metals

Article
The Study of Heat Treatment Effects on Chromium
Carbide Precipitation of 35Cr-45Ni-Nb Alloy for
Repairing Furnace Tubes
Nakarin Srisuwan 1, *, Krittee Eidhed 2 , Nantawat Kreatsereekul 1 ,
Trinet Yingsamphanchareon 3,4 and Attaphon Kaewvilai 3,4
Received: 30 November 2015; Accepted: 13 January 2016; Published: 19 January 2016
Academic Editor: Hugo F. Lopez
1 Thai-French Innovation Institute, King Mongkut1 s University of Technology North Bangkok, Bangsue,
Bangkok 10800, Thailand; natthawat.k@tfii.kmutnb.ac.th
2 Faculty of Engineering, King Mongkut1 s University of Technology North Bangkok, Bangsue, Bangkok 10800,
Thailand; krittee.eed@gmail.com
3 Department of Welding Engineering Technology, College of Industrial Technology, King Mongkut1 s
University and Technology North Bangkok, Bangsue, Bangkok 10800, Thailand;
trinet2518@hotmail.com (T.Y.); attaphonk@kmutnb.ac.th (A.K.)
4 Welding Engineering and Metallurgical Inspection, Science and Technology Research Institute, King
Mongkut1 s University and Technology North Bangkok, Bangsue, Bangkok 10800, Thailand
* Correspondence: nakrin.s@tfii.kmutnb.ac.th; Tel.: +66-2-555-2000 (ext. 2534); Fax: +66-2-586-9014

Abstract: This paper presents a specific kind of failure in ethylene pyrolysis furnace tubes. It considers
the case in which the tubes made of 35Cr-45Ni-Nb high temperature alloy failed to carburization,
causing creep damage. The investigation found that used tubes became difficult to weld repair
due to internal carburized layers of the tube. The microstructure and geochemical component of
crystallized carbide at grain boundary of tube specimens were characterized by X-ray diffractometer
(XRD), scanning electron microscopy (SEM) with back-scattered electrons mode (BSE), and energy
dispersive X-ray spectroscopy (EDS). Micro-hardness tests was performed to determine the hardness
of the matrix and the compounds of new and used tube material. The testing result indicated that
used tubes exhibited a higher hardness and higher degree of carburization compared to those of new
tubes. The microstructure of used tubes also revealed coarse chromium carbide precipitation and a
continuous carbide lattice at austenite grain boundaries. However, thermal heat treatment applied
for developing tube weld repair could result in dissolving or breaking up chromium carbide with
a decrease in hardness value. This procedure is recommended to improve the weldability of the
35Cr-45Ni-Nb used tubes alloy.

Keywords: ethylene pyrolysis; furnace tube; chromium carbide; heat treatment; carbide
dissolution; carburization

1. Introduction

1.1. Material for Ethane Pyrolysis Furnaces Tube

Ethylene (C2 H4 ) can be generated by the thermal cracking of ethane (C2 H6 ), which is passed
through a coil of reaction tubes externally heated to a temperature of 10001150 C in pyrolysis furnaces.
The decomposition of ethane into ethylene is represented by the reaction below (1) [1]. Carbon residue
from the combustion products can be deposited at the internal surface of the tube wall as adherent
coke and must be removed repeatedly via decoking in water vapor and air. Consequently, the internal
carbide formation can occur after a corrosion phenomenon called carburization, which reduces the

Metals 2016, 6, 26; doi:10.3390/met6010026 www.mdpi.com/journal/metals

Metals 2016, 6, 26 2 of 14

Metals 2016, 6, 26 2 of 14
mechanical properties of materials and causes damages [2,3]. Thus, the alloy material must be suitable
properties of materials
to accommodate the highand causes
process damages These
temperature. [2,3]. Thus, the selected
alloys are alloy material must
for better highbe suitable
creep to
strength,
accommodate the high process temperature. These alloys are selected
carburization resistance, thermal shock resistance and weldability. for better high creep strength,
carburization resistance, thermal shock resistance and weldability.
CC
2H 6 6pg(g)q
2H
CC
2H 4 4pg(g)q `
2H +HH22(g)pgq (1)
(1)

The Ni-Cr-Fe
The Ni-Cr-Fe alloys
alloys are
are known
known forfor producing
producing material
material for
for tubular
tubular coils
coils within
within an
an industrial
industrial
pyrolysis furnace.
pyrolysis furnace. They
Theyhave
havebeen developed
been developedforfor
using at elevated
using temperature
at elevated wherewhere
temperature relatively severe
relatively
mechanical stresses are encountered and high surface stability is required [4]. The structure of
severe mechanical stresses are encountered and high surface stability is required [4]. The structure of Ni-Cr-Fe
alloys consist
Ni-Cr-Fe alloysofconsist
the primary
of thephase of phase
primary austenitic FCC matrix
of austenitic FCC(Figure 1a),
matrix plus a1a),
(Figure variety
plusofa secondary
variety of
phases [5],phases
secondary which [5],
are which
the metal
are carbides
the metaldenoted
carbidesonly by the
denoted compound
only Mx C suchM
by the compound asxCMC,
suchMas
6 CMC,
and
M
M623 C
C and(M = Metals, C = carbide), as shown in Figure 1b.
6 M23C6 (M = Metals, C = carbide), as shown in Figure 1b.

-phase

(a)

Cr23C6

(b)
Figure
Figure 1.
1. Phases
Phasesof
of35Cr-45Ni-Fe
35Cr-45Ni-Fe alloy:
alloy: (a)
(a)primary
primary-phase;
-phase;and
and (b)
(b) secondary
secondary carbides
carbides phase.
phase.

Previously, the small additions of niobium (Nb) to the tube production were able to increase
Previously, the small additions of niobium (Nb) to the tube production were able to increase
their resistance to thermal shock, while the Nb acts as a carbide stabilizer. Moreover, the nickel and
their resistance to thermal shock, while the Nb acts as a carbide stabilizer. Moreover, the nickel and
niobium could be combined in the matrix of an alloy to form body-centered tetragonal (BCT) called
the metastable -Ni3Nb phase. This phase provides very high strength at low and intermediate
temperatures; however, it is unstable at high temperatures above 650 C [6,7].
Metals 2016, 6, 26 3 of 14

niobium could be combined in the matrix of an alloy to form body-centered tetragonal (BCT) called
the metastable -Ni3 Nb phase. This phase provides very high strength at low and intermediate
temperatures; however, it is unstable at high temperatures above 650 C [6,7].
The transition of carbides in the Ni-Cr-Fe alloys can be considered by the Ellingham diagram
(relation between temperatures and Gibs free energy; G) [8]. In the range of temperatures over 850 C,
the G of nickel carbide and iron carbide (Ni3 C and Fe3 C) are positive such that the formation
of these carbides are a nonspontaneous process. On the other hand, the G of chromium and
niobium are negative, which indicates that the chromium and niobium tend to combine with carbon
to form chromium carbides (Cr23 C6 or Cr7 C3 ) and niobium carbide (NbC and Nb2 C), called carbide
precipitation or sensitization [9]. The type of formed carbide depends on the contents of the metal
and carbon in the alloy. Moreover, the precipitation of silicon carbide (SiC) has also occurred in the
structure of Ni-Cr-Fe alloys, but temperature is a very important factor in the determination of which
polytype of SiC is formed [6].
From the carbide precipitation, the corrosion resistance of Ni-Cr-Fe alloy decreased while the
hardness and brittle were increased [10]. The change in microstructure and in the properties of the
Ni-Cr-Fe alloy is a serious problem in the repairing of tube furnaces by welding.

1.2. Weldability with Thermal Heat Treatment

In general, post-weld heat treatments (PWTH) are usually not required for the
non-precipitation-hardenable Ni-Cr-Fe alloy weldments except for an additional agreement between
the owner and the welding contractor. However, in dissimilar-metal welding (DMW), the identity and
properties of the two metals being joined, and of the filler metal joining them, must be considered.
For example, if the Ni-Cr-Fe alloy being joined has various different physical and metallurgical
properties after long-term service, preheat should be used to make a dissimilar-metal weld. Another
variable that should be considered might be the need for a post-heat treatment for reducing the
weldability problems from different materials [11]. Additionally, the formation of chromium carbides
is readily reversed by thermal heat treatment [9,12]. Therefore, the tubing repair process could consider
a dissimilar-metal weld as well as a pre-heat treatment as an important parameter. The failure of the
Ni-Cr-Fe alloy in the petrochemical industry has been studied, and the influence of carburization,
carbide formation, thermal treatment conditions and welding repair technology has been investigated
by some researchers [13,1319].
However, this study is related to the problems of the weld repair process of used tubes in ethylene
pyrolysis furnace from the petrochemical industry in Thailand. The failure analysis was performed via
visual inspection and hardness measurements of the used tubes. Chromium carbide precipitation was
investigated. The results obtained provide guidance on applications of weld repair procedures when
the Ni-Cr-Fe alloy tube has a difference level of carburization.

2. Materials and Methods

2.1. Material Verification

A Ni-based super alloy 35Cr-45Ni-Nb grade (Elemental composition: 45% Ni, 35% Cr, 14.5%
Fe, 1.8% C, 1.7% Si, 1% Nb and 1% Mn) was used as a material. This alloy does not belong to the
standardized ASME-II Part B code (Non-ferrous metal); however, it was typically used in carburizing
applications. The information and visual inspection of experimental material are shown in Table 1.
Metals 2016, 6, 26 4 of 14

Table 1. Information
Metals 2016, 6,of
26 35Cr-45Ni-Nb tube specimen and visuals inspection. 4 of 14
Metals 2016, 6, 26 4 of 14
Table 1. Information of 35Cr-45Ni-Nb tube specimen and visuals inspection.
Specimen Information
Table and Visual
1. Information Inspection
of 35Cr-45Ni-Nb Image
tube specimen and visuals inspection.
Metals Specimen
2016, 6, 26 Information and Visual Inspection Image 4 of 14
SpecimenDiameter (OD)Diameter Information 63.4 63.4
(OD) and Visual 0.2mm
Inspection
0.2 mm Image
Metals 2016, 6, 26 4 of 14
Table 1.Outside
Diameter (OD) wall of 35Cr-45Ni-Nb
Information Light
63.4 gray
tube
0.2 mm shade and visuals inspection.
specimen
Outside wall Inside wall Light graysmooth
Original
shadesurface
Outside wall
Tube No. 1 Table 1. Information Light gray shade
Tube No. 1 (New) Specimen Information and Visual Inspection
of 35Cr-45Ni-Nb tube specimen and visuals inspection. Image
Inside
Tube No.(New)
1
wallInside wall
Diameter (OD)
Original
Original smooth
smoothsurface
63.4 deposit,
0.2 mm
surface
No coke original
Specimen Visual
Outside Information
inspection
wall and VisualLightInspection
grayoriginal
shade Image
(New) No coke deposit,
roundness, no swell
Visual inspection Diameter (OD) No coke deposit,
63.4 0.2 mm original
VisualInside wall
inspection Original
roundness, smooth
nonoswell surface
Tube No. 1 Outside wall roundness,
Light gray swell
shade
(New) Location 9 m on the ground
Location Inside wall 9 mOriginal
No oncokethe smooth
ground
deposit, surface
original
Tube No. 1 Diameter
Visual (OD)
inspection 67.8 0.8 mm
Location 9roundness,
m on the ground no swell
(New)
Diameter Outside wall Black shade & rough surface
Tube No. 2 (OD)Diameter (OD) 67.8
No coke 0.8
67.8 0.8mm
deposit, mmoriginal
VisualInside wall
inspection Thin coke deposit
(Used) Outside wall Black roundness,
shade no swell
Tube No. Outside
2 wall Location Black shade 9 m&on& rough
the
rough ground surface
surface
Tube No. 2 (Used) Inside
Visualwall
Diameter (OD)
inspection
Blockage ofcoke
Thin67.8 cokedeposit
inside tube, poor
0.8 mm
(Used) roundness
Inside wall Outside Location
wall Thin
Black9cokem on deposit
shade the ground
& rough surface
Tube No. 2 Diameter
Visual (OD) Blockage of2 67.8
inspection
Location
cokeinside
m on mmtube, poor
0.8 ground
the
Inside wall Blockage of Thincoke coke deposittube,
inside
(Used) Outside wall Black shaderoundness
Visual
Tube No. 2inspection Diameter (OD) 65.0& rough
0.4 mmsurface
Inside wall poorThin
Blockage roundness
of coke
coke inside
deposit tube, poor
(Used)
Tube No. 3 Location
Outside
Visual wall
inspection 2
Blackm on
shade the &ground
rough surface
roundness
Location
(Used) DiameterInside
(OD)wall 2 m on the
Thin
65.0 ground
coke
0.4 deposit
mm
Blockage of coke inside tube, poor
Visual inspection
Location 2 m roundness
onsoot
Outside wall BlackAshade &the
roughground surface
Tube No. 3
Diameter (OD)Visual inspection
Diameter (OD) 65.0little

65.0 0.4 mminside
roundness
0.4 mm
tube,
(Used) Inside wall Thin coke
Poor deposit
Location 2 m on the ground
Outside wall Black Black shade & rough surface
TubeOutside
No. 3 wall Location shade
A little &
soot
1 65.0
m rough
oninside
the surface
mmtube,
ground
Tube No. 3 (Used) Diameter
VisualInside
(OD)
wall
inspection Thin coke0.4deposit
(Used) Diameter
Outside (OD)
wall BlackPoor 65.0
shade & rough
0.4 mmsurface
roundness
Inside
Tube No. 3 wall Thin coke deposit
Outside
Inside wallwall A little
Black soot
shade
Thin coke&inside
rough
deposit tube,
surface
Tube No. 4
(Used) Visual inspection
Location 1 mPooron the ground
Inside wall A little soot
Thin inside
coke deposittube,
roundness Poor
inside tube
Visual
(Used)inspection
Diameter (OD) A little
65.0soot
0.4inside
mm tube,
Visual inspection
Location roundness
1 Poor
m onroundness
the ground
Outside
Visualwall
inspection BlackNear
shade & rough
original surface
roundness
Tube No. 4 Diameter (OD) 65.0 ground
0.4 mm
LocationInside wall
Location 1 mcoke
Thin on
1 mthedeposit inside tube
on the ground
(Used) Outside wall Black shade & rough surface
Tube No. 4 Diameter (OD) 65.0 0.4 mm
Diameter (OD)
(Used) Inside wall 65.0
Thin coke 0.4 mm
deposit inside tube
SpecimenVisual 1inspection
No. Outside
and wall
used tubes No.Near24
Black original
shade & roundness
(after 6 years
rough of service at pressure 32 bar, and a
surface
Tube No. 4
Tube No. 4 (Used) Outside
temperature of wall
about 8001100
Inside wall
Visual inspectionC)Black
were shade
carefully
Thin coke & rough
cut into
deposit
Near original roundness
surface
the
insideoutside
tube diameter at 6.36.8 cm and 1.0 cm
(Used)
of thickness. After that, the new tube and used tubes were analyzed by an X-ray diffractometer, (XRD:
SpecimenInside wall
No. 1 Visual
and Eindhoven,
used Thin
tubesThe coke deposit
No.Netherlands),
24
Near(after
inside
6 aroundness
years tube
of service
Philips X-Pert-MPD, inspection original scanning electronat microscope
pressure 32(SEM:
bar, and
JEOLa
temperature
Visualof about
JSM-6310F,
Specimen No.8001100
inspection
Peabody,
1 and C)
MA,used
USA) were carefully
Near
with
tubes 24cut
original
back-scattered
No. into
(after 6the
roundness
electrons outside
years mode diameter at
(BSE),atand
of service 6.36.8 cmbar,
and and
1.0 cm
an energy-dispersive
pressure 32 a
of thickness.
temperature After
X-ray spectrometerthat, (EDS:
of about the new
8001100 tube
EDAX, andYork,
C) New
were used NY,tubes
carefully USA)
cut were
intowith analyzed
the outsideby
elemental an X-ray
mapping.
diameter diffractometer,
at 6.36.8 (XRD:
cm and 1.0 cm
Philips Specimen
X-Pert-MPD, No. Eindhoven,
1 and used The tubesNetherlands),
No. 24 (aftera 6scanning
years of service atmicroscope
pressure 32(SEM:bar, and a
of thickness. After that, the new tube and used tubes were analyzedelectron by an X-ray diffractometer, JEOL
(XRD:
temperature
2.2. Heat of about 8001100
Treatment, Hardness C)
and were carefully cut into the outside diameter at 6.36.8 cm and 1.0 cm
Microstructure
Specimen No. 1 andPhilips usedX-Pert-MPD,
JSM-6310F, tubes No.
Peabody, MA, 24 (after
USA)
Eindhoven,with 6 years ofa service
back-scattered
The Netherlands), electrons mode at pressure
(BSE),
scanning electron and an 32 (SEM:
bar, JEOL
and a
energy-dispersive
microscope
of thickness. After that, the new tube and used tubes were analyzed by an X-ray diffractometer, (XRD:
X-ray spectrometer (EDS: EDAX, of New York, NY, USA)
temperature of about 8001100JSM-6310F,The Peabody,
heat
C)
Philips X-Pert-MPD,were MA,
treatments USA)
carefully
Eindhoven,
with
specimens
cut
The
were
thewith
back-scattered
intoperformed
Netherlands),
elemental
electrons mode
in three
outside mapping.
(BSE), and
conditions,
a scanningdiameter
as an energy-dispersive
atreported
electron microscope6.36.8 in Table 2.
(SEM:cm and
JEOL
X-ray
Thespectrometer (EDS: EDAX,
specimens before (No. 1)New andYork,
afterNY, USA)
heat with elemental
treatment (No. 24)mapping.
were tested by the Vickers
1.0 cm of thickness. After JSM-6310F, Peabody, MA, USA) with back-scattered electrons mode (BSE), and an energy-dispersive
2.2.that,
Heat the newHardness
Treatment,
micro-hardness tube
testingand
and used
furthertubes
and Microstructure were
analyzed the analyzed
microstructure bybyancombining
X-ray diffractometer,
techniques of
X-ray spectrometer (EDS: EDAX,
andNew York, NY, USA) with elemental mapping.
(XRD: Philips X-Pert-MPD,2.2. The
Heat
SEM-BSE
Eindhoven,Treatment,
and EDS
heat treatments
Hardness
Themapping. Microstructure
ofNetherlands), a scanning
specimens were performed electron
in three microscope
conditions, as reported (SEM: JEOL
in Table 2.
JSM-6310F, Peabody, MA, The2.2.
USA) The Treatment,
Heat
specimens heat before
with treatments
(No.of1)specimens
Hardness
back-scatteredandand were
Microstructure
electrons
after performed
heat mode
treatment in (BSE),
three 24)
(No. conditions,
and an
were asenergy-dispersive
reported
tested by in Table
the 2.
Vickers
Table 2. Heat treatment conditions.
The specimens
micro-hardness beforeand
testing (No.further
1) and analyzed
after heatthe treatment (No. 24)bywere
microstructure tested bytechniques
combining the Vickersof
X-ray spectrometer (EDS: EDAX, The heatNew
Conditions
micro-hardness York,and
treatments
testing NY,
of USA)
specimens
Heat
further withperformed
were
Treatment
analyzed elemental
Methods mapping.
in three
the microstructure
conditions, as reported in Table 2.
Note techniques of
by combining
SEM-BSE and EDS mapping.
The specimens before (No. 1) and after heat treatment (No. 24) were tested by the Vickers
SEM-BSE and C1EDS mapping. Without heat treatment New tube (No. 1)
micro-hardness testing and further analyzed the microstructure by Used
combining techniques of
2.2. Heat Treatment, Hardness and
SEM-BSE and
Microstructure
C2 Pre-heat 600 C, 12.hHeat treatment
Table Cooled down in air
conditions. tube (No. 24)
C3EDS mapping.
Pre-heat 900 Table
C, 1 h2. HeatCooled
treatmentdown in air
conditions. Used tube (No. 24)
The heat treatments ofConditions
specimens Heat Treatment
Conditions were performedHeat Treatment
Table inMethods
2. Heat three conditions,
Methods
treatment conditions.
Note
as reported
Note in Table 2.
C1
For hardness testing, Without
each of heat treatment
specimen was divided into four New tube (No.
quadrants (area1) 14) for
The specimens before (No.comparing
1)
C2 and
C1 the after
Conditions Pre-heatheat
hardness treatment
Without
at different
600 C,
Heat h position
1 Treatment (No.
heat treatment
Cooledon down 24)
the cross
Methods
were areas
sectional
in air tested
Newastube
Used by
(No.the
shown
tube
Note 24) Vickers
(No.in1)Figure 2.
C2 Pre-heat 600 C, 1all
h Cooled down in air to the NACE
Used tube (No. 24)
micro-hardness testing and further
During theanalyzed
C3 C1 Pre-heatthe
micro-hardness microstructure
900testing,
C, 1 h specimens
Without Cooled
heat by
down
treatment combining
corresponded
in air techniques
Used Standard
Newtube
tube(No.of24)
(No. 1)SEM-BSE
TM 0498-98
C3 A370, with
and ASTM Pre-heat 900 C,
accepted 1 hsettingsCooled
load of 500 down
kg. in air Used tube (No. 24)
and EDS mapping. C2 Pre-heat 600 C, 1h Cooled down in air Used tube (No. 24)
For hardness
C3 testing, each
Pre-heat 900ofC,specimen
1h was divided
Cooled into four Used
down in air quadrants (area
tube (No. 24)14) for
For hardness testing, each of specimen was divided into four quadrants (area 14) for
comparing the hardness at different position on the cross sectional areas as shown in Figure 2.
comparing the hardness at different position on the cross sectional areas as shown in Figure 2.
During the Table 2.
For micro-hardness
hardness Heat
testing, treatment
each
testing, all conditions.
of specimens
specimen was divided into four quadrants (area
TM14) for
During the micro-hardness testing, all specimenscorresponded
correspondedto tothe
the NACE
NACE Standard
Standard TM 0498-98
0498-98
andcomparing
ASTM
and ASTM
the with
A370, hardness
A370, with
at different
accepted
accepted load
load
position on kg.
settings
settingsofof500
the cross sectional areas as shown in Figure 2.
500 kg.
During the micro-hardness testing, all specimens corresponded to the NACE Standard TM 0498-98
Conditions Heat Treatment Methods Note
and ASTM A370, with accepted load settings of 500 kg.
C1 Without heat treatment New tube (No. 1)
C2 Pre-heat 600 C, 1 h Cooled down in air Used tube (No. 24)
C3 Pre-heat 900 C, 1 h Cooled down in air Used tube (No. 24)

For hardness testing, each of specimen was divided into four quadrants (area 14) for comparing
the hardness at different position on the cross sectional areas as shown in Figure 2. During the
micro-hardness testing, all specimens corresponded to the NACE Standard TM 0498-98 and ASTM
A370, with accepted load settings of 500 kg.
Metals 2016, 6, 26 5 of 14
Metals 2016, 6, 26 5 of 14

1.5 mm. 0 Area

1
2
Metals 2016, 6, 26 3 5 of 14
1.5 mm. 4

1.5 mm. 0 Area

270 1 90
2
3ID OD
1.5 mm. 4
Figure 2. The
The location
location on
on the
the cross
cross section of tube specimen for micro-hardness testing.
270 90
All specimens were cut into smaller pieces and then mounted into Bakelite ID
cylinders. ODThereafter, the
All specimens were cut into smaller pieces and then mounted into Bakelite cylinders.
specimens surfaces
Thereafter, theFigure were
2. The polished
specimens onby
surfaces
location using
were
the abrasive
crosspolished
section SiCusing
by
of tube paperabrasive
specimen (No. 120, 240,
SiC 400,
paper
for micro-hardness 600, 800
(No.
testing. 120,and 1000).
240, 400,
After every step of polishing, the surfaces were etched in mixed solutions (40 mL
600, 800 and 1000). After every step of polishing, the surfaces were etched in mixed solutions (40 mL glycerol, 20 mL HCl
and 20% All
glycerol, HNO mL3). Additionally,
20 specimens
HCl were
and cut
20% the
into specimens
smaller
HNO pieceswere cleaned
and then mounted in an
intoultrasonic bath. Lastly,
Bakelite cylinders. the SEM-BSE
Thereafter, the
3 ). Additionally, the specimens were cleaned in an ultrasonic
specimens
combined with surfaces
EDS were polished
mapping were by using
used to abrasive
analyze theSiC paper (No. 120,
microstructure 240,
and 400, 600, composition.
elemental 800 and 1000).
bath. Lastly, the SEM-BSE combined with EDS mapping were used to analyze the microstructure and
After every step of polishing, the surfaces were etched in mixed solutions (40 mL glycerol, 20 mL HCl
elemental composition.
and 20%
3. Results HNO
and 3). Additionally, the specimens were cleaned in an ultrasonic bath. Lastly, the SEM-BSE
Discussion
combined with EDS mapping were used to analyze the microstructure and elemental composition.
3. Results and Discussion
3.1. Material Verification
3. Results and Discussion
3.1. Material Verification
A visual inspection of Specimen No. 1 found that it had no significant internal or external
3.1.
damage. Material
A visual
It showed Verification
inspection of Specimen
a good quality No. 1 found that
of structures withit had
no no significant
visible pits, no internal
depositor and
external damage.
no signs of
It showedAavisual
carburization. good quality
Oninspection
the other of of
structures
hand,
Specimen with
No. no
carburization visible
1 found pits,
reactions
that noand
it had deposit
no coke and nointernal
deposits
significant signswereof
orcarburization.
observed at
external
On the
different other
damage. hand,
configurations
It showed carburization
a in
good reactions
thequality
three height
of andpositions
cokewith
structures deposits wereSpecimen
studied.
no visible observed
pits, at different
No.
no deposit 2and
hadnotheconfigurations
most
signs of coke
deposits and signs of carburization, but also a roundness and shape that was significantlyat more
in carburization.
the three height On the
positionsother hand,
studied. carburization
Specimen reactions
No. 2 hadand coke
the mostdeposits
coke were
deposits observed
and signs of
different
carburization,
deformed configurations
thanbut in
also a roundness
Specimens the three
No. 3 andand height
No.shape positions studied.
that was significantly
4, respectively. Specimen
However, no moreNo. 2 had
deformed
cracking the most coke
than Specimens
in Specimens No. 2,
No. 3deposits
andNo.
or No.4and4, signs of carburization,
respectively.
were (Table 2).but
observed However, no also a roundness
cracking and shape
in Specimens No. 2,that
No. was significantly
3 or No. 4 weremore observed
deformed than Specimens No. 3 and No. 4, respectively. However, no cracking in Specimens No. 2,
(Table 2). 3 shows the XRD patterns of the Cr-Ni-Nb alloy before and after use in the pyrolysis furnace.
Figure
No. 3 or No. 4 were observed (Table 2).
Figure
Specimen No. 3 shows
1 exhibitedthe XRD patterns ofpeaks
both diffraction the Cr-Ni-Nb
corresponding alloytobefore
the and after use
austenitic (FCC) in phase
the pyrolysis
and the
Figure 3 shows the XRD patterns of the Cr-Ni-Nb alloy before and after use in the pyrolysis furnace.
1 austenitic (FCC)
furnace.
(BCT) Specimen
phase of No. 1
Cr-Ni-Nb exhibited
alloy both
and Nidiffraction peaks
3Nb, respectively, corresponding
as shown in
Specimen No. 1 exhibited both diffraction peaks corresponding to the austenitic (FCC) phase and the to the
Figure 3a. In the case of
phase and
Specimen (BCT)thephase
No. (BCT)
the
2, XRD
of phase
pattern
Cr-Ni-Nb of alloy
Cr-Ni-Nb
(Figure
and3b) alloy
Ni and Nithe
displayed 3 Nb,
3Nb, respectively,
respectively,
sameas major in as
shownpeaks shown3a. in
of FCC
Figure In Figure
and BCT
the 3a.ofIn the
phases
case as
casenew
the of Specimen
tube. Moreover,
Specimen No. 2,No.the2,XRD
the XRD pattern
Specimen
pattern (Figure
No. 2 exhibited
(Figure 3b) 3b)
thedisplayed
displayed additional the
the same major same
peaks major
which
peaks peaks
correspond
of FCC and BCT of phases
FCC
to theand BCT
carbide
as
phasestheas
structures newthe new
oftube.
NbC tube. Moreover,
(JCPDS
Moreover, Specimen
No. 00-038-1364),
Specimen No. 2 exhibitedNo.SiC 2 exhibited
the (JCPDS No.
additional the
peaksadditional
000-029-1129)peaksand
which correspond which correspond
Cr23carbide
to the C6 (JCPDS
to the
No. structures
00-035-0783). of
carbide structuresNbC (JCPDS
of NbC
This result No. 00-038-1364),
(JCPDS
clearly SiC
No. 00-038-1364),
indicated (JCPDS No. 000-029-1129)
SiC (JCPDS
that the precipitated and Cr
No. 000-029-1129)
carbide C
of the tube furnace
23 6 (JCPDS
and Cr23 C6
was
(JCPDSNo.No.
produced 00-035-0783).
in 00-035-0783).
the process This
ofresult
This
ethane clearly
result indicated
clearly
pyrolysis. that thethat
indicated precipitated carbide ofcarbide
the precipitated the tubeof furnace
the tubewas furnace
produced ininthe
was produced process
the processof ethane pyrolysis.
of ethane pyrolysis.

Figure XRD
3. 3.
Figure XRDpatterns
patterns of
of (a) the
thenew
newtube
tubeand
and(b)(b)
thethe used
used tube.
tube.
Figure 3. XRD patterns of (a) the new tube and (b) the used tube.
Metals 2016, 6, 26 6 of 14

Metals 2016, 6, 26 6 of 14
The microstructure of the Cr-Ni-Nb alloy and its carbide was observed by SEM-BSE and EDS
mapping, Theasmicrostructure
shown in Figure of the4. BSE is the alloy
Cr-Ni-Nb electronandsignal from was
its carbide elastic scattering
observed interaction
by SEM-BSE and between
EDS
electron
mapping,beam and atomic
as shown in Figurespecimen.
4. BSE isThis interaction
the electron signaldepends
from elasticon the atomicinteraction
scattering weight ofbetween
the atom.
The more heavy
electron beam and an atom
atomic is,specimen.
the moreThis a BSE signal can
interaction be generated,
depends givingweight
on the atomic resultsofinthea brighter
atom.
contrast. Therefore, the BSE is used to detect contrasts between
The more heavy an atom is, the more a BSE signal can be generated, giving results in a brighter areas with different elemental
compositions [19,20]. Figure
contrast. Therefore, the BSE 4a,b is shows
used tothe backscattered
detect contrasts electrons
between areas images (BEI)
with of Specimen
different elementalNo. 1
compositions
(the new tube), [19,20].
in which Figure
three4a,b showsphases
different the backscattered
(bright, gray electrons images
and dark) are(BEI)
found. of Specimen
The Nb, aNo. 1
heavy
(the new tube), in which three different phases (bright, gray and
element (high atomic number), exhibited more BSE than those of the lighter elements (low atomic dark) are found. The Nb, a heavy
elementand
number), (high atomic
thus number),
appeared exhibited
brighter in BEI.moreThe BSE than
gray those
area was of identified
the lighteraselements
the major (low atomic
part of the
number),
matrix alloy,and
whilethustheappeared
dark area brighter
in BEI in BEI. be
might The thegray area was identified
precipitated carbide. as the major part of the
matrix alloy, while
By elemental the darkthe
analysis, area EDSin BEI might be
mapping the precipitated
(Figure carbide. No. 1 confirmed a good
4ch) of Specimen
By elemental analysis, the EDS mapping (Figure
dispersion of elementals in the alloy. The EDS revealed that the results agreed 4ch) of Specimen No. 1toconfirmed
XRD, anda that goodthe
dispersion of elementals in the alloy. The EDS revealed that the results
matrix (Ni-Cr-Fe solid solution) was observed as austenitic (FCC), with a variety of secondary phases agreed to XRD, and that the
matrix (Ni-Cr-Fe solid solution) was observed as austenitic (FCC), with a variety of secondary phases
of -Ni3 Nb (BCT), a strengthener phase comprised of an austenite matrix. The small numbers of coarse
of -Ni3Nb (BCT), a strengthener phase comprised of an austenite matrix. The small numbers of coarse
chromium carbide precipitates were observed within the matrix and at grain boundaries. Moreover, the
chromium carbide precipitates were observed within the matrix and at grain boundaries. Moreover, the
mapping of Cr (Figure 4f) was found to be similar to the dark area in BEI (Figure 4b), which indicated
mapping of Cr (Figure 4f) was found to be similar to the dark area in BEI (Figure 4b), which indicated
that the chromium and carbon appeared as a small chromium carbide precipitation. However, this
that the chromium and carbon appeared as a small chromium carbide precipitation. However, this
carbide
carbidephase
phasecannot
cannotbe be observed
observed in inXRD
XRDbecause
because ofof
thethe detection
detection limitlimit ofXRD
of the the XRD technique.
technique.
In In
the
thecase
caseofofone
oneof of the used tubes
the used tubes(Specimen
(Specimen No.
No. 2), 2),
thethe
BEIBEIandand
EDSEDS(Figure(Figure
4ip) 4ip)
showed showed
the
themicrostructure
microstructureofofthe theaustenite
austenitematrix matrix and more Cr-rich carbides (Figure 4n).
and more Cr-rich carbides (Figure 4n). Moreover, a phase Moreover, a phase
separation
separation ofof
mixed
mixedNbC NbCand andSiC SiCwas wasfound,
found, shown
shown in in Figure
Figure4l,p.
4l,p.TheTheobtained
obtainedresults
resultsofof XRD
XRD andand
SEM-BSE
SEM-BSE with EDSEDS
with confirmed
confirmedthat the pyrolysis
that caused the
the pyrolysis carbide
caused theprecipitation in the microstructure
carbide precipitation in the
of microstructure
the Cr-Ni-Nb alloy. of the The carbide
Cr-Ni-Nb precipitate
alloy. The carbide decreased the tensile
precipitate decreased strength, creep
the tensile resistance
strength, creepand
corrosion
resistanceresistance, and increased
and corrosion resistance,the andbrittle fracture
increased property,
the brittle the hardness,
fracture property, and the ductility
the hardness, and of thethe
ductility
material of the material [21].
[21].

Figure 4. BEI and EDS mapping of (ah) Specimen No. 1 (new); and (ip) Specimen No. 2 (used).
Figure 4. BEI and EDS mapping of (ah) Specimen No. 1 (new); and (ip) Specimen No. 2 (used).
Metals
Metals2016,
2016,6,6,2626 7 of 1414
7 of

3.2. Heat Treatment, Hardness and Microstructure

3.2. Heat Treatment, Hardness and Microstructure
The hardness of specimens before (No. 1) and after heat treatment (No. 24) in four areas were
The hardness of specimens before (No. 1) and after heat treatment (No. 24) in four areas were
tested and compared, as shown in Figure 5.
tested and compared, as shown in Figure 5.

Figure5. 5.
Figure TheThe hardness
hardness valuevalue ofareas
of four fourinareas in each specimen
each specimen withheat
with different different heat (a)
treatments: treatments:
without
(a) without heat treatment;
(b) 600 C/1 h;
and
heat treatment; (b) 600 C/1 h; and (c) 900 C/1 h. (c) 900 C/1 h.
Metals 2016, 6, 26 8 of 14

Figure 5 presents the hardness of each specimen with various heat treatment conditions. Each bar
shows the hardness value averaged from two readings at four different positions on a cross section
of specimens. In condition C1 (without heat treatment), the lowest hardness value was observed in
Specimen No. 1 with an average value of 303 HV, as shown in Figure 5a. On the other hand, Specimen
No. 2 with thick coke deposit inside the wall of a higher position of the pyrolysis furnace had the
highest hardness value, average as 405 HV. However, the average hardness was reduced to 377 HV
and 367 HV for Specimen No. 4 and No. 3, respectively.
In Figure 5b, the effect of the heat treatment process showed a considerable decrease in the
hardness value of all specimens. In the case of condition C2 (annealing 600 C, 1 h/air cooled), the
average hardness values decreased to 288, 340 and 358 HV for Specimens No. 24, respectively.
However, the annealing temperature of condition C2 was within the range of sensitization, so
chromium carbide could be precipitated at grain boundary. Therefore, the hardness values of used tube
specimens were still greater and higher than that of Specimen No. 1 (average of 277 HV). In addition,
Specimen No. 2 was acquired from the top part of the furnace tube, where the high carbon content was
accumulated as coke and tended to form a large amount of carbide phase. Therefore, the significant
decrease of hardness in sample 2 after heat treatment at 600 C might be due to the superior loss of
these carbide grains when compared to those of Specimens No. 34 .
Relating to condition C3 (annealing 900 C, 1 h/air cooled), as shown in Figure 5c, the lowest
hardness values were determined to be 273, 244 and 253 HV for Specimens 24, respectively, when
compared to the heat treatment condition of C1 and C3. The hardness measurement indicated that
condition C3 was a suitable condition because it could change the hardness values of the used tubes
close to the new tube for avoiding cracking damage during the weld repair and can be used to improve
the weldability of 35Cr-45Ni-Nb alloy.
Furthermore, SEM/EDS analysis could confirm a significant reason for a using thermal heat
treatment to a 35Cr-45Ni-Nb used tube for welding repair. The microstructures of each specimen
at heat treatment conditions of C2 and C3 by using SEM/EDS mapping are shown in Figures 6
and 7 respectively.
In Figure 6a, after heat treatment, Specimen No. 1 showed that the white precipitate adjacent
to the grain boundaries was Nb-rich in the metastable -Ni3 Nb phase as shown by EDS mapping.
Whereas, a small number of chromium carbide precipitates were observed within the matrix and at
the grain boundaries. Thus, it could be suggested that the good mechanical properties were exhibited
because the phase transformation could not be observed in the microstructure of Specimen No. 1.
Figure 6bd shows the microstructures in the used tube specimen. Specimens No. 2 and No. 3
also revealed coarse chromium carbide precipitation and a continuous carbide lattice at austenite
grain boundaries, while the metastable -Ni3 Nb phase could not be observed in the matrix austenite.
Additionally, the SiC and NbC were separated from the matrix austenite, which corresponded to
the degree of hardness values. The microstructure of Specimen No. 4 showed small amounts of
SiC and NbC within the area of chromium carbide precipitation at grain boundaries. This could be
explained by the laws of thermodynamic and the Gibbs free energy such that the significant alloying
elements (such as Nb and Si) were quickly activated with carbon atoms and reduced the degree
of sensitization [15,2123]. Therefore, it could be recommended that condition C2 (annealing 1 h
(600 C)/air cooled) could not give a beneficial effect to ensure that the precipitation of Cr23 C6 was
dissolved properly in the used tube for repair welding procedure.
Metals 2016, 6, 26 9 of 14

Figure 6. Cont.
Metals 2016, 6, 26 10 of 14

Figure 6. BEI and EDS mapping of the 35Cr-45Ni-Nb specimens after 1 h of thermal heat treatment at
600 C: (a) Specimen No. 1; (b) Specimen No. 2; (c) Specimen No. 3; (d) Specimen No. 4.
Metals 2016, 6, 26 11 of 14

Figure 7. Cont.
Metals 2016, 6, 26 12 of 14

Figure 7. BEI and EDS mapping of the 35Cr-45Ni-Nb specimens after 1 h of thermal heat treatment at
900 C: (a) Specimen No. 1; (b) Specimen No. 2; (c) Specimen No. 3; (d) Specimen No. 4.
Metals 2016, 6, 26 13 of 14

In condition C3, the formation of the metastable -Ni3 Nb phase occurred in the austenite matrix,
as shown in Figure 7a. However, the degree of sensitization at grain boundaries was enlarged when
compared to Specimen No. 1 in the condition C2. This was due to the fact that, after annealing at high
temperature of 900 C, the higher cooling rate could increase the reverse transformation of carbide
particles [24].
Figure 7bd shows the microstructure of carbide precipitates. It was found that the particles of
chromium carbide were dispersed and discontinued in the matrix austenite, and the small particles
of SiC and NbC occurred in the area of chromium carbides precipitation. In addition, there might be
other factors affecting the hardness, such as the redistribution of the phase component in the alloy,
particularly Ni, Si and Nb phases. Therefore, the mechanical properties and weldability of used tube
specimens were enhanced.
As a result, it is suggested that condition C3 (annealing 900 C 1 h/air cooled) was a suitable
method for chromium carbides dissolution which help decreased the hardness values of the used
tuebes and might improved the weldability of furnace tube repair.

4. Conclusions
The aim of this work was to find an suitable heat treatment process to decrease the hardness
value and/or reduce the chromium carbide precipitation at grain boundary of material due to the
major problem in welding repair of ethylene pyrolysis tubes, a dissimilar material between used tubes
and new tubes. This experiment confirmed the carburization in the 35Cr-45Ni-Nb alloy tube after
long-term service at high temperature in an ethylene pyrolysis furnace. The carbide precipitation at
grain boundary of the austenite matrix was found to increase the hardness values of the specimen.
However, after thermal heat treatment (annealing 900 C 1 h/air cooled), a decrease in the carbide
precipitate in the austenite matrix and in the hardness value of each specimen was observed when
compared to those before heat treatment. The temperature range and cooling rate were important
influences for the dissolution of carbides and reverse transformation. Furthermore, the next study will
investigate parameters which are significant for the successful joints of furnace tube repair, such as
wire electrode, welding process and post-weld heat treatment in the welding procedures.

Acknowledgments: This research was funded by King Mongkut1 s University of Technology North Bangkok
(Contract No. KMUTNB-GEN-57-55). The authors are very grateful to IRPC Public Company Limited for
supporting information and materials that used in this experiment. Additionally, thanks to Chockchai Singhatham,
in support of sample preparation for hardness testing.
Author Contributions: N. Srisuwan performed reseach and wrote the article. K. Eidhed and N. Kreatsereekul
helped in the experimental part. T. Yingsamphanchareon and A. Kaewvilai assisted in the material characterization,
data analysis and revised manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

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