Accepted Manuscript

Failure Analysis of Stress Corrosion Cracking in Heat Exchanger Tubes during

Start-up Operation

Shugen Xu, Chong Wang, Weiqiang Wang

PII: S1350-6307(15)00052-7
DOI: http://dx.doi.org/10.1016/j.engfailanal.2015.02.005
Reference: EFA 2505

To appear in: Engineering Failure Analysis

Received Date: 6 November 2014

Revised Date: 29 December 2014
Accepted Date: 12 February 2015

Please cite this article as: Xu, S., Wang, C., Wang, W., Failure Analysis of Stress Corrosion Cracking in Heat
Exchanger Tubes during Start-up Operation, Engineering Failure Analysis (2015), doi: http://dx.doi.org/10.1016/
j.engfailanal.2015.02.005

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 Failure Analysis of Stress Corrosion Cracking in Heat Exchanger
Tubes during Start-up Operation
Shugen Xua*, Chong Wanga, Weiqiang Wangb
a. College of Chemical Engineering, China University of Petroleum (Huadong), Qingdao 266580, China;

b. School of Mechanical Engineering, Shandong University, Jinan 250061, China

* Corresponding author: Shugen Xu.

Tel：+86-531-86983482, E-mail: xsg123 @ 163.com.

Abstract

The cracking failure of a new heat exchanger during first start-up operation has been analyzed. Through the

investigation of the operating history of the equipment, analysis of the chemical compositions of tube material and

corrosion products, metallographic test of specimens with cracks, the cracking mode can be described as the

Stress Corrosion Cracking (SCC) of austenitic stainless steel. This kind of cracking was induced by the chloride in

high temperature steam and tensile stress. The residual tensile stress due to seal expansion has been proved by

numerical calculation. The pre-heating steam which was polluted by the catalyst with chloride is the main reason

for the tube cracking in this case.

Keywords: Stress corrosion cracking, Austenitic stainless steel, Heat exchanger tube, Start-up operation

1 Introduction

Shell-tube heat exchangers are widely used in chemical, petroleum, medicine and nuclear industries. Crack

development in tube and tube sheet region of a stainless steel heat exchanger is a common problem. Such crack is

propagated by stress corrosion cracking or thermal fatigue, or localized corrosion [1]. The local stress levels,

arising from a combination of the applied loading, as well as thermal and residual stresses, contribute to the

failure scenario. The Stress Corrosion Cracking (SCC) of austenitic stainless steels may occur when an alloy is

simultaneously subject to the tensile stress and a specific corrosive fluid [2, 3]. The SCC of austenitic steel in a

certain medium, such as hot chloride and hot alkaline solutions is a common failure mode in the process

industry. Engineers have investigated this kind of SCC in a variety of ways, and lots of prevention solutions have

1
been proposed [4-7]. Many SCC failure cases during long time service in process plants have been introduced in

the history. However, a new stainless steel heat exchanger tubes were also cracking during 8 days start-up

pre-heating operation. It is uncommon and should be analyzed carefully. In this paper, a failure case of heat

exchanger tubes during start-up operation will be discussed. The intention of this paper is not to figure out the

micro mechanism and mode of SCC of austenitic stainless steel, but to show the reason and the characterization of

SCC of a new austenitic steel tube during start-up operation.

2 Descriptions of the failure case

In 2014, a tube-shell heat exchanger E101/E102 for dimethyl ether to propylene project failed due to the leak of

tubes during the first start-up operation. The specification of the heat exchanger E101/E102 is listed in Table 1.

E101 and E102 are assembled in one vessel with the serial tube side, as shown in Fig.1. In the normal production

process, the feed fluid of reactor R101, water and dimethyl ether are heated in shell side of E101. The water and

methanol are heated in shell side of E102. The products of R101, water and propylene are cooled down in tube

side of E101 and E102. In the first star-up operation, R101 and E101/102 are heated by the high temperature

steam from the boiler, as shown in Fig.1.

E101/102 was fabricated in May 1, 2014, and tried to start-up in June 21, 2014. The pre-heating steam flows

through R101 to heat the catalyst bed, and then pre-heats E101/E102 through tube side. The temperature increased

from 30°C to 320°C during 4 days and kept constant in the later 4 days. The leakage of E101/E102 was found in

June 28, 2014. The tube cracks locate in the end of seal expansion section, Zone-I and Zone-II, as shown in Fig.2.

The inner surface of failed tubes was corroded, on which some redish brown corrosion products were observed.

Some circumferential cracks in inner and outer surfaces of tube can be found. Fig.3 shows the appearance of

cracks in Zone-I of Tube-A. No obvious plastic deformation can be found around the fracture zone. Fig.4 shows

the appearance of cracks in Zone-II of Tube-B. The cracks originated in inner surface and propagated to the outer

surface, as shown in Fig.3 (b).

2
 Table 1 The specification of the heat exchanger E101/E102

E101 E102
Designation
Shell side Tube side Shell side Tube side

Water, Water, Water, Water,

Operating fluid
Dimethyl ether Propylene Methanol Propylene

Design pressure/ MPa 0.8 0.35 0.8 0.35

Working pressure/ MPa 0.33 0.13 0.431 0.125

Design temperature/ 450 550 200 420

Working temperature(in/out)/ 155/340 483.5/383 150.7/150.7 383/153

Hydro-test pressure/MPa 1.26 0.66 1.03 0.66

Heat transfer surface/ m2 336.5 918.4

Material of tubes S30409 S30408

Material of shell and head S30408

Material of tube-sheet S30408

Fig.1 The pre-heating steam flow during start-up operation.

3
 Fig.2 The location of cracks, Zone-I and Zone-II.

(a) Outer surface (b) Inner surface

Fig.3 Cracks in Tube-A of E101 (Zone-I)

4
 (a) Outer surface (b) Axial cross-section (polished)
Fig.4 Cracks in Tube-B of E102 (Zone-II)

3 Failure analysis and results

3.1 Chemical composition
According to the manufacture specification, the Tube-A and Tube-B were made of S30409 and S30408. They

are equivalent to TP304H and TP304 stainless steel according to ASME code.

Specimens from the Tube-A and Tube-B were analyzed by spectral analysis for their chemical composition.

The measured results and their standard requirements of tube-A and Tube-B are shown in Table 2 and Table 3,

respectively. According to the specification of the material of tubes which are used, we can find that the

composition of Tube-A and Tube-B meet the requirement of GB/T13296-2007 Boiler, heat exchanger with

stainless steel seamless pipe[8] and GB/T 222-2006 Permissible tolerances for chemical composition of steel

products[9].
Table 2 Chemical composition of tube-A (wt.%)
Element C Si Mn P S Cr Ni
GB13296-2007
0.04~0.1 ≤1.00 ≤2.00 ≤0.035 ≤0.030 18.0~20.0 8.00~11.0
（S30409）

GB/T 222-2006
±0.01 ±0.05 ±0.04 +0.005 +0.005 ±0.20 +0.15/-0.1
Permissible tolerances
Measured 0.038 0.398 1.131 0.0346 0.0033 18.681 7.944

5
 Tabble 3 Chhem
micaal coomppositioon of tuube--B (wt.%)
E
Elem
mentt C Sii M
Mn P S Crr Ni
G
GB1132996-22007
≤
≤0.007 ≤11.000 ≤
≤2.000 ≤
≤0.0035 ≤00.0330 177.00~199.000 8.000~111.00
（S3304409）
G
GB//T 222-220006
±
±0.001 ±00.055 ±
±0.044 +
+0.0005 +0.0005 ±00.200 +0.15//-0.11
P
Perm
misssiblee tolleraancees
M
Meaasured 00.032 0.44866 1.0188 00.03351 0..00775 177.602 8.1170
33.2 M
Miccrosstru
uctu
ure
Inn orrderr to evaaluaate tthe m
matteriaal m
micrrosttructuree, sppecimeens from
mTTube-A
A annd T
Tubee-B weere ppreppareed ffor optiicall

m
metaalloograaphiic teest.

Fiig.55 (a)) sho

owss thhe m m llurggicaal struccturre of Tuubee-B is sshow
micrrostrructturee off Tuube-A. Thee metal wn in F
Fig.5 (bb). T
Thee

m Tubee-A andd Tuubee-B are bassicaally sim

micrrosttruccturees oof T milarr. The
T m miccrosstruccturre cconssistss off ausstenniticc grainss annd a

ffew nonnmeetallic iincllusionss. Thhe aaustteniitic graiin is finne aand som

me of tthem
m shhow
w tw
win bbouundaaries.

Geneerally sspeaakinng, ffor thee Nii-Crr auustenniticc stainllesss steeel, thiss kiind of m
G mal. Acccorddingg too
miccrosstruccturre iss noorm

the origginaal m
mateerial meta
m llurrgical sstructurre pphottos,, wee caan cconfirm
m thhat no obvviouus m
micrrosttruccturee chhannge hass

hhapppened dduriing thee staart-uup ooperratioon. Thee crrackks w

weree noot duue tto thhe ddeteeriorratioon oof m
mateeriaals.

((a) Tubbe-A
A ((b) Tubbe-B
B
F
Fig..5 M
Metaalluurgiccal struuctuure oof T
Tubee-A
A andd Tuubee-B (etcchedd byy aqqua reggia )

33.3 M
Miccro app
peaaran
nce of ccraackss

The tube piiecees w

T withh craackks w
weree cuut frrom
m thee tuube andd prrepaaredd forr thhe m
metaallurrgiccal eexaaminnation. Figg.6 aandd

Fig.77 sh
F how
w thee apppearannce of cracks in the cirrcum
mferrenttial crooss-ssecttionn off Tuube-A aand Tubbe-B
B, rresppectiivelly. T
Thee

ccracck oorigiinatted from

m thhe iinneer suurfaace,, annd thhen greew tthrooughh thhe tuube waall. C
Craackss weere inittiateed fr
from
m diifferrentt

me.. Thhe craccks aree oobviioussly braanchhed,,

ppoinnts, andd hhavee thhe ddiffeerennt llenggthss deepenndinng oon thee initiattionn tim

6
eespeeciaally neaar thhe tiip oof thhe m
mainn crrackk. Thhe ccraccks proopaggateed enntirrely in a traansgrannulaar m
modde.

Accoordiing to tthe craack apppearrancces disscusssedd abbovee, thhe cracckinng rreasson andd m
A mode caan bbe ddescribbed as thee

S
SCC
C off auustenniticc sttainllesss steeel. Thhey all hhavve thhe bbrannchees aand proopaggateed ffrom
m innnerr sidde ttowaard outter sidee off

the ttubees. IIt shhouuld bbe nnoteed thhat thee innner tube suurfaace iis inn coontaact w
withh thhe coorroosivve fl
fluidd duuring opperaatioon. T
Thee

ccracck innitiaatioon eeasilly hhapppenns inn a struuctuure undder the tennsilee state of streess. Thhe foolloowinng ssecttionns ddiscuuss thee

ssenssitivve flluidd annd thhe teensile streessees inn thee strructturee thaat innduucedd thee SC
CC..

F
Fig.6 O
Optticall miicroograaph of ccraccks in ttubee-A (etcched byy aqqua reggia)

F
Fig.7 O
Optiicall miicroograaph of ccraccks in ttubee-B (etcchedd byy aqqua reggia)
33.4 C
Corrrossion
n prrod
ductts

Inn orrderr to detterm

minee thhe ccorroosioon pprodductts inn thhe ccraccks, thee ennerggy-specctrum
m sscannninng w
was perrforrmeed. T
Thee

ssam
mple surrfacce w
was exaaminnedd by Scannningg Electrroniic M
Micrrosccopee (S
SEM
M). Figg.8 sshow
ws the apppearrancce oof frractturee

ssurfface. Many
M y coorroosionn prroduuctss caan bbe seeen. Thhe cchem mpossitioons in tthe craack of T
miccal ccom Tubbe-A
A weere exaaminnedd

bby E
Eneergyy D
Dispeersiive Spectrrom
meteer (E
EDS
S), whhichh arre listeed iin T
Tablle 44. T
Thee major mentt is Fee, and thee
m r ellem

7
nonmetallic elements are S, O, and Cl.

Fig.8 Corrosion products at fracture surface.

Table 4 Chemical composition of corrosion products using SEM/EDS (wt.%).

Element C N O Na Si S Cl Ca Cr Mn Fe Ni

Weight 6.21 2.63 18.09 4.86 2.75 11.64 0.36 0.20 10.66 0.98 37.83 3.79

The heat exchanger tube is only slightly corroded, but corrosion products were found in the pipe between R101

and E101. The location of this pipe is shown in Fig.1. The appearance of corrosion products are shown in Fig.9.

The powder was examined by X-Ray Diffraction (XRD), the spectra result is shown in Fig.10. With the technical

analysis, it can be confirmed that the main compound is Fe2O3. 100g power was added to 1L water and the

solution was prepared. Using potentiometric titration method, it can be calculated that the chloride concentration

in the solution is 1292 mg/L. Thus, the weight concentration of chloride in the powder is 1.292%.

The condensate liquid of pre-heating steam from the inlet and outlet of R101 was tested by potentiometric

titration. The result shows the concentration of chloride from outlet is 7000mg/L, while from inlet is 20mg/L. It

means the steam was polluted through R101. Further investigation shows that the catalyst contains a great many

of chloride.

8
 Fig.99 Coorroosioon pprodducts

Figg.100 XR
RD ressult of ccorrrosiion prooduccts

33.5 S
Streess staate iin tu
ubees

menntal invvesttigaationn coonclludeed tthatt thee tuube failled as a reesultt off SC

The expperim
T CC tthatt iniitiatted at tthe tubbe siide..

Thiss cooncllusioon sshouldd be supppoortedd byy thhe teensiile sstress. Thee opperaatingg sttresses inccluddingg ressiduual streessees frrom
T m

ffabrricattionn annd w
welddingg aree coompplicatedd. T weldd annd hheatt efffectt zone hhas beeen sstuddiedd byy
The weeldinng sstresss inn thhe w

X
Xu, et aal [110,111].. Acccorrdinng too thhe loocattionn off craackss, itt cann bee coonclludeed thhat thee ressiduual sstreess ddue to eexppanssionn

fform
mingg iss thee m CC.. Thhereeforre, tthe Finnite eleemeent model is empployyedd to preedicct thhe eexppanssionn
mainn faactorr too SC

fform
mingg strresss in this seectioon.

9
 A 2D axi-symmetric of the pipe welding model was established in ABAQUS10.0, as shown in Fig.11. The

dimension of geometry is shown in Fig.2. The FE meshing of welded joint is shown in Fig. 12. In total, 18423

nodes and 16972 elements were meshed. The element used in the model is an axi-symmetric 4-node reduced

integration element.

The material of tube and tube-sheet is austenitic stainless steel S30409.The welding metal is assumed to have

the same material properties as S30409 steel. For mechanical analysis, mechanical properties of the materials are

incorporated, as listed in Table 5. Elastic strain is modeled using the isotropic Hooke’s law with Young’s modulus

and Poisson’s ratio. For the plastic strain, a plastic model was employed with Von Mises yield surface,

mechanical properties and linear kinematic hardening model. Kinematic hardening was considered because

material points undergo both loading and unloading in the forming process, which has been widely used in the

forming residual stress simulation.

Fig.11 Geometry model

Fig.12 Finite element mesh

10
 During the structural analysis, boundary conditions should be applied to prevent the rigid body motion.

Because of the axi-symmetry of the FE model, the displacement of tube surface is constrained in the

axial-direction.

The expansion tool with the rigid body property is used to expand the tube. The plastic deformation and stress

occurred when the expansion tool removed. The contact status between the tube and tube-sheet hole are modeled

by using surface-to-surface contact pairs. The coefficient of friction between two contact surfaces is assumed to

be 0.2.The residual axial stress and hoop stress contours are shown in Fig.13(a) and Fig.13 (b), respectively. The

peak tensile axial stress in the inner surface is 212.2MPa, and the peak tensile hoop stress is 187.7MPa.

Table 5 Material properties for S30409 steel.

Young’s Modulus Poisson’s Yield strength Ultimate tensile strength Elongation (%) Density
(MPa) ratio (MPa) (MPa) (kg/m3)
199000 0.28 206 610 69 8010

(a) Axial stress (b) Hoop stress

Fig.13 Residual stress contour of tube to tube-sheet

4 Reasons for the tube cracking

From the results of the test of material composition, microstructure, crack appearance, the corrosion product

composition, and the steam quality, the reasons for failure can be described as follows:

The chemical composition and the microstructure indicate that the material of tube is S0409 and S30408, and

the material composition and structure did not deteriorate during start-up operation. The crack appearance shows

11
an obvious SCC characterization of austenitic steel in chloride solution. The sensitive medium of SCC must exist

in the tube side, because the crack originated on the inner surface of tube. The steam quality data give us a

powerful proof that the service environment contains chloride. The peak axial and hoop stress are 212.2 MPa and

187.7 MPa. Therefore, the basic reason for tube failure is the SCC of austenitic steel in hot steam with chloride.

5 Conclusions

From the analysis above, the following conclusions can be drawn: Failure analysis revealed that heat exchanger

tube cracking was caused by SCC. The residual tensile stresses due to seal expansion are the stress reason for the

SCC. The pre-heating steam which was polluted by the catalyst with chloride during start-up operation is the basic

reason for SCC.

Acknowledgment

The authors wish to express their gratitude for the financial support by National Natural Science Foundation of

China (Grant No.51404284).

References

[1] Azevedo CRF, Beneduce Neto F, Brandi SD, Tschiptschin AP. Cracking of 2.25Cr-1.0Mo steel tube/stationary

tube-sheet weldment of a heat-exchanger. Eng Fail Anal 2008; 15(6):695-710.

[2] Chahardehi A, Brennan F P, Steuwer A. The effect of residual stresses arising from laser shock peening on fatigue crack

growth. Eng Fract Mech 2010; 77(11): 2033-2039.

[3] Mochizuki M. Control of welding residual stress for ensuring integrity against fatigue and stress-corrosion cracking.

Nucl Eng Des 2007; 237(2): 107-123.

[4] C. Garcia, F. Martin, P. De Tiedra, et al. Effects of prior cold work and sensitization heat treatment on chloride stress

corrosion cracking in type 304 stainless steels. Corrosion science 2001; 43:1519-1539.

[5] Jongmin Lee, Shinho Han, Kyoungmun Kim, Heongkee Kim, Ungi Lee. Failure analysis of carbon steel pipes used for

underground condensate pipeline in the power station. Eng Fail Anal 2013; 34: 300-307.

[6] Bilal Saleem, Furqan Ahmed, Muhammad Asif Rafiq, Mohammad Ajmal, Liaqat Ali. Stress corrosion failure of an X52

grade gas pipeline. Eng Fail Anal 2014; 46: 157-165.

[7] Sui Rongjuan, Wang Weiqiang, Liu Yan, Li Dong, Li Wei, Root cause analysis of stress corrosion at tube-to-tubesheet

joints of a waste heat boiler. Eng Fail Anal 2014; 45: 398-405.

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[8] The standard of People’s Republic of China. GB/T13296-2007 Boiler, heat exchanger with stainless steel

seamless pipe. [in Chinese]

[9] The standard of People’s Republic of China. GB/T 222-2006 Permissible tolerances for chemical composition of

steel products. [in Chinese]

[10] Xu Shugen, Wang Weiqiang. Numerical investigation on weld residual stresses in tube to tube sheet joint of a heat

exchanger. Int J Press Ves Pip 2013; 101: 37-44.

[11] Xu Shugen, Zhao Yanling. Using FEM to determine the thermo-mechanical stress in tube to tube-sheet joint for the SCC

failure analysis. Eng Failure Anal 2013; 34: 24-34.

13
Highlights:

Failure analysis revealed that heat exchanger tube cracking was caused by SCC.

Residual tensile stresses due to seal expansion are the stress reason for SCC.

Steam polluted by chloride during start-up operation is the media reason for SCC.

14