006 DUPONT CONFIDENTIAL

11

Density vs. Specific Volume

Inverse Relationship Density = 1 / Specific Volume Specific Volume = 1 / Density Density important to part weight Specific volume important to molding conditions Use PVT diagrams to highlight difference

10/12/2006 DUPONT CONFIDENTIAL

12

PVT Diagrams
Plot of specific volume vs. temperature at different pressures Easy to find
Tg Tm Glass transition temperature Melting point

Easy to see how

Volume increases with increasing temperature Volume decreases with increasing pressure Crystalline polymers undergo a rapid volume change at Tm which is missing in amorphous polymers Volume changes between RT and processing temperatures are: 1015% amorphous polymers 2025% crystalline polymers This difference in volume change is the primary reason for differences in shrinkage and warpage

10/12/2006 DUPONT CONFIDENTIAL

13

PVT Data on Nylon 66 and PC

1.10

1.05

Specific Volume, cc / g

Tm
1.00

Nylon 66

0.95

Tg
PC

0.90

0.85

0.80 0 100 200 300 400 500 600 700

Temperature, F

10/12/2006 DUPONT CONFIDENTIAL

14

PVT Data on Nylon 66 and PC

1.10

P=0
1.05

Specific Volume, cc / g

1.00

Nylon 66
P = 15,000 psi P=0

0.95

0.90

P = 15,000 psi
0.85

PC
0.80 0 100 200 300 400 500 600 700

Temperature, F
10/12/2006 DUPONT CONFIDENTIAL

15

Amorphous PVT Diagram

Softening

Specific Volume

P=0
Thermal Expansion

Injection
P = 14,500 psi
Temperature
Compression

10/12/2006 DUPONT CONFIDENTIAL

16

Amorphous PVT Diagram

Cooling

1. Decrease pressure expansion 2. Decrease temperature due to cooling shrinkage 3. Best result constant volume

Specific Volume

0 2 3 1

Temperature

10/12/2006 DUPONT CONFIDENTIAL

17

Amorphous PVT Diagram

Effects on Molding Rules
Injection Pressure Pressure Transducer

Time

After filling time:

Means:

Constant volume

No movement through gate Injection pressure led by cavity pressure (via transducer)

10/12/2006 DUPONT CONFIDENTIAL

18

Amorphous Polymer
Post-Molding Deformation

Internal stresses From over packing

Deformation

or stress cracking

Molecular orientation during molding may also cause these phenomena.

10/12/2006 DUPONT CONFIDENTIAL

19

Molding Amorphous Polymers

Overpacking is a major concern
Parts stick in mold Parts crack during ejection Residual internal stress

Optimum molding conditions

Inject using high pressure Pack pressure should decrease with time constant volume High mold temperatures reduce internal stress

10/12/2006 DUPONT CONFIDENTIAL

20

Crystalline PVT Diagram

Melting Injection Crystallization
Melting
0 11,600 psi

Specific Volume

During melting process (solid liquid) volume x 16% Crystallization Shrinkage by ~14%; Voids created have to be filled with liquid polymer

Temperature

Crystallization under constant pressure

10/12/2006 DUPONT CONFIDENTIAL

21

Crystalline Polymer
Post-Molding Deformation

Cold mold

Poor crystal structure

Post shrinkage recrystallization with time and temperature

Deformation

10/12/2006 DUPONT CONFIDENTIAL

22

Controlling Crystallization During Molding

Mold Temperature
The higher the mold temperature, the higher the crystallinity

Pressure
Low pressure increases rate of crystallinity

Stress During Crystallization

Can produce orientation

10/12/2006 DUPONT CONFIDENTIAL

23

Typical Melt Viscosity

Amorphous Crystalline

A typical crystalline polymer will have a lower melt viscosity at its standard processing conditions vs typical amorphous polymers. This translate into lower pressure to fill the part.
Note - axis have different scales

Many resins are available in multiple flow ranges

10/12/2006 DUPONT CONFIDENTIAL

24

Venting
Vent depths are a function of resin viscosity and the time it takes the resin to form a rigid skin. High viscosity Deep Vents

Low viscosity

Shallow Vents

Typically vent for crystalline resins are more shallow than for amorphous resins. Crystalline
PA 6,6 PBT POM PP 0.0003 0.0005 inch 0.0005 0.0007 inch 0.0005 0.0010 inch 0.0005 0.0012 inch

Amorphous
ABS PMMA PC 0.0010 0.0015 inch 0.0015 0.0020 inch 0.0015 0.0025 inch

10/12/2006 DUPONT CONFIDENTIAL

25

Modulus vs. Temperature

Crystalline and Amorphous Polymers
Modulus
Processing window

High Crystallinity
Rigid

Amorphous

Delta between Tm and processing temperature (crystalline) less than between Tg and processing temperature (amorphous)

Low Crystallinity

Tg
C

Tg
A

Tm
C

Temperature

Amorphous resins need to cool more prior to ejection from the mold
10/12/2006 DUPONT CONFIDENTIAL

26

Estimated Maximum Ejection Temperature

Crystalline and Amorphous Polymers
Amorphous ABS PC PS 80C 120C 65C Crystalline 6,6 nylon PBT POM PP 160C 165C 150C 80C

Amorphous resins need to cool more prior to ejection from the mold. An approximate maximum ejection temperature is 0.45MPa deflection temperature 15C.

10/12/2006 DUPONT CONFIDENTIAL

27

Injection Molding Cycles Amorphous / Crystalline Plastics

Calculated Cooling Time vs Wall Thickness - Median Melt and Mold Temperatures
35.0 30.0 25.0 20.0 15.0 10.0 5.0 0.0 0 1 2 3 4 Wall Thickness (mm)

Cooling Time (sec)

6,6 nylon abs pc pp pbt ps pom pe

10/12/2006 DUPONT CONFIDENTIAL

28

Injection Molding Cycle Amorphous Crystalline

Close Eject Open
Screw stationstationary

Close Fill time Eject Open MATERIAL UNDER PRESSURE Safety time Fill time

Hold pressure time

COOLING TIME

COOLING TIME

MATERIAL UNDER PRESSURE Hold

pressure time

Dosing

Dosing

Actual times are dependent on specific resin, mold design and processing conditions. Crystalline resins can usually be ejected right after gate freeze occurs. Cooling time is only needed to recover screw. Faster cycle times are frequently possible.
10/12/2006 DUPONT CONFIDENTIAL

29

Other Processing Considerations

Shrinkage
Typically molds cut for amorphous resins need to be re-cut for crystalline resins and vice versa.

Gating
Gates for crystalline resins are larger than for amorphous resins

Surface appearance
Surface appearance differs due to crystalline resins being opaque and amorphous resins being clear.

Tool wear
Little definitive data comparing wear. Generally believed that tool wear is similar for both types of resins. Typically dominated by additive and fillers

General trends are seen for both amorphous and crystalline resins, however, specific differences are grade dependent.

10/12/2006 DUPONT CONFIDENTIAL

30

Typical Range (flow and cross flow) of Shrinkage

Crystalline and Amorphous Polymers

Amorphous
ABS PC PS 0.5-0.7% 0.5-0.7% 0.2-0.8%

Crystalline
6,6 nylon PBT POM PP 1.0-2.5% 1.0-2.0% 2.0-3.5% 1.0-3.0%

Higher shrinkage of crystalline resins makes them more prone to warping. The difference in shrinkage between flow and cross flow directions becomes more important as absolute shrinkage increases. The presence of glass fiber reinforcement can increase the difference between flow and cross flow shrinkage.

10/12/2006 DUPONT CONFIDENTIAL

31

Gating, Filling of the Mold, Hold Pressure

Crystalline Style
t = 0.05s

Amorphous Style

Crystalline Style
t = 0.09s

Amorphous Style

0.05 Sec Crystalline Style

t = 01.5s

0.09 Sec Amorphous Style Crystalline Style

t = 03.0s

Amorphous Style

1.50 Sec

3.00 Sec

Molding crystalline resins using amorphous style gates can cause problems with shrinkage, warp, mechanical properties and appearance
10/12/2006 DUPONT CONFIDENTIAL

32

Hold Pressure Packing

Crystalline Style
t = 08.0s

Amorphous Style

Crystalline Style
t = 09.0s

Amorphous Style

8.00 Sec Crystalline Style

t = 18.0s

9.00 Sec Amorphous Style Crystalline Style

t = 24.0s

Amorphous Style

18.0 Sec

24.0 Sec

Molding crystalline resins using amorphous style gates can cause problems with shrinkage, warp, mechanical properties and appearance
10/12/2006 DUPONT CONFIDENTIAL

33

Typical Tool Steels

A.I.S.I. Type Steel Type Analysis - % C Mn Ni Cr Mo Si V Toughness Wear Resistance Usual Working RC D-2 A-2 A-6 L-6 H-13 P-20 S -7 420S.S.

1.5 0.50 12.0 1.0 0.3 0.9 Low High 58 61

1.00 0.8 5.0 1.0 0.3 0.2 Med Med 59 62

0.70 2.0 1.0 1.0 0.3 Med Med 58 60

0.70 0.35 1.75 1.0 0.25 High Fair 58 62

0.35 0.35 5.0 1.5 1.0 1.0 High Fair 50 54

0.35 1.25 0.40 High Poor 30 36

0.50 3.25 1.5 X-High Med 58 60

0.15 1.0 13.5 0.5 1.0 Med Fair 48 54

Resins (recommendations for cavities)

10/12/2006 DUPONT CONFIDENTIAL

Filled resins long working life

Un-filled Corrosion Resistance

34

Crystalline vs Amorphous Polymers

Some broad similarities and differences between amorphous and crystalline resins have been reviewed. The differences seen in properties and processing are based on fundamental differences in the structure of the polymers and intermolecular forces that hold the molecules together. Some differences can be overcome by part design or optimization of processing conditions while other differences can not.

10/12/2006 DUPONT CONFIDENTIAL

35

Copyright 2006 DuPont or its affiliates. All rights reserved. The DuPont Oval Logo, DuPont, The miracles of science, Kalrez, Viton, Vamac, Hypalon, Hytrel, Crastin, Rynite, Thermx, Zytel, and Delrin are registered trademarks or trademarks of DuPont or its affiliates.

10/12/2006 DUPONT CONFIDENTIAL