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Engineering Failure Analysis 12 (2005) 623633

www.elsevier.com/locate/engfailanal

Cracks and precipitate phases in 321 stainless steel weld of

ue gas pipe
a,*
K.S. Guan , X.D. Xu b, Y.Y. Zhang b, Z.W. Wang a

a
Research Institute of Process Equipment, East China University of Science and Technology, Shanghai, 200237, PR China
b
Jinan branch, China petrochemical corporation, Jinan 250061, PR China

Received 14 April 2004; accepted 8 May 2004

Abstract

The present work studies the AISI304 weld cracking mechanism of AISI321 austenite stainless steel of ue gas pipe,
which served up to 60,000 h at 650700
C. The performance and microstructure of failed material were characterized
by impact test, optical microscopy, scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy
(EDS), X-ray diraction (XRD). The results show that cracks ware caused by embrittlement of weld metal and thermal
stress. Needle like r-phase precipitation during service is primarily responsible for signicant degradation in mechanical
properties and microstructures of weld metal. Needle type r-phase is a severe stress-raiser and plays a role as crack
initiator at the interface with matrix. In addition, maximum equivalent stress is about 175 MPa in the elbow which
is near to the yield stress of the steel. It is highly possible that a crack will be initiated under above stress condition
and will propagate faster along embrittled r-phase. Several approaches should be employed to control r-phase precip-
itation in weld. These approaches include: decreasing content of ferrite and M23C6 carbide in weld and selecting Nb
added weld wire during welding.
 2004 Published by Elsevier Ltd.

Keywords: Austenite stainless steels; Precipitates; Sigma-phase; Cracks; Welds

1. Introduction

Austenitic stainless steels with the approximate composition 18% chromium, 10% nickel and additions
of molybdenum, titanium or niobium are today widely used in components designed for high temperature
applications like boilers, superheaters and chemical reactors. Additions of titanium or niobium prevent

*
Corresponding author. Tel.: +86 21 6425 3055; fax: +86 21 6425 3810.
E-mail address: guankasishu@ecust.edu.cn (K.S. Guan).

1350-6307/$ - see front matter  2004 Published by Elsevier Ltd.

doi:10.1016/j.engfailanal.2004.05.008

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624 K.S. Guan et al. / Engineering Failure Analysis 12 (2005) 623633

Table 1
Material specication and design parameters of the reformer tubes
Element C Mn Si S P Cr Ni Ti Fe
Base metal 0.06 1.24 0.74 0.010 0.023 17.72 9.86 0.35 Balance
Weldment 0.07 1.85 0.43 0.006 0.025 20.70 9.91 <0.01 Balance

precipitation of grain boundary carbides and contribute to precipitation hardening by the formation of
MX-type carbides. The contents of chromium improve the corrosion resistance of the material, but also
make the austenite unstable with respect to formation of chromium-rich carbides and intermetallic phases
due to prolonged exposure to high temperature. Formation of an intermetallic phase known as r-phase is a
severe problem when using standard austenitic stainless steels at elevated temperatures. The presence of r-
phase not only results in harmful inuence on the mechanical properties of the material , but also reduces
its corrosion resistance by removing chromium and molybdenum from the austenitic matrix [15]. It is well
known that morphology, size and distribution of precipitates give rise to dierent eects on the mechanical
behaviour of austenitic stainless steels [6,7]. So it is necessary to understand the metallurgical process taking
place in the material under elevated temperature for better safety and economy.
The present work studies the AISI304 weld failure mechanism of AISI321 austenite stainless steel ue
gas pipe which served up to 60,000 h at 650700
C. The ue gas pipe is a component of recovery system
of catalytic cracking unit of petrochemical plant. The recovery reaction of catalyst particles takes place in
the recovery reactor whose high temperature ue gas ows through the pipe to be reused. The ue gas pipe
is vertically installed. The material was originally obtained as 8 mm thick commercial plate product of
AISI321, made by rolling and welding using AISI304 weld wire. Outer diameter is 1316 mm. The design
temperature of the pipe is 700
C. the outside of the pipe is covered with a layer of mineral wool to maintain
temperature. Outer surface of the pipe is maintained between 650 and 700
C during service. The material
specication is given in Table 1 (see Fig. 1).
The gas owing through the pipe was mainly COx, vapour, and catalyst particles, with 200 ppm NOx
and 1100 ppm SOx, at a pressure of 0.3 MPa. The dew point of acid medium of the ue gas is 138
C. After
60,000 h of service, many cracks are detected on the weldment of the pipe near elbow. The cracks are lon-
gitudinal and vertical in the circumferential weldment. Some cracks have penetrated across the wall. Fig. 2
shows an actual photograph of an as-received sample. This work is aimed at evaluating the mechanical
properties, and investigating the causes of failure. The performance and microstructure of failed material
are characterized by impact test, tensile test, optical microscopy, scanning electron microscopy (SEM)
equipped with energy dispersive spectroscopy (EDS), X-ray diraction (XRD).

Fig. 1. Schematic diagram of ue gas pipe.

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K.S. Guan et al. / Engineering Failure Analysis 12 (2005) 623633 625

Fig. 2. Photograph of as-received sample, cracks on inner surface.

2. Visual examination

Both inner and outer surfaces of the failed tubes are examined. The penetrated cracks are longer in
inner surface than that in outer surface. Some cracks are observed only on inner surface which have
not yet propagated to outside. That is to say, the cracks originate from inner surface and propagate
to outer surface. There is no indication of any localized damage in the form of pits. No wall thinning
and plastic deformation is observed near the cracks which reveals that the failure is brittle fracture in
nature.

3. Experimental and results

3.1. Tensile strength and impact energy

Tensile tests at room temperature (25
C), Charpy impact test at both room temperature and 700
C
of the service exposed pipe are performed. Standard specimens are made from the service exposed
materials as per ASTM E8-79 specication. Samples are fabricated from the longitudinal direction of
the tube. Tensile test is carried out only on the base metal, and impact test is carried out both on base
and on weld metal, from the longitudinal direction of the service tube. The average value is taken after
three specimens per condition were tested. The fracture surfaces through the impact tested specimens
are examined by scanning electron microscopy in order to identify the fracture characterizations. The
values of the yield strength (0.2% proof stress) and ultimate tensile strength (UTS) and impact energy
with temperature of testing are shown in Tables 2 and 3. The tests show that the tensile strength is
increased compared with normal AISI 321 steel, but ductility and toughness are lower than normal
AISI 321 steel. The data given in Tables 2 and 3 shows a rather brittle fracture.

Table 2
Tensile strength of the service exposed pipe
r0.2 (MPa) rb (MPa) d5 (%) W (%) Temperature (
C)
Test result 281.79 652.63 34.3 24.27 25
ASTM standard P20 P520 P40 25
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626 K.S. Guan et al. / Engineering Failure Analysis 12 (2005) 623633

Table 3
Sharpy impact energy of the service exposed pipe (size of specimens 5 mm 10 mm 55 mm)
Temperature (
C) Akv (J)
Base metal 25 16
Weld metal 25 9
Base metal 700 31
Weld metal 700 15

3.2. Microstructure

Optical metallographic samples of cross-sections are prepared from the failed weld. Microstructures ob-
served near inner surface and outer surface in the failed zone are shown in Fig. 3. No grain boundaries are
found in the weld, but large amounts of second-phase precipitation are observed. The precipitated phase is
needle-like and coarse. The amount of precipitated phase near inner surface is not as much as in outer
surface.
Fig. 4 shows microstructures of base metal near the failed weld, which is not single austenitic grains ex-
pected from this grade of steel under normalized condition. Precipitation of phases in grain boundaries is
obvious and some particles inside the austenitic grains are also found. The morphology of precipitates is
blocky. Near inner surface, the blocky precipitates had agglomerated. Size of the precipitates varied be-
tween 10 and 20 lm.
Fig. 5 shows the micro-morphology of cracks at weld zone. Cracks are intergranular following the sen-
sitized grain boundaries on HAZ zone, but the main crack is transgranular as illustrated in Fig. 5(b). Since
the precipitates occur not only along grain boundaries but also inside grains, the cracks, which propagate
along with these precipitates, are intergranular and transgranular.

3.3. SEM of fracture surface

Fig. 6 shows the micromorphology of original fracture surface on weld. The fracture surface is covered
by large amount of precipitates and oxides. However, the cracks propagate alone with brittle precipitates.

Fig. 3. Microstructures of cross-section of failed weld: (a) near inner surface in weld, 200; (b) near outer surface in weld, 200.
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K.S. Guan et al. / Engineering Failure Analysis 12 (2005) 623633 627

Fig. 4. Microstructures of cross-section of base metal near inner surface.

Fig. 5. optical micrograph of crack tips: (a) cracks on molten zone; (b) extensive intergranular and transgranular cracks on HAZ.

Results of SEM fractography study of specimens after the impact tests (at room temperature and 700
C)
are given in Figs. 7 and 8.
Large amounts of precipitates are present. The fractography showed, in general, brittle fracture in the
impact-fractured specimens. The fracture is along precipitates, is rather brittle and presents many second-
ary cracks on fracture surface. However, ductile fracture at periphery of these precipitates is present. Since
matrix metal around these precipitates possesses good ductility and toughness, when the fracture takes
place along these precipitates, the surrounding metal matrix presents overloaded ductile fracture. So the
fractography looks like dimple fracture.
Impact specimen at 700
C in Figs. 7(b) and 8(b) presents the same fracture characteristics with that in
Figs. 7(a) and 8(a), respectively. However, the size of precipitates is smaller than the ones observed on the
specimen impact tested at room temperature. Since the metal should posses similar size of precipitates in all
the specimens, this is due to higher ductility of matrix metal around the precipitates at 700
C than at room
temperature, the matrix undergoing higher strain before fracture. Precipitates are wrapped partly by elon-
gated matrix and look smaller in size.
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628 K.S. Guan et al. / Engineering Failure Analysis 12 (2005) 623633

Fig. 6. SEM of fractography, fracture along precipitates 2000.

Fig. 7. SEM surface of impact specimen for weld joint impact specimen: (a) at room temperature, 2000; (b) impact specimen at 700

C, 2000.

3.4. Precipitates

It is important to know what kind of phases have precipitated during service at about 700
C. Table 4 is
chemical composition of precipitates using SEM/EDS for weld and base metal. From the ratio of [Fe]/[Cr],
we can deduce that the precipitates are probably r phase. The chemical composition of r can vary in a
relatively large range. In Fe base alloy, r is rich in Fe. The chemical composition of r-phase given in Table
4 is near to the results of Minami [1] and Kallqvist [7].
In order to further identify the structure of precipitates, XRD is used to characterize the structure of the
phases. XRD pattern obtained from the bulk metal matrix is shown in Fig. 9. The XRD measurement
shows intense peaks at 43.58
, 50.8
, and 74.7
assigned to structure of austenite. Another peak appears
at about 45
which represent CrFe compound belonging to r-phase. According to above analysis, the pre-
cipitates both of the needle type in weld and blocky type in base metal are mainly r-phase.
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K.S. Guan et al. / Engineering Failure Analysis 12 (2005) 623633 629

Fig. 8. SEM surface of impact specimen for served base metal: (a) impact specimen at room temperature, 1000; (b) impact specimen
at 700
C, 2000.

Table 4
Chemical composition of precipitates using SEM/EDS on weld and base metal (wt%)
Distribution Cr Ni Fe Ti Si Mn O
Weldment 38.59 2.95 56.39 0.38 0.71 0.98
Base metal 25.52 5.77 50.67 0.52 2.78 14.5

Fig. 9. XRD pattern of bulk metal.

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630 K.S. Guan et al. / Engineering Failure Analysis 12 (2005) 623633

4. Discussion

The following results can be obtained from the experiments: large amount of needle like r-phase
present in weld, blocky type r-phase in base metal. The ductility and toughness have signicantly
reduced in the material, especially in weld. The cracks that have been observed in the weld metal in
the present case could be due to the following reasons: (1) embrittlement of material caused by r-phase
precipitation (r-phase may originate from transformation of d-ferrite, and/or austenite and/or carbides,
the d-ferrite could be formed during welding); (2) excessive stress in the weld caused by pipe structure
and thermal expansion.

4.1. Eect of number and morphology of precipitates

The precipitation reactions are considered to be of primary importance in controlling the mechanical
properties of the weld metals, and can result in signicant reduction in weld metal ductility and toughness.
Much of the deterioration in properties can be directly attributed to the formation of secondary phases such
as M23C6 and the intermetallic r- and v-phases [7,8]. r-Phase is a common precipitate in austenitic steel
which is hard and brittle intermetallic phase of normal composition FeCr. The crystal structure has a
tetragonal unit cell (space group P42/mnm), containing 30 atoms per unit cell with lattic parameters
a = 0.88 nm and c = 0.4544 nm [9].
Morphology of precipitates can have important eect on the mechanical behaviour [6]. Especially, needle
like precipitates are more likely to reduce the ductility and toughness [10]. The r-phase is needle like in weld
and blocky type in base metal. r-Phase of needle type is more severe stress-raiser than blocky type, in addi-
tion, the precipitation is smaller in base metal than in weld, the reduction of ductility and toughness in base
metal is not as much as in weld. So the cracks take place only in weld.

4.2. Origin of stress

r-Phase precipitation is related to service temperature and independent of stress. Even with the embrit-
tlement of the weld metal, the cracks cannot take place without stress. So it is necessary to analyze the ac-
tion of stress. Three types of stresses, mainly presented in the pipe are: (1) thermal stresses due to thermal
expansion, (2) mechanical stress due to the internal pressure, and (3) welding residual stress. Generally, the
stress generated due to pressure of 0.3 MPa is very small and can be neglected. Welding residual stress is
present after welding, especially in elbow of the pipe where thermal expansion is inhibited. However, after
long agin at about 700
C, the stress should be released. So welding residual stress can be also ruled out.
Then, the main contribution to the stress is thermal expansion of the pipe. Finite element method (FEM) is
introduced to calculate the thermal stress. It is found that the maximum equivalent stress is of order 175
MPa in elbow which is near to the yield stress of the steel.

4.3. Precipitate phases and sequence

Precipitation in austenitic stainless steel has been widely studied in the literatures. For AISI 300 series
austenitic SS with or without Nb/Ti addition, precipitation of M23C6 and r can take place during heat
treatments in the temperature range from 650 to 850
C [1113]. However, carbide and r-phase, especially
Ti or Nb stabilized austenitic steel, which is a preferential precipitation, is not well understood.
This failure case is AISI 304 austenitic weld without Ti or Nb addition. Detected Ti content in weld,
which came from diusion of base metal, is very little and can be neglected. Base metal is Ti stabilized AISI
321 austenitic steel. Since cracks take place only in weld, following discussion about the precipitates mainly
relates to the austenitic steel without Ti addition. In this failure case, precipitate at weld is r-phase, which
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K.S. Guan et al. / Engineering Failure Analysis 12 (2005) 623633 631

can be derived in three ways: (1) transformation of austenite, (2) transformation of d-ferrite, (3) transfor-
mation of carbide M23C6.
(1) Eect of austenite. In fully austenitic weld metal r-precipitation may start at austeniteaustenite
grain boundaries [14]. We do not think r-precipitated directly from austenite in this case. Precipitates
are signicantly lower in base than in weld. If r-precipitates directly from austenite, base metal should have
same amount of precipitates because base metal has almost the same chemical composition as weld, except
for Ti content. Moreover, Ti promotes r-phase precipitation.
(2) Eect of d-ferrite. Fully austenitic steel is liable to hot cracking which occurs during weld meal solid-
ication. This cracking takes place due to segregation of impurity elements such as S, P and other elements
leading to low melting point phases. It is well known that the d-ferrite in HAZ or weld in austenitic steel
benets resistance to hot cracking. A certain amount of d-ferrite (58%) will scavenge the impurities and
take care of a certain amount of thermal strain [4].
If service involves exposure at temperatures in the range 550850
C, rapid transformation of the
ferrite to the embrittling r-phase occurs, because d-ferrite is not in a state of equilibrium at these
temperatures [13,15]. Carbide precipitation takes place at the austeniteferrite grain boundaries. After
carbon has been used up, the remaining d-ferrite changes into r-phase, if its alloying element content
is high enough [16]. Because d-ferrites are enriched in bcc stabilizing elements, notably Cr and Mo, the
reaction to intermetallic phases, takes place more rapidly. The d-ferrite converts to r-phase and alloy
carbides by two step eutectoid reaction. The rst step leads to the formation of austenite and a Cr-rich
carbide (M23C6) by a lamellar eutectoid reaction. r-Phase forms as a result of a second eutectoid reac-
tion [17].
Generally, this failed weld should contain certain amount of ferrite. The constitution of austenitic steels
after thermal aging may also be predicted from the relevant isothermal sections of the FeCrNi equilib-
rium diagram. Fig. 10 shows that the compositions of the various austenitic steels, fall within the two-phase
(c + r) eld at 650
C [13].

Fig. 10. Part of isothermal section of FeCrNi equilibrium diagram at 650
C.
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632 K.S. Guan et al. / Engineering Failure Analysis 12 (2005) 623633

Fig. 11. As welded joint of AISI 321 steel with 304 wire, 500.

(3) Eect of carbide M23C6. It is well known that carbide precipitation occurs in HAZ during welding.
Generally, carbide precipitation is easy because this only requires carbon diusion to the sites with highest
concentration of strong carbide formers like Cr, Mo, etc. [16]. However, in this case, no carbides are ob-
served in HAZ. Can the carbide transform to r-phase during long term heating at 650 to 700
C? Gener-
ally, the precipitation of r upon heat treatment in the temperature range from 650 to 850
C can be strongly
accelerated by the pre-existence of carbides in the steel, particularly those of the Cr23C6and Cr7C3 type
[18,19]. So we deduce that M23C6 is formed immediately after welding, then these carbides transform to
r-phase after long-term service at elevated temperatures. In order to verify this, we carried out a weld joint
using the same materials and welding procedures. That is the base metal is AISI 321 steel and weld wire is
AISI 304 steel. The metallography of precipitates of weld joint is shown in Fig. 11. EDS analysis shows that
the precipitate is blocky type Cr-rich carbide with 88.43%Cr7.52%Fe4.05%Ni.
Based on above analysis, we can deduce the following precipitation sequence. During welding, d-ferrite
and large amount of carbide M23C6 is formed. While in service at about 700
C, M23C6 and ferrite trans-
formed to r-phase. So a large quantity of r-phase is obtained in the weld metal. Base metal has no original
ferrite and M23C6, so the precipitates are few compared with weld. So we can reduce the weld precipitates
by decreasing content of ferrite and M23C6 carbide in the weld. For the former, selecting proper chemical
composition of weld wire can eliminate ferrite. However, this gives rise to the danger of hot cracking during
welding. This can be avoided by proper welding procedures. For the latter, adding Nb to weld wire. In this
case, r-phase is converted directly or indirectly from the ferrite and carbide, so Nb present in weld can de-
crease carbide which can equally decrease r-phase.

5. Conclusions

The failure of the pipe weld is caused by embrittlement of weld metal and thermal stress. Needle like r-
phase precipitation during service is primarily responsible for signicant degradation in mechanical prop-
erties and microstructures of AISI 321 base and AISI304 weld austenitic steel. Needle type r-phase is severe
stress-raiser and plays a role as crack initiator at the interface with matrix. In addition, maximum equiv-
alent stress is of order 175 MPa in elbow which is near to the yield stress of the steel. It is highly possible
that a crack will be initiated under above stress condition and will propagate faster along embrittled r-
phase. Several approaches should be employed to control r-phase precipitation in weld. These approaches
include: decreasing content of ferrite and M23C6 carbide in weld and adding Nb to weld wire.
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K.S. Guan et al. / Engineering Failure Analysis 12 (2005) 623633 633

References

[1] Minami Y, Kimura H, Tanimura M. Creep rupture properties of 18 Pct Cr-8 Pct Ni-TI-Nb and type 347H austenitic stainless
steels. Journal of Materials for Energy Systems 1985;7(l):4554.
[2] Sritharan T, Jones H. Creep of austenitic stainless steels at low stresses. Mechanical behaviour and nuclear applications of
stainless steel at elevated temperatures. London: The Metals Society; 1982. p. 99105.
[3] Schwind M, Kallqvist J, Nilsson JO et al. r-phase precipitation in stabilized austenitic stainless steels. Acta mater
2000;48:247381.
[4] Ghosh S, Chowdhury SG, Mukhopadhyay NK, Das G, Das SK, Bhattacharya DK. Failure analysis of a weld repaired steam
turbine casing. Eng Failure Anal 1998;5(3):20518.
[5] Mudali UK, Dayal RK, Gnanamoorthy JB, Rodriguez P. Relationship between pitting and intergranular corrosion of nitrogen-
bearing austenitic stainless steels. ISIJ International 1996;36:799806.
[6] Balikci E, Mirshams RA, Raman A. Fracture behavior of superalloy IN738LC with various precipitate microstructures. Mater
Sci Eng 1999;A265:5062.
[7] Smith JJ, Farrar RA. Inuence of microstructure and composition on mechanical properties of some A1S1 300 series weld metals.
Int Mater Rev 1993;38(1):2551.
[8] Wasnik DN, Dey GK, Kain V, Samajdar I. Precipitation stages in a 316L austenitic stainless steel. Scripta Mater
2003;49(2):13541.
[9] Kallqvist J, Andren HO. Microanalysis of a stabilized austenitic stainless steel after long term ageing. Mater Sci Eng
1999;A270:2732.
[10] Thomas RG, Keown SR. Stress relief of austenitic weldments:microstructural and mechanical property eects. Mechanical
behaviour and nuclear applications of stainless steel at elevated temperatures. London: The Metals Society; 1982. p. 308.
[11] Ayer R, Klein CF, Marzinsky CN. Instabilities in stabilized austenitic stainless steels. Metall Trans A 1992;23(9):245567.
[12] Schweinsberg DP, Sun B, Otieno-Alego V. Corrosion and inhibition of aged 347 grade stainless steel boiler tubes. Journal of
Applied Electrochemistry 1994;24(8):8037.
[13] Harries DR. Physical metallurgy of FeCrNi austenitic steels. Mechanical behaviour and nuclear applications of stainless steel at
elevated temperatures. In: Proceedings of the international conference. London: The metals society; 1982. p. 115.
[14] Borst K, Pohl M. Precipitation eects in austenitic stainless weld metals. Steel Res 1990;61(6):25861.
[15] Okabayashi H. Mathematical approach to r-phase precipitation in austenitic stainless steel welds. Mater Trans JIM
1996;37(5):9704.
[16] Grover HK, Wickens A. Eect of minor elements on long term creep rupture properties of 316 austenitic stainless steel. In:
Proceedings of the international conference. London: The metals society; 1982. p. 817.
[17] Tseng CC, Shen Y, Thompson SW, Mataya MC, Krauss G. Fracture and the formation of r-phase, M23C6, and austenite from d-
ferrite in an AISI 304L stainless steel. Metall Mater Trans A 1994;25(6):1147.
[18] Garin JL, Mannheim RL. r-Phase formation upon solidication rate in heat-resistant steels. Mater Sci Forum 2003;426
432(2):13016.
[19] Chen TH, Yang JR. Eects of solution treatment and continuous cooling on r-phase precipitation in a 2205 duplex stainless steel.
Mater Sci Eng A 2001;311(l2):2841.