Accepted Manuscript

Stress Corrosion Cracking of Stainless Steel Pipes for Methyl-Methacrylate

Process Plants

Gimo Yang, Kee Bong Yoon, Young Chul Moon

PII: S1350-6307(12)00236-1
DOI: http://dx.doi.org/10.1016/j.engfailanal.2012.10.018
Reference: EFA 1863

To appear in: Engineering Failure Analysis

Received Date: 9 September 2012

Revised Date: 27 October 2012
Accepted Date: 28 October 2012

Please cite this article as: Yang, G., Yoon, K.B., Moon, Y.C., Stress Corrosion Cracking of Stainless Steel Pipes
for Methyl-Methacrylate Process Plants, Engineering Failure Analysis (2012), doi: http://dx.doi.org/10.1016/
j.engfailanal.2012.10.018

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
STRESS CORROSION CRACKING OF STAINLESS
STEEL PIPES FOR METHYL-METHACRYLATE
PROCESS PLANTS

Gimo Yang 1, Kee Bong Yoon2* and Young Chul Moon3

1,3 2
Graduate Students and Professor Respectively, Department of
Mechanical Engineering, Chung Ang University
84 Huksuk-ro, Dongjak, Seoul 156-756, Korea
1
Currently at EXCELAB Inc., Daejeon, Korea

* Corresponding Author:
(Tel) +82-2-820-5328
(Mobile) +82-10-3267-5327
(Fax) +82-2-812-6474
(E-Mail) kbyoon@cau.ac.kr

September, 2012

Manuscript for Submission to Engineering Failure Analysis

1
 ABSTRACT

In a Methyl Methacrylate (MMA) plant, tree-like transgranular cracks were found near the

weld of a pipe that had been used for transferring MMA material at 60℃ and 1.9 kg/cm2.

The pipe was made of ASTM A312 TP304 stainless steel.

In this study, it was shown that the failure was due to the stress corrosion cracking (SCC)
caused by the chloride that remained in the pipe. Corrosion pitting occurred on the inside
surface of the pipe. The stress corrosion cracking started from the pits and grew out through
the thickness. Concentrated chloride was found in the deposit stuck to the pipe in addition to
the pre-process MMA materials. Many work-hardened grains were observed in the area of
SCC, providing the evidence of high residual stress due to welding, which could serve as the
driving force for the SCC. Recommendations are made for preventing further failure due to
SCC in such cases.

Keywords: Stress Corrosion Cracking, Methyl Methacrylate, Failure Analysis, Pipe,

Chloride, Pitting, Weld

2
1. Introduction

Failure analysis has revealed that very often a crack was located near welds in the
components of a process plant. In order to identify the cause of failure, examination of the
fracture surface, inspection of the microstructure near the crack, measurement of mechanical
properties and chemical analysis are usually employed [1].
Various kinds of stainless steel are widely used in process plants due to their high resistance
to corrosion, good weldability and superior material properties at high temperature. However,
the austenitic stainless steel that is mainly used for petrochemical pipes is vulnerable to stress
corrosion cracking [2], which is a major concern in many process plants [3-7].
In this study, cracking failure of a welded stainless steel pipe was investigated. The failed
pipe had been used for Methyl Methacrylate (MMA) for several months before cracking
occurred. Suggestions for preventing similar failures are made based on the findings obtained
from the failure analysis.

2. Experimental Procedures

2.1 Cracked Specimen

A Methyl Methacrylate (MMA) process plant was shut down after four months operation
due to cracking of a pipe above a column. Field replications were taken at five locations
inside of the pipe near the flanges. Cracks were observed at four locations as shown in Fig. 1.
A pipe section was taken out and brought to the laboratory for failure analysis.
Figure 2 shows a picture of the cracked pipe and a drawing showing the location of the
crack. This figure indicates that the cracking occurred near the welded part above the column
for transferring the pre-process MMA material. The pipe was made of ASTM A312 TP304

stainless steel. The design temperature and pressure were 150℃ and 1.9 kg/cm2, respectively.

This MMA transferring pipe failed unexpectedly after only four months of operation. The

actual operating temperature and pressure before the failure were 110℃ and 0.77 kg/cm2

3
respectively, which were lower than the design conditions. The section of the cracked pipe
taken out for failure analysis was delivered to the laboratory as shown in Fig. 3.

2.2 Experiments
Figure 3(a) shows the received cracked pipe. It was broken easily by applying a small
bending force by hands, which means that many cracks already existed and penetrated
through the thickness. Figure 3(b) shows a black deposit on the inside surface of the pipe. A
metallography specimen was taken at location (c) as shown in Fig. 3(c), which shows the
main crack tip region of the failed pipe.
Careful visual inspection was conducted for the received pipe specimen. Metallographic
examination near the crack tip was conducted to investigate how the crack propagated. In
order to observe the location of the primary crack and the welding region, the pipe was cut
along the line A-A shown in Fig. 4. Electrolytic etching with Oxalic acid was applied with 1
A of current for 50 seconds on the cross cut area to distinguish the welded part from the
parent metal. Fractography of the fracture surface was also conducted. The deposit found
inside of the pipe was chemically analyzed. Energy Dispersive Spectrometer analysis (EDS)
and wet chemical analysis were employed for verifying and identifying the corrosion-
inducing chemicals.

3. Results and Discussion

3.1 Cracking
Figure 4 shows outside and inside surfaces of the crack tip area of the specimen taken from
the failed specimen of Fig. 3(c). The crack was formed in the circumferential direction
parallel to the weld. It was several millimeters away from the weld as shown in Fig. 4(a). The
main crack was visually observable since the crack surfaces were separate with each other.
However, many other secondary cracks were only observable with a microscope. On the
inside surface of the specimen, pit-type corrosion was observed and deposits were found
stuck to the surface as shown in Fig. 4(b). The secondary cracks were revealed by wet-

4
grinding of the primary crack tip region as shown in Fig. 5. The primary crack was generated
in the parent metal and grew in a serrated pattern. It is inferred that the secondary cracks were
formed parallel to each other at a specific angle to the primary crack before the primary crack
was formed. Then, the primary crack was formed and grew, combining secondary cracks and
jumping to the other neighboring secondary cracks consecutively. It can be argued that the
directions of the secondary cracks are perpendicular to locally dominating stress such as the
residual stress that remained after welding. The direction of the primary cracks is
perpendicular to the far field stress which is the system stress caused by bending of the pipe.
The primary cracking of the pipe occurred at the location of the maximum bending moment
due to the weight of the vertical pipe above the column as shown in Fig. 2(b).
The cross sectional region along the cutting plane A-A is shown in Fig. 6. The primary
cracks started at the inside surface in the region 5 mm away from the welded area. In this
region, intergranular sensitization was clearly observed by metallography. It can be argued
that the cracks occurred in the heat affected zone (HAZ) that extended up to 5 mm from the
weld fusion line for stainless steel welding. It was reported that intergranular sensitization
causes the material to exhibit formation of grain boundary Cr-carbides [2]. However, this was
not the cause of the failure, since trans-granular cracking rather than inter-granular cracking
was observed.

3.2 Metallography
Metallographic inspection was conducted at three locations indicated in Fig. 6: (a) the
welding fusion line, (b) the heat affected zone where two primary cracks were formed and (c)
the parent metal region far from the weld and primary cracks. The results are shown in Fig. 7.
In Fig. 7(a), the grain size of the parent metal near the welding fusion line is larger than that
of the grains observed at the other two locations (b) and (c). Grain coarsening must have
occurred because of the heat input during the welding. A typical austenitic stainless steel
microstructure is shown in Fig. 7(c) at a location far from the cracks. The grains in Fig. 7(c)
were smaller than those shown in Fig. 7(a).
A microstructure with heavily etched grain boundaries was observed in the grain structure
between the primary cracks as shown in Fig. 7(b). A probable reason for this microstructural

5
appearance is the sensitization of the grain boundary due to heating during the welding or
environmental factors such as chemical components that originated from the internal fluid of
the pipe.
The cross-sectional microstructure along the B-B line indicated in Fig. 4 is shown in Fig. 8.
No evidence of corrosion pitting was found on the outside surface of the pipe as shown in Fig.
8(a). On the other hand, corrosion pits were observed on the inside surface of the pipe. The
stress corrosion cracking started from these pits as shown in Fig. 8(b). The direction of the
crack growth was from the inside to the outside of the pipe which can be recognized in Fig. 6.
Figure 9 shows a magnified crack propagation pattern, indicating a transgranular crack
showing tree-branch patterns. This shape of the crack confirmed that the failure mechanism
was stress corrosion cracking.
Work-hardened microstructures were observed at many grains around the cracks as shown
in Fig. 9(b). These were not observed at any other locations far from the cracks or near the
welding where the grain coarsening occurred. Therefore, it was inferred that work-hardened
grains appeared due to the residual stress caused by welding [8]. Hence, the existence of
these work-hardened grains meant that considerable residual stress was present. This residual
stress must be a driving force for the stress corrosion cracking of the pipe. The fracture
surface of the pipe crack is shown in Fig. 10, revealing a typical transgranular brittle fracture
surface.

3.3 Chemical Analysis

The deposit taken from the inside surface of the failed pipe was analyzed using an Energy
Dispersive Spectrometer (EDS) and the results are shown in Fig. 11. It was confirmed that
the deposit contained chloride which is one of the well-known components causing pitting
corrosion and stress corrosion cracking in stainless steels. In order to measure the amount of
chloride in the deposit and determine the original source of the chloride, quantitative
measurement of chloride using ion chromatography was conducted with the deposit and with
the MMA pre-process material. The results showed that the concentration of the chloride in
the deposit was 23,400 ppm which is a very high concentration. The chloride was also found
in the MMA material at a concentration of 229 ppm. It was reported that a small amount of

6
chloride less than 10 ppm can cause stress corrosion cracking in austenitic stainless steel at

operating temperatures of over 60℃ [9]. The operating temperature of the cracked pipe was

around 110℃ and the chloride concentration was far over 200 ppm, indicating sufficient

conditions for stress corrosion cracking of the pipe.

3.4 Cause of Failure

In general, stress corrosion cracking (SCC) occurs when the following three conditions are
met: i) susceptible material, ii) tensile residual stress and iii) corrosive environment which
includes corrosion inducing ion and electrolyte materials such as water [2,4].
The material involved in the current failure analysis is A312 TP304 stainless steel which is
known to be susceptible to SCC in chloride environments. The work-hardened microstructure
observed around the major cracks was evidence of residual stress that remained after welding.
Also the failed pipe had moisture inside during the processing. The chloride was found in the
deposit on the inside surface of the failed pipe. Hence, all three necessary conditions for the
SCC were met.
Pitting corrosion occurred as a result of chloride ions in the deposit attached to the inside
surface of the pipe. Cracks initiated from the pits and grew driven by chloride ions and
residual stress from welding. Eventually, the SCC crack grew through the thickness
penetrating the MMA pipe. The chloride was from the pre-process MMA material.

3.5 Preventing Failure

Stress corrosion cracking can be avoided by eliminating the causing factors. The following
solutions are suggested.
Three identical MMA process plants had been operated when the cracking was found. Two
other plants did not suffer the SCC problem. These two plants had received pre-process
MMA materials from a domestic provider, but the third plant that suffered the SCC problem
received MMA material containing chloride from a foreign provider. Hence, elimination of

7
the chloride from the MMA materials is the most effective way of preventing the stress
corrosion cracking.
Reduction of the residual stress near the welding region was also recommended. Heat
treatment is required to remove stress after the fabrication and welding of the pipe. The
effectiveness of the stress-removing treatment can be examined by surface metallography
using the field replication method. The work-hardened grains in the heat affected zone should
be minimized. It was also recommended to use highly corrosion-resistant material for the
pipe, such as duplex steel [10], though it may not be adoptable for economic reasons.
One last but minor recommendation was smoothing the inside surface of the welded area.
Because of the abrupt change of diameter involved with connecting two pipes of different
sizes, deposits accumulated at the step near the welded joint (Fig. 6). The chloride was
absorbed in the deposit and caused pitting corrosion. Hence, by removing the deposit where
the chloride can accumulate, the risk of SCC can be reduced

4. Conclusions

Failure analysis was conducted for a cracked A312 TP304 stainless steel pipe used for
transferring the pre-process Methyl Methacrylate (MMA) material. The design temperature

and pressure of the pipe were 150℃ and 1.9 kg/cm2, respectively.

A crack was located near the weld and showed a tree-like cracking path with transgranular
nature. It was concluded that the failure was due to stress corrosion cracking caused by the
chloride that remained inside the pipe. Corrosion pitting occurred on the inside surface of the
pipe. The stress corrosion cracking started from the corrosion pits and grew throughout the
thickness. Concentrated chloride was found in the deposit of the MMA material attached to
the inside of the pipe.
Many work-hardened grains were observed in the area where the stress corrosion cracking
occurred. This is evidence that the residual stress after welding was considerably high, which
could provide the driving force for SCC. Recommendations are made for preventing further
failure due to SCC for the case in this study.

8
Acknowledgments
This work was supported by the National Research Foundation of Korea (NRF) grant
funded by the Ministry of Education, Science and Technology (grant No.20110031537). This
work was also supported by the Human Resources Development Program of the Korea
Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the
Korean government Ministry of Knowledge Economy (No. 20114030200020).

9
References
[1] T. Helgesen, A. Tjernaes, G. Heiberg, E. Heier, Failure investigation and condition
assessment using field metallography, Eng. Fail. Anal. 12(6) (2005) 974-985.
[2] D. A. Jones, Principles and Prevention of Corrosion, 2nd ed., Prentice-Hall, 1996.
[3] M. Suresh Kumar, M. Sujata, M. A. Venkataswamy, S. K. Bhaumik, Failure analysis of a
stainless steel pipe, Eng. Fail. Anal. 15 (2008) 497-504.
[4] S. Wang, Conditions for stress corrosion cracking to occur from crevice corrosion sites
and related electrochemical features, Mater. Corros. 55 (2004) 901–908.
[5] D. A. Wheeler, D. E. Rawl Jr., M. R. Louthan Jr., Metallurgical evaluation of stress
corrosion cracking in large diameter piping, Mater. Charact. 32 (1994) 25–33.
[6] R. C. Yin, A.H. Al-Shawaf, W. Al-Harbi, Chloride-induced stress corrosion cracking of
furnace burner tubes, Eng. Fail. Anal. 14 (2007) 36–40.
[7] Y. Wang, Y. B. Lu, H. L. Pan, Failure analysis of a hydro-processing reactor, Eng. Fail.
Anal. 16 (2009) 11-18.
[8] D. N. French, Metallurgical Failure in Fossil Fired Boilers, 2nd ed., A Willy-Interscience
Publication, 1992, pp. 243-245.
[9] J. Woodtli, R. Kieselbach, Damage due to hydrogen embrittlement and stress corrosion
cracking, Eng. Fail. Anal. 7 (2000) 427-450.
[10] Y. Harada, N. Tsuchida, K. Fukaura, Joining and shaping fit of dissimilar materials by
shot peening, J. Mater. Process. Technol. 177 (2006) 356-359.

10
List of Figures
Fig. 1 – Field replication result at inside surface of the pipe

Fig. 2 – Location of cracking at the pipe above the column in a Methyl Methacrylate plant

Fig. 3 – Cracked pipe taken out for failure analysis

Fig. 4 – Outside and inside surfaces of the pipe specimen near the crack tip area

Fig. 5 – Crack-tip region of the primary crack with many connecting secondary cracks

Fig. 6 – Cross sectional area near the weld showing the primary cracks (along the cutting line

A-A shown in Fig. 4)

Fig. 7 – Microstructures of welding fusion line, heat affected zone and parent metal of the

cracked pipe

Fig. 8 – Microstructures of the cross-section along the line B-B shown in Fig. 4

Fig. 9 – Stress corrosion cracking and nearby microstructure

Fig. 10 – Fracture surface showing transgranular brittle facture due to SCC

Fig. 11 – EDS spectrum of the deposit material taken from the inside of the failed pipe

11
(a) Inspection at inside surface of the pipe (b) Cracks at replication location

(c) Crack tip region

Fig. 1 – Field replication result at inside surface of the pipe

12
 Pipe Cracking
(b) (c) location

Column

(a) Overall view of the pipe on column (b) Drawing of the pipe and column

(c) Cover of the pipe on the flange (d) Cracking and leaking area revealed
after removing the cover ‘A’

Fig. 2 – Location of cracking at the pipe above the column in a Methyl Methacrylate plant

13
 (c)
50mm

(a) Cracked pipe section (DD=356mm)

Fig. 4(a)

(b) Corrosion deposit (c) Metallography specimen machined

at the inside surface of the pipe from the cracked pipe

Fig. 3 – Cracked pipe taken out for failure analysis

14
 (a) Outside surface

(b) Inside surface

Fig. 4 – Outside and inside surfaces of the pipe specimen near the crack tip area

15
Fig. 5 – Crack-tip region of the primary crack with many connecting secondary cracks

Fig. 6 – Cross sectional area near the weld showing the primary cracks

(along the cutting line A-A shown in Fig. 4)

16
 (a) Welding fusion line (region (a) of Fig. 6)

(b) Heat affected zone where the primary cracks were formed (region (b) of Fig. 6)

17
 (c) Parent metal far from the welding zone (region (c) of Fig. 6)

Fig. 7 – Microstructures of welding fusion line, heat affected zone

and parent metal of the cracked pipe

18
 (a) Outer section

(b) Inner section

Fig. 8 - Microstructures of the cross-section along the line B-B shown in Fig. 4

19
(a) Crack growth pattern showing stress corrosion cracking (X50)

(b) Work-hardened structure near the crack tip area (X400)

Fig. 9 – Stress corrosion cracking and nearby microstructure

20
 Fig. 10 - Fracture surface showing transgranular brittle facture due to SCC

Fig. 11 – EDS spectrum of the deposit material taken from the inside of the failed pipe

21
Research Highlights

z Failure analysis for cracked A312 TP304 SUS pipes used for transferring the MMA
material is reported.
z The failure was due to stress corrosion cracking caused by the chloride remained
inside the pipe.
z Many work-hardened grains were observed in the area where the stress corrosion
cracking occurred.
z The hardened grains are evidence that the residual stress after welding was
considerably high and became driving force for SCC.

22