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STUDIES ON THE STRESS CORROSION CRACKING

(SCC) BEHAVIOR OF VARIOUS METALS AND ALLOYS


USED IN THE DESALINATION AND POWER PLANTS
1


T.L. Prakash, John OHara and Anees U. Malik

Research & Development Center,
Saline Water Conversion Corporation
P.O.Box # 8328, Al-Jubail 31951, Kingdom of Saudi Arabia

SUMMARY

Corrosion problems in desalination plants can increase substantially the operation and
maintenance cost. The shutdowns resulting from the failures of components due to
corrosion are extremely expensive. Stress corrosion cracking (SCC) is one such
corrosion failure commonly encountered due to combined action of stress and corrosion
medium.

This report describes a study on the Stress Corrosion Cracking (SCC) behavior of alloys
resulting from the synergistic action of corrodents such as chlorides, oxidants, H
2
S, etc.
In this study, the threshold stresses for SCC have been determined for few generic alloys
namely; carbon steel, 316L, 317L, 904L, 430 and Monel 400 used in the desalination
plants. The standard Proof Rings and U-Bend samples in NACE and SHELL solutions
containing H
2
S are used for the purpose. Electrochemical polarization measurements
were performed on these alloys in the specified environments to study the effect of
electrochemical potential on the intergranular SCC. Fractographic analyses were
conducted by Scanning Electron Microscopy supplemented by Energy Dispersive
Spectroscopy. The test results showed that the intergranular and transgranular SCC
fracture of carbon steel and alloy 430 in H
2
S environment occurs only in the limited
potential environment, where as, the alloys viz., 316L and 317L are immune to SCC
under the condition of test performed. The alloy Monel 400 was also found susceptible
to SCC in presence of H
2
S.



1
Issued as Technical Report TR 3804/APP 90001 in October 1999. A paper entitled Studies on the Stress
Corrosion Cracking Behavior of Few Alloys used in the Desalination Plants was presented at the WSTA 4
th
Gulf
Conference, Bahrain, 13-18 Feb. 1999.
2 2 8 2
Fractography of alloy 430 indicated that the failure is attributed mainly to the sulfide
stress cracking due to synergistic action of sulfide and chloride that had greatly
enhanced the sensitivity of phases present in the alloy. A tentative ranking of the alloys
has been established on the basis of the threshold stress values obtained from the tests
conducted.

1 INTRODUCTION

One of the major factors that control the use of structural alloys in desalination industry
is its resistance to corrosion in marine environments and other distillation conditions.
The high chlorinity of seawater associated with its complex salt composition render it
inherently corrosive to many structural alloys. Its deleterious effects on ocean
interfacing structures have been documented and the wealth of information is compiled.
In spite, we continue to experience corrosion related problems on structures that must
interface with the marine environment. Stress Corrosion Cracking (SCC) is one such
problem which essentially controls and determines the suitability of materials from a
wide range of materials as they are very expensive modes of failures, of particular
relevance to desalination and power plants.

SCC is a stress assisted anodic process as a result of synergistic action of ions, such as
Cl- , H
2
S and oxidants like elemental sulfur present in the solution. The susceptibility to
SCC is influenced by factors like environmental condition, temperature, hardness of the
material, level of applied stress and microstructure of the material. The SCC of
materials in acidic solutions containing dissolved hydrogen sulfide (H
2
S) has been
termed as sulfide stress cracking (SSC). The failure characteristics in SSC are most
consistent with a hydrogen embrittlement mechanism where the fracture modes are
mostly intergranular. The literature available on SCC is quite vast, hence the present
literature survey is restricted to the following sections keeping in view of the objectives
of this project.


2 2 8 3
In the past it was thought by several investigators that SCC of a given alloy occurs only
in limited range of specific environments [1]. Subsequently, the above notion was
diluted when it was found that SCC occurs in wide range of environments including
pure water [2,3]. A brief account of literature information on few important categories
of structure alloys where SCC/SSC occurs by environment interaction is given below.

The carbon steels are prone to SCC in carbonate, bicarbonate, acetates and phosphate
environments and is identified as the main reason of cracking in natural gas transmission
lines. In low alloy steels, oxygenated water at high temperature, NaNO
2
- Na
2
SO
4

solutions, alkaline chloride solutions such as NaCl - Ca (OH)
2
under pitting conditions
[4,5], and anhydrous ammonia - methanol solution [6] in the presence of chloride caused
SCC. Studies on J-55 and N-80 steels have shown that H
2
S containing chloride
solutions promote SSC [7]. Similar observation was also made in AISI 1075 steels and
hardness of steel is also found to influence the SCC [8]. Strong tendency of SCC in
carbon steels have been noticed in diethanolamine and manoethanolamine solutions [9],
0.5M NaHCO
3
and 0.5M Na
2
CO
3
solutions at 70
o
C at high stress levels [10] and CO
2

environment [11]. Synergistic effect of low concentration chloride in bicarbonate
solutions [12] and low concentration of sulfate [13] causing SCC in low alloy steels
have also been reported. The effect of sulfide in NACE standard solution (5% NaCl +
0.5% Acetic acid) was found different from SHELL standard solution (solution
containing 0.5% Acetic acid) in the promotion of SCC for high strength low alloy steels
[14].

In austenitic stainless steels, SCC was well known since three decades. The cracking
was mainly due to chloride (which were neutral at high temperature, acid at low
temperature) and hydroxide solutions [15]. Thiosulphate environments of weld-
sensitized stainless steels have shown SSC [16]. SCC have been reported at ambient
temperature [17] and at 90
o
C [18] in materials with sensitized microstructure in chloride
containing aqueous environments and in 0.1M NaCl or synthetic seawater at 90
o
C for
SS 304 and 316 alloys [19]. Alloys SS 304 and 316 was more susceptible to SCC in HCl
and H
2
SO
4
[0.82 K Mol / m
3
] solutions [20]. Ferritic stainless steels (type AISI 405)
were reported to be susceptible to SCC at 288
o
C in aqueous environments [21]. It was
also reported that ferritic steels of type AISI 430 shown lesser susceptibility to SCC in
chloride solution when compared to sulfate solution [22]. Martensitic stainless steel
1.1 Metal - Environment I nteraction
2 2 8 4
type AISI 420 (13 Cr SS) was found prone to SCC in H
2
S environment and resistant in
CO
2
environment. The CO
2
- H
2
S - Cl
-
system inhibited SCC by favoring the formation
of protective layer [23]. In duplex stainless steels SSC is severe at 160
o
C in 25% NaCl
containing dissolved H
2
S and also in aerated brine solutions [24]. SCC was noticed at
ambient temperature in solution of sulfide/3.5 wt % NaCl containing sulfide [25,26].

The nickel base alloys viz., C-276 and alloy 825 were susceptible to SSC in HCl
oxidizing solution containing H
2
S. In chloride containing solution the SSC has been
observed at temperatures above 204
o
C [24]. The copper base alloys are subjected to
SCC in environments like ammonia, sulfur dioxide, organic complexing solution like
acetates, tartrates and sulfate solutions [27].

1.2 Threshold Stress for SCC

As the name implies the threshold stress is the stress below which no SCC occurs. The
main purpose of determining the threshold stress for SCC is to establish a ranking order
under given condition of metal environment combination, heat-treated microstructure,
type of stressing and its magnitude. An exact threshold stress for a given condition is
difficult to define. However, the relative ranking seems quite obvious.

The material which shows highest SCC resistance for a given environment may show
susceptibility to SCC when it is heat-treated to different microstructure. For example,
threshold stress in SCC of carbon and low alloy steels was found to be influenced by
heat treatment when it is studied using 5% NaCl - 0.5% Acetic acid solution containing
3000 ppm of H
2
S [28]. The heat treatment carried out gave untempered Martensitic
structure which is attacked by H
2
S and resulted in low threshold stress values for
cracking. From the result of series of test in Drop Evaporation Test on highly alloyed
stainless steel and duplex stainless steels as indicated by their threshold stress values, it
was seen that the highly alloyed stainless steels such as 654 SMO (UNS S 32654) was
most resistant to SCC than the duplex stainless steels viz., 2205 (UNS S 31803) [29] and
least resistant was 304 (UNS S 32304) [30].


2 2 8 5
The fractography in SCC was used mainly for two purposes. First being failure mode
determination and the other was for the studies of fracture mechanics. The conventional
metallography and Scanning Electron Microscopy (SEM) were widely employed for this
purpose. SEM fractography had been used in SCC tested stainless steel samples to
determine the crystallography of cracking and to determine the mechanism of fracture.
Normally, transgranular fracture was noticed in SCC [31]. In this study, the cleavage
nature of transgranular cracking which is typical of SCC was established.

1.4 I nfluence of Metallurgy

The metallurgical aspects of the material have profound influence on SCC. The grain
boundary segregation and phase transformation in steel strongly affect SCC. It was
found that substitutional elements like Molybdenum in specific environment typically of
type caustic medium, could affect SCC [32]. But, it is not true for all elements or in all
solutions. Similarly the phase transformation occurring by aging process, heat
treatment, cold working, etc. may or may not have beneficial effects. The example of
beneficial effect to SCC was seen by over-aging of Aluminum-Zinc alloys, whereas,
such over-aging is not found beneficial in Aluminum Lithium alloys [33].

1.5 Electrochemical Aspects

The SCC in specific environments is strongly correlated with localized (pit or crevice)
corrosion. The importance of electrochemistry is in the understanding of kinetics of
SCC in the context of changed local environment. The measurement of repassivation
potential of localized corrosion would represent the lowest potential at which special
local environment can be maintained and SCC propagation occurs in this special
environments. Another factor is the critical potential for SCC. If these two potentials
are determined and made to coincide by the alterations in the composition of alloys or
environment (with the help of local chemistry) new SCC resistant alloys can be
developed or mitigation of SCC could be achieved. Two outstanding examples of the
electrochemical contribution to SCC are the development of inexpensive steel [33]
without high nickel content which resist SCC upto 140
o
C with 20% NaCl. The other
being the usage of anodic protection from the understanding of electrochemistry, which
is used worldwide.

1.3 Fractography
2 2 8 6
The prevalence of SCC in desalination plant occupies a major share when compared to
other modes of material failure. In recent years many major SCC failures have been
reported from Desalination plants. The details of the failure is briefly described in
Appendices 1 through 4. Although there have been better understanding of the
corrosion mechanism with the help of environment analysis, metallography,
fractography, etc., the diversity in the failure modes and the associated mechanisms are
highly complex and not completely understood, still remain to be explored.

It is clear from the above literature review that till to date no data is available to
determine the susceptibility of various metals and alloys to SCC resulting from
synergistic action of corrodents which are normally encountered in Desalination and
Power Plants. The present investigation, although less comprehensive, is aimed to carry
out a systematic study of such phenomenon and to understand the nature and mechanism
so that occurrence of SCC can be minimized.

2. OBJECTIVES

The objectives of the proposed work are the following :
(i) To investigate the susceptibility of materials viz., stainless steels of grade AISI
316L, AISI 317L, AISI 430 and 904, Monel 400 and Carbon steel to SCC in the
standard NACE and SHELL solutions (i) containing saturated .H
2
S gas and (ii)
containing 0.1M Na
2
S.

(ii) To establish a ranking order with regard to SCC resistance for the above alloys
by determining the threshold stress.

(iii) To carry out fractography on the SCC failed specimen using Scanning Electron
Microscope to understand the mechanism of cracking.

(iv) To assess the effect of electrochemical potential on the alloy passivity to
corrodent species by performing the electrochemical polarization measurements
in the specified environments.
2 2 8 7

3. EXPERIMENTAL DETAILS

The materials selected for this study are CS (Carbon Steel), AISI 316L& 317L
(austenitic stainless steel), 430(ferritic stainless steel) and 904 (super austenitic stainless
steel) and Monel 400 (nickel base alloy). The chemical composition and the mechanical
properties of these alloys are shown in Table 1. The materials selected are typical
commercial alloys normally used in desalination and power plants.

3.1 Stress Corrosion Cracking Tests

3.1.1 Round and flat tensile samples:

Round and flat tensile samples of CS, 316L, 317L, 430 and Monel 400 were machined
from rod/sheet material stocks. All the materials selected were of mill finished
commercial grades. The schematic drawing of round test sample is shown in Figure 1,
the photograph of sheet sample is shown in Figure 2. The tests were carried out in
Cortest Proof Rings [34] with corrosion testing environment chamber. An hour meter
and H
2
S gas manifold were used to measure the time of failure of specimen and H
2
S gas
monitoring during test respectively. The photographs of the Cortest Proof Ring and
Cortest Proof Rings Battery with hour meter and manifold are shown in Figure 3.

The media employed for the tests were (i) NACE solution (having composition 5%
NaCl + 0.5% CH
3
COOH) prepared from distilled water and continuously bubbled with
H
2
S to maintain H
2
S saturation in solution. (ii) SHELL solution (having composition
0.5% CH
3
COOH) prepared from distilled water and continuously bubbled with H
2
S to
maintain H
2
S saturation as in (i).

The samples were tested in ambient temperature with the Cortest Proof Ring at 70, 80,
85 and 90% of their respective 0.2% yield stress (YS) with the help of loading nut and
calibration charts. During the test H
2
S was continuously bubbled in the solution. The
time to rupture of the samples were recorded. The samples those have crossed 500 hours
without rupture were withdrawn from the test. During the test, samples were periodically
withdrawn for examination of any initiation of cracks or corrosion pit development.
2 2 8 8

3.1.2 U-Bend Samples

A U-bend specimen is prepared generally through a rectangular strip that is bent 180
degrees around a predetermined radius and maintained in the resulting constant strain
condition during stress corrosion testing. The specimens are most easily be made from
sheet or strip. The main advantage of U-Bend specimen is that it is simple and most
useful for detecting large differences between SCC resistances of different alloys in the
same environment or one alloy under different metallurgical conditions or one alloy in
several environments.

The U-Bend specimen is stressed by bending the specimen to U-shape in a fixture either
manually or through Universal Testing Machine (UTM) and maintaining it in the same
shape by means of bolts and nuts. When U-Bend sample is stressed the material in the
outer fibers of the bend is strained into the plastic region. The total strain on the
outside of the bend is given by the following equation:
T
= ---------- When T << R
2 R


where, T = specimen thickness, and
R = radius of bend.

The value of outer fiber stress can be obtained by the stress-strain curve of the test
material by using the value of strain as determined by the above equation.

The U-Bend samples from the strips of 316L, 317L, 430 and 904 were prepared in UTM
using a fixture. The preparation of a typical test sample is shown in Figure 4. The
actual making of samples through fixture in an UTM is shown in Figure 5.

The testing of the samples are carried out in a plastic containers. By immersing in
solutions having specified corrodents. The media employed for the tests were (i)
NACE solution (same composition as that of round samples) containing 0.1M Na
2
S. (ii)
SHELL solution (same composition as that used for round samples) containing 0.1M
Na
2
S.

2 2 8 9
The samples were tested in ambient temperature. These samples outer fiber are stressed
to approximately 70, 80, 85 and 90% of their respective 0.2% yield stress (YS) by
bending them to corresponding diameter with help of rollers as detailed above. The
samples outer fiber surface was critically examined with help of magnifying glass for
crack freeness before they are immersed in the media selected. The samples are
withdrawn periodically for the purpose of inspection (every week) till they have crossed
500 hours without any appearance of cracks at the outer most fiber surface. The samples
those crossed 500 hours without crack appearance were continued up to 2000 hours.

The data obtained from U-Bend samples are quantitative and procedure allows for
multiple and field-testing. The limitation of their test is that actual volume of material
tested is relatively small (only small portion of the bend radius, i.e., outer most surface
experiences the highest stress) [35]. Hence very accurate results are difficult to obtain in
this test.


3.2 Electrochemical Tests

The electrochemical polarization techniques were performed to measure the absolute
corrosion rates. Tafel plots were generated for this purpose on samples by polarizing the
specimen about 300 mV anodically (positive- going potential) and cathodically
(negative-going potential) from the corrosion potential, E
corr
. The potential is stepped in
staircase waveform. The resulting current is plotted on a logarithmic scale. The
corrosion current I
corr
is obtained from Tafel plot by extrapolating the linear portion of
the curve to E
corr
. The corrosion rate was calculated from the I
corr
.

Experiments were carried out on the samples using EG&G model 273 Potentiostat with
Softcorr Corrosion Software M342. A saturated calomel electrode was used as reference
electrode. Photograph of the potentiostat along with cell is shown in Figure 6.
Graphite electrodes were used as auxiliary electrodes. Button samples of 14 mm dia and
2 mm thick were machined from rod/ sheet stock of sample material. They were
polished at one side to 600 # grade paper. The media employed in the electrochemical
tests are i) NACE solution ii) Natural seawater iii) Natural seawater containing varied
amounts of sulfide ion concentration obtained by dissolving known quantities of sodium
2 2 9 0
disulfide crystal iv) SHELL solution and v) SHELL solution containing known amount
of sulfide ion concentration.

4. RESULTS AND DISCUSSION

The results of the SCC tests carried out on round and flat tensile samples are shown in
Figure 7 & 8. The results revealed that the SCC occurred more readily in CS samples
in NACE solution and SHELL solution saturated with H
2
S at stress ranges of 70, 80, 85
and 90% YS. The alloys 430 and Monel 400 are also found susceptible to SCC only
when they are stressed to 90% YS in NACE solution containing H
2
S. The alloys 316L
and 317L were found immune to SCC in all the condition of tests in NACE or SHELL
solutions containing H
2
S.

The results of the SCC tests carried out on U-bend samples are shown in Tables 2
through 9. The results obtained were almost identical to that of round tensile samples
except that the time taken was quite considerable for SCC onset due to nature of sulfide
ion present in the medium. SCC occurred in the alloy 430 in NACE + 0.1M Na
2
S
media stressed to 90% YS. The first appearance of crack was noticed after 1344 hrs in
samples stressed to 90% YS, whereas first appearance of cracking was observed after
1920 hours of testing in sample stressed to 85% YS (Table 4). The intensity of
cracking/pitting was however less in medium of SHELL + 0.1M Na
2
S (Table 9) when
compared to cracking in NACE +0.1 M Na
2
S medium. The 316L, 317L and 904L
samples were however free from SCC was observed upto 2000 hours of exposure. The
photographs of typical alloy 316L samples after exposure are shown in Figures 9 &10
The photographs of samples of alloy 430 when exposed up to 1344 hours (70, 80,
85 & 90% YS) in NACE + 0.1M Na
2
S and close up view of cracks associated with
pitting are shown in Figures 11 & 12, respectively. The photograph of alloy 430
samples exposed up to 1920 hrs (70, 80, 85 & 90% YS) in SHELL + 0.1M Na
2
S
solution is shown in Figure 13. Due to some limitation of U-bend test, as explained in
earlier section, the results are not discussed in detail.

The fracture of SCC tested round and flat samples of CS and alloy 430 were analyzed in
Scanning Electron Microscopy (SEM). The fractures revealed intergranular as well as
transgranular mode of crack propagation (Figures 14 & 15). Branching of secondary
cracks from the primary cracks, which is typical of SCC failure mode were noticed. The
2 2 9 1
Energy Dispersive Spectrum obtained during SEM fractography at fracture crack tips
containing corrosion products showed sulfur rich regions (Figures 14b & 15b). This also
confirms the onset of SCC due to sulfide activity.

The threshold stress for CS in NACE and SHELL solution is 75% YS, whereas it is
85% for 430 and Monel 400 alloys in NACE solution. Such threshold stress was not
found to exist for the 430 and Monel 400 alloys in SHELL solution at all the stress
levels. The alloys 316L and 317L, however, did not show any threshold limits up to
90% YS either in NACE or SHELL solutions containing H
2
S. It is possible that
threshold stress might be greater than the YS of these materials. CS has shown greater
susceptibility to SCC in the tested medium when compared to other alloys (Figures 7 & 8)


Sulfides play a dominant role in the structural steels particularly in their resistance to
sulfide stress cracking. The water present would obviously assist the corrosion
mechanism. The reaction will be of the type

H
2
S + Fe FeS + 2 H

The nascent hydrogen is then expected to embrittle the alloy. The presence of chloride
all the more aggravate corrosion leading to early failure of steel. The instances of
Sulfide Stress Cracking of stainless steels have been reported [36] wherein failure of
specimens have been promoted in high chloride environment (>25% NaCl) at elevated
temperature and pressure saturated with H
2
S. The chloride content used in some of the
test being 5% , it is conceivable that the stainless steel of type 316L and 317L are less
likely to be affected by H
2
S as evidenced in the experiment. The effect of H
2
S in
SHELL solution suggest that except CS, other alloys were immune to SCC. CS was
found prone to SCC > 75% YS. The synergistic effect of chloride in presence of oxidant
(CH
3
COOH) and H
2
S to promote SCC in alloys 430 and Monel 400 at stresses > 85%
YS was clearly demonstrated as seen from the results of NACE solution experiment
(Figure 7).

The presence of H
2
S seems to have exerted a strong influence on the repassivation
which is manifested by cracking in alloy 430. The hydrogen embrittlement is well
known in alloy 430 particularly when cathodically protected. It is possible that
2 2 9 2
embrittlement is brought about by ferrite phase of the alloy much more than austenite
[37]. It is also known that cracking of ferrite taken place by mechanical twinning [38],
in this respect, hydrogen embrittlement could greatly enhance the sensitivity of ferrite to
cracking. This point is very important at low temperature and indeed evidenced in the
fractography performed on the failed samples of alloy 430 (Figures 15a & b). Cracked
regions had contained products rich in sulfides as determined in EDAX. Reports have
been published elsewhere that high ferrite duplex stainless steels (70% ferrite) is
inferior to that of low ferrite duplex stainless steels (50% ferrite) for hydrogen
embrittlement [39].

The Tafel plots generated from potentiostatic polarization experiments are shown in
Figures 16 through 23. The data obtained from the electrochemical experiments are
shown in Tables 10 & 11. The results obtained from NACE solution and natural
seawater containing 0.1M of sulfide indicated that alloys 316L and 317L showed higher
current densities relative to the Monel 400. The current density in natural seawater
solution for alloy 430 with 0.1M sulfides was lowest can be attributed to the
development of a stable passive film over the surface of the alloy.

The electrochemical data from the SHELL solution revealed that lowest current
densities for 317L alloy in 0.1M sulfide solution, while the highest was observed for
alloy Monel 400 except CS. In general, for all the alloys studied, high sulfide content
moved the corrosion potential to active direction thus enhancing localized corrosion.
Lowest current densities exhibited by alloys 316L and 317L indicated that they are least
susceptible to corrosion in presence of sulfide.

From the results of electrochemical tests it is seen that the synergistic effect of chloride
and sulfide on the corrosion behavior were prominent particularly for alloys 316L and
317L. For alloys 430 and Monel 400 such effect were not noticed. However, under the
influence of stress as noticed from the SCC test results, the trend was reverse. It is
plausible that the passive films formed over the alloy 430 and Monel 400 was less stable
and get disrupted easily, leading to SCC.

The data generated in this investigation suggests a tentative ranking of alloys could be
made with respect to their susceptibility to SCC. On the whole, at ambient temperature,
austenitic steels (alloys 316L, 317L and 904L) were better resistant than the Monel 400
2 2 9 3
and alloy 430 in solutions containing chloride and sulfide ions when stressed beyond
80% YS. The tentative ranking can be expressed as (in order of most resistant to SCC):

316L, 317L & 904L > Monel 400 > 430 > CS





5. CONCLUSIONS

The following conclusions are drawn on the basis of investigations carried out.

(i) In solutions containing sulfide, the chlorides demonstrated the synergistic effect
promote SCC in alloys 430 and Monel 400 at stress levels > 85% YS.
(ii) Alloys 316L and 317L were found SCC resistant under all conditions of
the tests performed.
(iii) Alloys 316L and 317L had shown higher current densities relative to the other
alloys in presence of specified oxidant, chloride and sulfide ionic species. Under
the influence of stress, they were least susceptible to corrosion.
(iv) CS was found prone to SCC at stress levels > 75% YS in solutions containing
specified amounts of sulfide, chloride and oxidants.
(v) A tentative ranking of the alloys have been established on the basis of threshold
stress value in solutions containing chloride and sulfide ions (in the order of
increasing resistance to SCC) 316L, 317L, 904L > Monel 400 > 430 > CS.
(vi) The failure of alloy 430 is mainly attributed to sulfide stress cracking as sulfides
greatly enhanced the sensitivity of phases present in the alloy to cracking as
evidenced from fractography.
(vii) Sulfide ion displaces the corrosion potential in active direction thereby
increasing the risk for localized corrosion for all the alloys studied.

6. RECOMMENDATIONS

(1) From the investigation carried out it is apparent that austenitic stainless steels of
type AISI 316L, 317L and high alloy 904L are the alloys of choice in
desalination plant environments containing high chloride. In these steels if any
stresses arising from fabrication, fit-up, welding and differential heating could
2 2 9 4
increase the susceptibility of these alloys to SCC and hence these stresses should
be avoided in practice.

(2) Chlorides and sulfides do cause SCC in carbon steel and alloy 430. Although it
is not possible to eliminate chlorides in desalination plants, meticulous care
should be exercised to minimize their introduction as an effective and essential
alloy. Satisfactory use of these alloys could be permitted by minimizing the
fabrication stress and cold work avoiding thermal insulation and gasket material
high in chloride, avoiding elastomers, lubricants, sealants and other material
containing halogens.

(3) Alloy Monel 400 is deemed to have moderate susceptibility to SCC in
desalination plant environment containing chlorides. However, its successful
use could be made by decisively controlling the stress levels, water chemistry,
design parameters, thermo-hydraulic characteristics, presence and absence of
crevices and biological activity as evidenced from the reported Bio-Corrosion of
Monel 400 bolts by sulfur reducing bacteria [40] in Al-Jubail intake system.

7. FURTHER SCOPE OF SCIENTIFIC WORK

(1) The susceptibility of alloys to SCC is significantly affected by the synergistic
action of chloride in presence of sulfide. Hence further testing is therefore
required to determine sources and levels of sulfide and possible prevention
approach in desalination process.

(2) Temperature plays dominant role in the repassivation and hydrogen
embrittlement of alloy 430. Hence the response of ferrite phase to temperature
changes should obviously be further investigated. It is likely that at high
temperature hydrogen embrittlement (cathodic cracking) decreases while
repassivation (anodic cracking) is very much accelerated which are not only
important from metallurgical and scientific view point, it is also of practical
interest since alloy 430 is one of the major material of construction in many
pumps used in Line 3 (water transmission system of SWCC).

2 2 9 5
(3) Due to lack of standardized test method for particular application, more test
results should be obtained on enlarged list of commercial alloys from various
laboratories and industries which can be realistically compared and used by
design engineers to select materials which will ensure reliable operation in
environments where stress corrosion cracking or sulfide stress cracking could be
a problem.



2 2 9 6

Table 1. Chemical Composition and Mechanical Properties of Alloys

A. Chemical Composition:

S. Alloy UNS Composition (%) Others
No. No. Fe Cr Mo Ni C Cu Mn Si
1 Mild
Steel
J2503 Bal 0.5
Max
0.2
Max
0.5
Max
0.25
Max
0.3
Max
1.2
Max
0.6 0.04P,0.04S
2 316L S31603 Bal 16.0 3.0 11.0 0.02 0.2 1.0 1.0 0.04P,0.02S
3 317L S31703 Bal. 18.5 3.2 13.5 0.02 - 1.0 - 0.08 N
4 904L N08904 Bal. 20 4.74 24.5 0.017 1.4 1.5 - 1.4Cu,1.0Si
5 430 S43000 Bal. 18.0 - - 0.12 - 1.0 1.0 0.04P,0.03S
6 Monel
400
N4000 2.5 - - 66.5 0.3 Bal. - 0.5 0.024S



B. Mechanical Properties (Room Temperature)

S.No. Alloy UNS
No.
0.2% Yield
Stress (Mpa)
UTS
(Mpa)
Elongation(%)
1 Carbon steel J2503 179 324 30
2 316L S31603 170 485 35
3 317L S31703 216 525 40
4 430 S43000 205 450 28
5 904L N08904 220 490 35
6 Monel 400 N08904 172 480 30

2 2 9 7
Table 2. U-Bend Specimen Testing of AISI 316L Exposed to NACE Solution
Containing 0.1M Na
2
S

S.No. Applied Stress
( % of YS)
Time of first
appearance of
crack (Hours)
Appearance of
surface/cross
section
Remarks
1 70 NFC NC -
2 70 NFC NC -
3 75 NFC NC -
4 75 NFC NC -
5 85 NFC Brown coloration
over the bent
portion
No cracking
6 85 NFC --DO-- --DO--
7 90 NFC --DO-- --DO--
8 90 NFC --DO-- --DO--

NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change


Table 3. U-Bend Specimen Testing of AISI 317L Exposed to NACE Solution
Containing 0.1M Na
2
S

S.No. Applied Stress
( % of YS)
Time of first
appearance of
crack (Hours)
Appearance of
surface/cross
section
Remarks
1 70 NFC - -
2 70 NFC - -
3 75 NFC - -
4 75 NFC - -
5 85 NFC - -
6 85 NFC - -
7 90 NFC Brown coloration
over the bent
portion
-
8 90 NFC --DO -


NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change

2 2 9 8
Table 4. U-Bend Specimen Testing of AISI 430 Exposed to NACE Solution
Containing 0.1M Na
2
S

S.No. Applied
Stress
( % of YS)
Time of first
appearance of
crack (Hours)
Appearance of
surface/cross
section
Remarks
1 70 NFC NC -
2 70 NFC NC -
3 75 NFC NC -
4 75 NFC NC -
5 85 1920 Few pits at outer
radius
-
6 85 1920 --DO--- -
7 90 1344 Pitting at few
places over the
bent radius
Cracking is prominently
associated with pitting over
the bent radius when test
contd. Beyond 1920 hrs.
8 90 1344 Moderate pitting
at few places over
the bent radius
--DO---

NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change

Table 5. U-Bend Specimen Testing of AISI 904L Exposed to NACE Solution
Containing 0.1M Na
2
S

S.No. Applied Stress
( % of YS)
Time of first
appearance of
crack (Hours)
Appearance of
surface/cross
section
Remarks
1 70 NFC NC -
2 70 NFC NC -
3 75 NFC NC -
4 75 NFC NC -
5 85 NFC NC -
6 85 NFC NC -
7 90 NFC Faint brown
coloration over
the bent radius
No cracking
8 90 NFC --DO-- --DO--


NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change
2 2 9 9
Table 6. U-Bend Specimen Testing of AISI 316L Exposed to SHELL Solution
Containing 0.1M Na
2
S

S.No. Applied Stress
( % of YS)
Time of first
appearance of
crack (Hours)
Appearance of
surface/cross
section
Remarks
1 70 NFC NC -
2 70 NFC NC -
3 75 NFC NC -
4 75 NFC NC -
5 85 NFC Faint brown
coloration over
the bent radius
No cracking
6 85 NFC --DO-- --DO--
7 90 NFC --DO-- --DO--
8 90 NFC --DO-- --DO--
NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change


Table 7. U-Bend Specimen Testing of AISI 317L Exposed to NACE Solution
Containing 0.1M Na
2
S

S.No. Applied Stress
( % of YS)
Time of first
appearance of
crack (Hours)
Appearance of
surface/cross
section
Remarks
1 70 NFC NC -
2 70 NFC NC -
3 75 NFC NC -
4 75 NFC NC -
5 85 NFC NC -
6 85 NFC NC -
7 90 NFC Brown coloration
over the bent radius
No cracking
8 90 NFC --DO-- --DO--


NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change

2 3 0 0
Table 8. U-Bend Specimen Testing of AISI 904L Exposed to NACE Solution
Containing 0.1M Na
2
S

S.No. Applied Stress
( % of YS)
Time of first
appearance of
crack (Hours)
Appearance of
surface/cross
section
Remarks
1 70 NFC NC -
2 70 NFC NC -
3 75 NFC NC -
4 75 NFC NC -
5 85 NFC NC -
6 85 NFC NC -
7 90 NFC NC -
8 90 NFC NC -


NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change


Table 9. U-Bend Specimen Testing of AISI 430L Exposed to SHELL Solution
Containing 0.1M Na
2
S

S.No. Applied Stress
( % of YS)
Time of first
appearance of
crack (Hours)
Appearance of
surface/cross
section
Remarks
1 70 NFC NC -
2 70 NFC NC -
3 75 NFC NC -
4 75 NFC NC -
5 85 NFC NC -
6 85 NFC NC -
7 90 1920 Small pits and
cracks are seen at
outer radius.
Hair line cracking
distributed all along
the bent radius
8 90 1920 --DO-- --DO--


NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change
2 3 0 1

Table 10. Potentiostatic Polarization data from NACE Solution and Natural
Seawater (NSW).

S.No. Material Electrolyte E corr
(mv)
I corr
( A/cm
2
)
CR
(mpy)
1 316L i) NACE Solution
ii) NSW
iii) NSW + 0.064 M Sulfide
iv) NSW + 0.1 M Sulfide
-59.6
-216
-348
-389
1.53
0.32
0.31
24.64
0.67
0.13
0.137
10.84
2 317L i) NACE Solution
ii) NSW
iii) NSW + 0.064 M Sulfide
iv) NSW + 0.1 M Sulfide
-212
-261
-383
-392
0.58
0.31
0.39
15.72
0.26
0.13
0.17
8.17
3 430 i) NACE Solution
ii) NSW
iii) NSW + 0.064 M Sulfide
iv) NSW + 0.1 M Sulfide
-332
-65
-480
-503
0.47
0.16
16.72
1.62
0.21
0.06
7.35
7.12
4 Monel
400
i) NACE Solution
ii) NSW
iii) NSW + 0.064 M Sulfide
iv) NSW + 0.1 M Sulfide
-207
-244
-315
-601
9.53
8.85
1.61
7.98
3.7
3.45
0.63
3.11


Table 11. Potentiostatic Polarization data from SHELL Solution

S.No. Material Electrolyte E corr
(mv)
I corr
( A/cm
2
)
CR
(mpy)
1 Mild
Steel
i) SHELL Solution
ii) SHELL Solution + 0.1 M
Sulfide
-705
-715
57.88
37.71
25.46
16.59
2 316L i) SHELL Solution
ii) SHELL Solution + 0.1 M
Sulfide
-100
-72
1.31
4.81
0.57
2.11
3 317L i) SHELL Solution
ii) SHELL Solution + 0.1 M
Sulfide
-62
-125
0.34
3.87
0.15
1.7
4 430 i) SHELL Solution
ii) SHELL Solution + 0.1 M
Sulfide
-150
-215
0.93
1.6
0.41
0.7
5 Monel
400
i) SHELL Solution
ii) SHELL Solution + 0.1 M
Sulfide
-492
-450
9.96
11.89
3.88
4.64

2 3 0 2






Figure 1. Schematic Drawing of Round Tensile SCC Test Sample





Figure 2. Photograph of sheet tensile samples

2 3 0 3




Figure 3. Photographs of Cortest Proof Ring (a) Sample set up, (b) Battery of
Proof Ring under test.


2 3 0 4



(4) U-Bend Sample With Bolt and Nut
(5) Final U-Bend Sample
(1) Flat Strip of Sample Piece
(2) Sample Between Roller Fixture and Ram
(3) U-Bend Sample Formation Over Ram
Figure 4. Schematic Diagram of U-Bend Sample Preparation Stages
2 3 0 5




Figure 5. Photographs showing (a) making of a U-Bend sample through fixture
In an Universal Testing Machine, (b) Universal Testing Machine.


2 3 0 6




Figure 6. Photographs of (a) EG&G Potentiostat assembly (b) Corrosion Cell


2 3 0 7








F i g u r e 7 . S C C o f a l l o y s i n N AC E S o l n . C o n t a i n i n g Hy d r o g e n S u l f i d e
7 5 8 0 8 5 9 0
3 0 0
4 0 0
5 0 0
6 0 0
T i m e t o F a i l u r e ( H r s . )
0 .2 O f f s e t Y i e l d S t r e n gt h %






















316, 317, 430, 400, MS
316, 317, 430, 400
316, 317, 430, 400
316, 317
Indicates no failure
400
MS
430
2 3 0 8









Figure 8. SCC of Alloys in SHELL Solution Containing Hydrogen Sulfide
75 80 85 90
300
400
500
600
0.2 Offset Yield Strength %
Time to Failure (Hrs.)



316, 317, 430, 400, MS
316, 317, 430, 400 316, 317, 430, 400 316, 317, 430, 400
CS
Indicates no failure
2 3 0 9






















Figure 9. Photograph of U-Bend samples (alloy 316L) stressed to
70%, 80%, 85% & 90% YS exposed to NACE solution
containing 0.1 M Na
2
S. Exposure time 1344 hrs




Figure 10. Photograph of U-Bend samples (alloy 316L) stressed to
70%, 80%, 85% & 90% YS exposed to SHELL solution
containing 0.1 M Na
2
S. Exposure time 1344 hrs



2 3 1 0
































Figure 11. Photograph of U-Bend samples (alloy 430) stressed to 70%, 80%,
85% & 90% YS exposed to NACE solution containing 0.1 M
Na
2
S. Exposure time 1344 hrs
















2 3 1 1















































Figure 12. Photograph of U-Bend (alloy 430) stressed to 90% YS exposed to
NACE solution containing 0.1 M Na
2
S. Exposure time 1344 hrs.
(a) Cross section view (b) End view showing pits and cracks.
2 3 1 2
































Figure 13. Photograph of U-Bend (alloy 430) stressed to 70%, 80%, 85% & 90%
YS exposed to SHELL solution containing 0.1 M Na
2
S. Exposure time
1344 hrs.







2 3 1 3


















0 5 10
Energy (keV)
0
1000
2000
3000
Counts
C
O
Fe
P
S
Cl
Ca
Cr
Mn
Fe
Fe
Cu


Figure 14. SEM Fractrograph of SCC tested CS sample. a) Fractrograph
showing intergranular and intragranular fracture modes. b) EDAX
spectrum taken at crack tip.




2 3 1 4








0 5 10
Energy (keV)
0
500
1000
Counts
O
S
Cr
Cr
Fe
Fe
Ni
Cu
Cu


Figure 15. SEM Fractrograph of SCC tested 430 alloy sample. (a)
Fractrograph showing intergranular and intragranular
fracture modes, (b) EDAX spectrum taken at a crack tip.


2 3 1 5





































Figure 16. Potential Polarization Curves (Tafel Plots) Showing the
Effect of Varied Sulfide Content on 316L. 1-NACE
Solution, 2-Natural Seawater, 3-Natural Seawater +
0.06M Sulfide and 4 - Natural Seawater + 0.1M sulfide.
2 3 1 6




Figure 17. Potential Polarization Curves (Tafel Plots) Showing the Effect of
Varied Sulfide Content on 317L. 1-NACE Solution, 2-Natural
Seawater, 3-Natural Seawater + 0.06M Sulfide and 4 - Natural
Seawater + 0.1M sulfide.
















2 3 1 7











Figure 18. Potential Polarization Curves (Tafel Plots) Showing the
Effect of Varied Sulfide Content on 430 alloy. 1-NACE
Solution, 2-Natural Seawater, 3-Natural Seawater + 0.06M
Sulfide and 4 - Natural Seawater + 0.1M sulfide.










2 3 1 8



































Figure 19. Potential Polarization Curves (Tafel Plots) Showing the
Effect of Varied Sulfide Content on Monel 400 alloy. 1-
NACE Solution, 2-Natural Seawater, 3-Natural Seawater +
0.06M Sulfide and 4 - Natural Seawater + 0.1M sulfide.














2 3 1 9













Figure 20. Potential Polarization Curves (Tafel Plots) Showing the
Effect of Sulfide Content on 316L. 1-SHELL Solution and
2- SHELL Solution + 0.1M sulfide.








2 3 2 0












Figure 21. Potential Polarization Curves (Tafel Plots) Showing the Effect of
Sulfide Content on 317L. 1-SHELL Solution and 2- SHELL Solution +
0.1M sulfide.









2 3 2 1














Figure 22. Potential Polarization Curves (Tafel Plots) Showing the
Effect of Sulfide Content on 430 Alloy. 1-SHELL
Solution and 2- SHELL Solution + 0.1M sulfide.







2 3 2 2













Figure 23. Potential Polarization Curves (Tafel Plots) Showing the Effect of
Sulfide Content on 400 Alloy. 1-SHELL Solution and 2- SHELL
Solution + 0.1M sulfide.








2 3 2 3







APPENDIX- 1




SCC FAILURE OF INTERMEDIATE BEARING SUPPORT



LOCATION : Main Seawater Pump, Assir Plant


CAUSE : Residual stresses at rim and arm joint due to improper
manufacturing practice combined with local seawater corrosion.


MATERIAL : Ni-Resist Cast Iron (ASTM - A 493 D
2
).


























Figure 24. SCC Failure Photograph of Intermediate Bearing Support


2 3 2 4








APPENDIX - 2




SCC FAILURE OF SEAWATER INTAKE PIPE COLUMN



LOCATION : Seawater intake system, Shoaiba, Plant Phase-1


CAUSE : Cumulative buildup of residual stresses at the column inner
surface due to water hammering effect during operation combined
with local seawater corrosion


MATERIAL : Ni-Resist Cast Iron
























Figure 25. SCC Failure Photograph of Seawater Intake Pipe


2 3 2 5




APPENDIX - 3
SCC FAILURE OF STEAM TURBINE BLADES

LOCATION : C-8, Turbine # 81 Blade, Al-Jubail Plant

CAUSE : High stress at the pits of the trailing edges.

MATERIAL : 17- 4 PH Stainless Steel




















a) Photograph showing pits at trailing edges of the blade.














b) Microphotograph showing transgranular and intergranular failure mode,
X 400

Figure 26. SCC Failure Photographs of Steam Turbine Blades
2 3 2 6




APPENDIX - 4




SCC FAILURE OF BRINE RECIRCULATING COLUMN



LOCATION : Al-Jubail Plant, Phase-1


CAUSE : Presence of residual stresses due to improper heat treatment
during fabrication of column pipe.


MATERIAL : Ni-Resist Cast Iron

























Figure 27. SCC Failure Photograph of Brine Re-Circulating Column Pipe




2 3 2 7




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2 3 3 0