JMEPEG (1997) 6:534-544 9 International

The Susceptibility of 90Cu-10Ni Alloy to

Stress Corrosion Cracking in
Seawater Polluted by Sulfide Ions
A. El Domiatyand J.N. Alhajji

Electrochemical polarization measurements and slow strain rate tests (SSRT) of a 90Cu-10Ni alloy in
highly sulfide polluted seawater were conducted to investigate stress-corrosion cracking (SCC) behav-
ior. The severity of the SCC depends on the sulfide concentration in the seawater. The severity increases
as the concentration increases. Because the major time in SCC is spent in the initiation process of the
propagating crack, the fracture toughness has only a minor effect in the component life failed by SCC.
The SCC behavior of CDA706 is strictly linked to sulfide concentration in the range of 100 to 1000 ppm.
The general corrosion of Cu-Ni alloys in low (<100 ppm) and high (>100 ppm) sulfide polluted seawater
increases due to the selective copper dissolution. Cyclic polarization measurements confirmed that the
corrosion rate decreases slightly as the sulfide concentration increases. Pitting tendency was high in the
low concentration range of sulfide and low in the high concentration range. The presence of stresses in
SCC removes the protective layer as it increases during testing of the specimen or during the actual ser-
vice of a component. The authors propose that film rupture occurred, and two proposed SCC mecha-
nisms were operational, namely sulfide stress cracking associated with the anodic dissolution in the low
sulfide concentration range and hydrogen embrittlement, which was dominant in the high sulfide
concentration range. It was found that a synergism exists between sulfide and stress that enhances
the effect of the latter.

Keywords testing method called the automated stress corrosion ring

CDA706, copper-nickel alloy, corrosion, crack
initiation, crack propagation, fracture toughness,
intergranular corrosion cracks, open circuit potential,
polarization, seawater, slow strain rate tests,
stress-corrosion cracking, sulfide
1. Introduction
Copper alloys are used extensively in water distribution
systems, water treatment units, and condensers and heat ex-
changers, where fresh or salt water is used for cooling. These
units are often the critical components for the processing plant
in electricity generating, oil, and chemical industries. The use
of copper alloys in any o f these engineering applications is
often limited by its susceptibility to stress-corrosion cracking
(SCC). The selection of a specific alloy for a certain applica-
tion is usually based on laboratory test results that were ob-
tained in the simulated environment.
Three main methods for SCC testing include constant load,
constant strain, and constant strain rate. Constant load and con-
stant strain rate techniques are more discriminating but gener-
ally require large loading frames. Conversely, constant strain
tests require only small loading devices, and a large number of
specimens can be tested simultaneously under different stress
levels. The criterion for SCC resistance in this type o f test is the
time to initiate and propagate a micro crack, which can be seen
at low power magnification, not the time to failure, because the
specimens do not fail. Because each testing technique has ad-
vantages and disadvantages, there is a need for a simple and re-
liable SCC test method. A simple automated stress corrosion
A. E! Domiaty and J.N. Alhajji, Kuwait University, Safat 13060,
Kuwait.
(ASCOR) test was developed by Schra and Groep (Ref 1) to
test aluminum alloys according to A S T M G 44. A specific load
decrease (2%) is used as the criterion for SCC initiation. The
main advantages o f the ASCOR test method are that a large
number of specimens can be tested simultaneously, and the
SCC initiation lines can be determined according to a clearly
defined criterion without time consuming and subjective in-
spections and without disturbing the test procedure. The slow
strain rate test (SSRT) uses (Ref 2) tensile test specimens
mounted in stiff-frame machines and strained at the rate of 10-7
to 10-5 s-1 in the presence of a specific environment. Strain
rates in this range promote SCC, but the absence of cracking is
no ensurance of immunity to SCC. Various methods are used to
assess the results when SCC is observed (Ref 3). These include
the area under the stress-strain curves, time to failure, crack ve-
locity, and the ratio of fracture stress in a medium to fracture
stress in air.
1.1 Slow Strain Rate Testing
Because of the distinct advantage o f rapidity of the slow
strain testing (SST) technique in the assessment of SCC sus-
ceptibility, the present investigation employed SST for the
SCC studies on copper-nickel alloys in a sulfide polluted envi-
ronment. If the strain rate is too high, ductile fracture occurs be-
fore the necessary corrosion reactions take place. However, at
too low a strain rate, corrosion can be prevented by repassiva-
tion or film repair so that the necessary reactions of bare metal
cannot be sustained. The optimal strain rate for testing the SCC
susceptibility depends primarily on the metal/environment
system or the crack propagation rate (CPR). Usually for a sys-
tem in which the CPR is small, a slow strain rate is required,
and in cases where the CPR is high, a relatively fast rate is suit-

534---Volume 6(4) August 1997 Journal of Materials Engineering and Performance

 able. For admiralty brass in sulfite or nitrate solution, the CPR
is approximately 10-7 m/s for which a strain rate of 10-5 s -1 is
adequate. In the late 1960s, Parkins (Ref 3) described a test
arrangement where an immersed tension specimen in a cor-
rosion solution polluted at a slow constant extension rate.
The data obtained from SSTs provide corrosion engineers
with a greater degree of confidence in choosing compatible
material/environment combinations. Not only can this method
satisfy pass/fail criteria, but it can also provide data to judge the
relative degree of SCC susceptibility among test variables,
conditions that cause SCC to result in a lower maximum load
and a loss of ductility. Therefore, by comparing maximum
load, reduction in area or elongation and noting the degree of
secondary cracking, a particular variable can be judged to re-
tard or accelerate cracking.
In addition to the testing methods for SCC, attention should
be focused on the corrosion/film formation tendency of un-
stressed specimens in a particular environment. The corrosion
behavior of copper-nickel alloys in unpolluted and sulfide pol-
luted seawater was investigated by Eiselstein et al. (Ref 4).
They found that the copresence of sulfide and oxygen in seawa-
ter results in corrosion rates much higher than those measured
when the alloy is exposed alternately to sulfide and oxygen. In
aerated sulfide polluted seawater, accelerated corrosion ap-
pears to be the result of the sulfide preventing the formation of
a protective oxide corrosion product layer. The behavior of
70Cu-30Ni alloy in quiescent sulfide polluted and unpolluted
seawater at 25 ~ was examined by Beccaria et al. (Ref 5).
They demonstrated that the presence of sulfides enhances the
average corrosion rate in a range of concentration (0 to 10 ppm)
while promoting preferential copper dissolution. In deaerated
seawater, corrosion behavior was found to be strictly linked to
sulfide concentration. In low polluted seawater, the mean cor-
rosion rate of the alloy increases, and slightly selective dissolu-
tion occurs. In highly polluted sea water, the corrosion rate
decreases while slightly selective nickel dissolution occurs.
The corrosion of copper-nickel alloys in sulfide-polluted
seawater was also studied by Alhajji and Reda (Ref 6-11). They
found that sulfide concentration plays a major role in the corro-
sion process. They concluded that sulfide acts as a catalyst, and
the copper sulfide is the first compound to precipitate in sulfide
polluted seawater.
Most of the early information regarding the SCC of copper
alloys was based on service experience. Such information is
useful but qualitative, and the environmental constituents or
conditions that led to the cracking are unknown. In the past sev-
eral decades, the study of SCC was greatly accelerated, and the
causes and the mechanisms for the cracking behavior were ad-
dressed. The SCC of copper-nickel alloys was studied by
Thompson (Ref 12), and he found that the alloys are practically
immune to SCC in seawater. Popplewell and Gearing (Ref 13)
showed that only a few of these 25 copper-base alloys are sus-
ceptible to SCC in industrial and marine environments. Using
the SST technique, Habib and Husain (Ref 14) concluded that
the most severe SCC was observed on the 70Cu-30Ni specimen
in seawater with 3120 ppm sulfide at 25 ~ It was also con-
cluded that the 90Cu-10Ni and 70Cu-30Ni alloys are suscepti-
ble to SCC in sulfide seawater, which was based on the ratio of
ultimate tensile strength, elongation percent, and time to fail-
Journal of Materials Engineering and Performance
ure of samples tested in solutions compared to those tested in
air at moderate temperature.
In this study, an experimental program was conducted using
the SST technique to determine the susceptibility of Cu-Ni al-
loys in sulfide polluted seawater. This experimental program
included a scanning electron microscope (SEM) study of the
fracture surface as an important assessment tool that was
missed by some investigators (Ref 14) to determine the type of
fracture and gain an insight into fracture mechanism. Also, the
potential drop technique is used during the test to determine the
onset of crack initiation. In addition, various electrochemical
tests were conducted under unstrained conditions to elucidate
the mechanism responsible for the appreciable increase in cor-
rosion tendency and the embrittling effect on 90Cu- 10Ni in the
presence of sulfide.
2. Experimental Procedures
2.1 Materials
The material used for this study was 90Cu-10Ni (CDA706)
in the form of tube, as received from the supplier. The inner and
outer diameters of the tube were 15.5 and 19 mm, respectively.
The mechanical properties of the materials were determined by
the standard tensile test performed according to ASTM E 8-83.
Flat specimens of 15 mm diameter and 2.5 mm thickness were
subjected to various electrochemical tests under unstrained
conditions to evaluate the corrosion and pitting tendency of the
specimen under the various environmental conditions. Figure 1
shows the corrosion test specimen dimensions. Figure 2 shows
the tensile test specimen mounted in the corrosion cell.
2.2 SCC Test Cell and Procedures
Figure 2 represents a schematic drawing of the entire strain-
ing electrode/corrosion cell assembly. The corrosive cell is a
plexy glass tube with a rubber cork in the lower end and a plexy
glass plate on top. The specimen in the form of a pipe was
mounted (Fig. 2) and subjected to uniaxial loading by the In-
stron testing machine. The cell was designed so that the gage
length of the specimen is surrounded by the corrosive environ-
ment. The counter electrode was in the form of cylindrical
platinum mesh surrounding the entire gage length of the speci-
men and reference electrode. The cell was connected to the po-
tentiostat to monitor the potential change during the SSRT.
Testing was limited to aqueous solutions at room temperature
l j LAPPED
OneSideSURFACE
Only 8- 10R M $
I
I
2.5mm
Fig. 1 A schematic diagram of the test specimen used in the
corrosion tendency evaluation
Volume 6(4) August 1997--535
in different concentrations o f sulfide in seawater at 0, 100, 300, 0 2 + 4H20 + 4e- --> O H - (cathodic reaction) (1)
500, and 1000 ppm.

Cu + H S - --> Cu (HS-)ad s (2a)

2.3 Electrochemical Tests

Samples of CDA706 were prepared by a wet grinding proc- Ni + H S - --> Ni (HS-)ads (2b)
ess with 240-grit SiC paper and wet polished with 600-grit SiC
paper until previous coarse scratches were removed. Then the
specimens were rinsed and dried. These procedures were com- Cu (HS-)ad s--~ Cu (HS) + e - (3a)
pleted one hour prior to the experiment (Ref 8). Corrosion
measurement experiments were conducted using synthetic Ni (HS-)ads---> Ni (HS) + + 2e- (3b)
seawater. This was prepared with distilled water and standard
seawater salt. Standard seawater salt (Marinemix and Bio-Ele-
ments from Wiegandt G M B H & Co., F. R. Germany) was used Cu (HS) ~ Cu + + HS - (4a)
to reduce the variability effects resulting from conducting
measurements using natural seawater. The sulfide was intro- Ni (HS) + --~ Ni 2+ + HS - (4b)
duced in the seawater using research grade sodium sulfide
(Na2S). The level of sulfide in the seawater was checked by the
iodometric method of analysis (Ref 9). Analytical grade 2Cu + + H S - + OH-----> Cu2S$ + H20 (5a)
chemicals were used in all experiments.
Electrochemical corrosion measurements were taken at 20
Ni 2+ + H S - + O H - ---->NiS$ + H20 (5b)
~ for all previously mentioned conditions using a computer
controlled potentiostat/galvanostat (EG&G; Z.I. Petite Mon-
tagne Sud, France). A modified electrochemical corrosion test Once the cuprous-sulfide and nickel-sulfide are formed, it is
cell was used, in which a large cylindrical platinum mesh concluded that the intensification of corrosion is not directly
counter electrode was incorporated to obtain a uniform electri- linked with the dissolved sulfide in the electrolyte but rather
cal field among the working, reference, and counter electrodes. with a secondary effect caused by the action of Cu2S or NiS,
Preliminary corrosion measurements were always performed where the sulfides act as effective cathodes (Ref 22). The ad-
for 4 h using small amplitude cyclic voltammetry (SACV) over sorption o f H S - i o n s (reactions 2a,b) creates negatiye potential
the range of +_5 mV from Et= 0 as previously explained (Ref 9). that increases the speed of the hydrogen discharge reaction
In addition, cyclic potentiodynamic scans were run after 4 h to through another simultaneous cathodic reaction as follows
gain an insight into the corrosion mechanism in the presence of (Ref 22):
a sulfide pollutant. The electrochemical tests were run with a
saturated Calomel electrode (SCE). The stability o f the SCE H S - + e - --+ Hads + S = (6)
was checked following each experiment against a fresh SCE to
ensure the reliability of the experiments. The scan rate o f the
experiments was 0.166 mV/s. The experiments were con- Hads + Had s --->H 21" (7)
ducted repeatedly with fresh samples under the same environ-
mental conditions to obtain reproducible results. Generally, where S = at the pH of the solution (9.7 to 9.75) is not stable, and
reproduced results were excellent. thus the following reaction takes place:

S = + H20 ~ H S - + OH- (8)

3. Resultsand Discussion
and thus, hydroxide ions are produced resulting in a localized
An electrochemical study for the unstressed 90Cu-10Ni al- increase in the pH of the solution and in the formation of hy-
loy specimens in unpolluted and sulfide polluted seawater was droxides that occur through the followingreactions:
completed prior to the assessment of SCC susceptibility of the
alloy in these environments. It is known (Ref 6-11, 15-21) that Cu + + O H - ~ Cu (OH),I, (9a)
sulfide results in a serious deterioration of Cu-Ni alloys be-
cause of the film formation/breakdown tendency o f cop-
per/nickel corrosion in sulfide environments. The following Ni 2+ + 2 O H - --->Ni (OH)2,1, (9b)
mechanisms are proposed to counteract the effects of sulfide on
this alloy. The formation of sulfides occurs through the following reac-
tions:
3.1 Proposed Corrosion Mechanism of Cu/Ni Alloys in
Seawater 2Cu + + S = --> Cu2S,l, (lOa)
Generally, in sulfide polluted seawater, the following se-
quence of reactions are possible : Ni 2+ + S = ---->NiS,[, (10b)

536---Volume 6(4) August 1997 Journal of Materials Engineering and Performance

Thus, corrosion products are brittle, nonadherent, and consist This shift in potential is directly related to the reaction occur-
of a nonprotective mixture of hydroxides and sulfides of cop- ring on the surface as outlined earlier. Clearly, increasing sul-
per and nickel. The hydrogen produced by reactions 6 and 7 is fide concentration results in the most active shift in potential,
adsorbed on the surface, and the specimen becomes susceptible and hydrogen evolution then becomes a possible cathodic par-
to hydrogen cracking and enhances the brittling effect of sul- tial process. In addition to reactions 6 and 7, another reaction
fide. This is particularly important in this study because the becomes significant (Ref 24):
tests were performed at SST (Ref 23), and the film produced
was nonprotective.
2H20 + 2e- --~ H 2 1"+ 2OH- (11)
Figure 3 shows the corrosion potentials of CDA706 in sul-
fide-polluted seawater. It shows that increasing sulfide levels
result in a shift in corrosion potential in the active direction. This reaction further supports the earlier supposition that
sulfide also plays an indirect role in inducing hydrogen crack-
Apptmd ing. It is proposed that film rupture occurred, and two major
:=';to. SCC mechanisms were operational, namely sulfide stress
cracking associated with the anodic dissolution and hydrogen
embrittlement. Figure 4 shows that increasing the sulfide con-

/~ i~ To Che po~enr ... I,..I... I I...I...

$CK r e f e r e n c e electrode

0.8

Ttta~ 1
elecCro~e 0.6

_-: :
~ 0.4
"N
R~bloer
I- -- -- -XA t
cork

r~st~ ~ ~~/ 0.2 84

N"

0E ~ ' "
~ Te~s;le I I I I I
toad from
t h e te$~,ng
0 200 400 600 800 1000 1200
mac~ne
Sulfide Concentration, ppm
Fig. 2 A schematic diagram of the cell utilized in slow strain (a)
rate test (SSRT) cell for stress-corrosion cracking (SCC)
evaluation
.... I .... I .... I .... I .... I .... I ....
[]

/
-0.83 .... I .... I .... I .... I .... I .... I .... 0.8 #1
[Sulfide] e

"--'•
>.
-0.84 -
I--o- -300ppm I J
I§
0.6 ie
~1.,. I --""" 500 PPm I ~
"-" -0.85 -

##
-0.86 - 0.4
i#
,133
-0.87 -
,~o,< 0.2
.[]
-0.88 t><> o_O o_o. ~ o - o ~ "0-<>oL~176
~-~ Q o

3rrT~'l.'.'.', i . . . . i . . . . I . . . . i .... i , . a
-0.89 i i i i i i

'32~_B ~. B.O ~.B ~. El-13 O. B ~ Q~} E]-B 43 fB

0 0.5 1 1.5 2 2.5 3 3.5
.... i .... I .... I .... i .... i .... i ....
-0.9 I I I I I I log [Sulfide Concentration, (ppm)]
0 0.5 1 1.5 2 2.5 3 3.5
(b)
Time (Hours)
Fig. 4 The corrosion tendency of the 90Cu-10Ni alloy
Fig. 3 Open circuit potential diagram for unstrained 90Cu- (CDA706) in aerated sulfide polluted seawater. (a) Linear plot.
10Ni alloy in sulfide polluted seawater (b) Semi-log plot.

Journal of Materials Engineering and Performance Volume 6(4) August 1997--537

centration results in a sharp increase in the corrosion tendency The present research used very high sulfide concentrations
of the Cu-Ni alloy under investigation. It should be emphasized ranging from 100 to 1000 ppm in seawater as the primary cor-
that these tests were performed over a relatively short duration, roding medium for this SCC study. The polarization diagram
and a significant corrosion product layer did not form that (Fig. 5, 6) shows that the increase in potential in the anodic di-
could lead to a leveling off or decrease in the corrosion rate rection yielded an increase in current in the region close to the
over time due to diffusion limitations of the sulfide ions. equilibrium potential. After the initial active dissolution, re-
duction in anodic current values was noted for further increase
in potential and remained little affected by the potential o f -
O.6 .... I .... I ....
I
, ....
I
r ....
I .... I,,,
300 mV versus SCE for all sulfide polluted systems. It was re-
ported (Ref 9) that the cuprous-oxide films formed during the
I I initial exposure to unpolluted seawater were relatively smooth
0.4
and nonporous, while the sulfur containing films, presumed to
tU
O be stoichiometric and substoichiometric forms of cuprous-sul-
0.2 fide, were relatively thick and porous. It was further stated that
....."
.tu
the presence o f dissolved sulfide or sulfide oxidation prod-
r" ucts does not lead directly to accelerated corrosion, but
CD 0
rather that the porous cuprous-sulfide corrosion product
O formed in the polluted water interferes with the normal
12.
-0.2- growth of the protective oxide films on subsequent exposure
to unpolluted seawater.
-o.4 ........., I . . . . . . . . . . . . I .... I .... The present research studies were performed under stagnant
-8 -7 -6 -5 -4 -3 -2 -1 conditions; the temporary passive tendency of the corrosion
log (I ].tAJcrn2) product layer formed during the anodic polarization was noted
for the concentrations of sulfide and the decrease in the in-
Fig.5 Cyclicpotentiodynamicdiagramsfortheunstrained crease in the sulfide concentration. This behavior was observed
90Cu- I0Ni alloyin seawater up to the potential value of approximately -300 mV versus

as .... I .... I .... I .... l .... I .... .... I .... I .... I .... I .... I .... I.--
I s ~ , ~ t e r . 3oo ppm s ~ ~
I -o.~ ~_......-- ~

-o.4

==~

.m .4).8

-0.8
o.
-1
S

. . . . ! . . . . ! . . . . ! . . . . ! . . . . ! . . . . . . . . i . . . . ! . . . . t . . . . i . . . I i , , ,, i, , ,
i i ! ! i -1.2 ! i i ! i i

-7 -6 -5 -4 -3 -2 -1 -9 4 -? -6 -5 -4 -3 -2

log (I gA/cm z) log fl gA/cm z)

(a) (b)

"0.2 .... [ .... I .... I .... I .... 0.5 .... I .... I .... I .... I .... I ....
I
..... ~NllwRler § 1000 ~ Sulfide I
i o $

-0.4 .:.."(':'~
0
Ikl . . . . . . . . . . . .

-0.6 |
>8
OR
t,-

G)
-0.8
t
a5
o~
-0.5
gi!' ......
..::._ ....... - D

n o. "" . . . . . . . . F
-1 S

. . . . | . . . . i . . . . ! . . . . i . . . . | . . i . . . . ! . . . . t . . . . i . . , , f , , , .
-1~. , , , , -1.5 ! ! i i !

-8 -7 -6 -5 -4 -3 -7 -6 -5 -4 -3 -2 -1

log (I l.tMcm 2) log (I I.tMcm 2)

(c) (d)

Fig. 6 Cyclic potentiodynamic diagrams for the unstrained 90Cu-10Ni alloy in sulfide polluted seawater

538---Volume 6(4) August 1997 Journal of Materials Engineering and Performance

SCE for all cases. However, increases in potential beyond this dissolution, and the behavior was the same for all sulfide pol-
value of - 3 0 0 mV, close to the equilibrium potential of the luted systems, irrespective o f the concentration.
90Cu-10Ni alloy in an unpolluted system resulted in the active

400 3.1 Mechanical Results

350 Figure 7 shows the engineering stress-engineering strain

curves for the 90Cu-10Ni alloy in the various environments.
300.
Table 1 gives the mechanical properties obtained from the
/'21~, :.- t .
standard tension test at room temperature. Typically, SCC se-
250- ,/~r 9 'L s ~=
verity is expressed as the ratio of a parameter from the SCC
~ , 200- L
~
curve to the same parameters of the baseline curve. As this ratio
~J decreases in unity, the SCC severity increases. Several parame-
r.~
150
i' !t i ters that are available for comparison include maximum load,
r.,/'j total elongation, area under the curve, and failure load. The true
100

50
Table 1 Mechanical properties of the 90Cu-10Ni alloy
from the s t a n d a r d tension test at r o o m t e m p e r a t u r e
0
0.1 0.2 0.3 0.4 0.5 0.6 Alloy property Cu/Ni:90/10
Tensilestrength,MPa 350
Strata (ram/ram) Yieldstrength(0.2% offset),MPa 180
Elongation,% 36
Fig. 7 Stress-strain diagram for the 90Cu-10Ni alloy in air and Reductionin area, % 63
sulfide polluted seawater during slow strain rate testing (SSRT)

40 9 -.I---I.--1...I...I... t .... t .... t .... t .... t .... t .... I .... !

3S- I

~
30- e~

25- ~0

[] 20" ' 012 I

15
, , , i . . . t . . . I . . . i . . . ! . . i
10 i i ! i |

0 2OO 400 600 8OO 1000 1200 !0 ~ . . . . 1' 2' 3~

Sulfide Concentration (ppm) log [Sulfide Concentration (ppm)]
(a) (b)

0.35 ...I-.-I...I...I...I.. .... I .... I .... I .... I .... I .... I ....

.-= o.25
I
~! o.2
I
. . . . i . . . . i . . . . n . . . . t . . . . i . . . . i.
. . I 9 9 . I . . . t . . . t 9 . . * . . . 0.1
0.1 i ! ! ! ! !

0 '
200 460 '
600 '
800 i~ 1200 o 0.5 ! 1.5 2 2.5 3 3.5
Sulfide Concentration (ppm) log [Sdfide Concentration (ppm)]
(c) (d)
Fig. 8 The embrittling effect of sulfide concentration during slow strain rate testing (SSRT) for the 90Cu-10Ni alloy in seawater. (a) Per-
cent elongation. (b) Percent elongation (semi-log plot). (c) True fracture strain. (d) True fracture strain (semi-log plot)

Journal of Materials Engineering and Performance Volume 6(4) August 1997--539

fracture stress and true fracture strain can also be used to evalu- brittling effect of increasing the sulfide concentration on the re-
ate SCC severity. duction in toughness of the Cu-Ni alloy measured by the area
Measurements of the reduction in area and elongation per- under the 6-~ curve. Table 2 reports stereo microscopic obser-
cent are indicators of specimen ductility loss in SSRT, which vations and shows a general increase in the density and distri-
provides a convenient parameter for evaluating SCC severity. bution of secondary stress corrosion cracks with an increase in
Figure 7 shows the stress versus strain curve resulting from sulfide concentration. Figures 8(a) and (b) show the embrit-
SSRT for the CDA706 alloy exhibiting SCC. Ductility loss can tling effect of sulfide concentration during SSRT for 90Cu-
also result from causes other than SCC (Ref 25), for example, 10Ni in seawater. Clearly, high levels of sulfide pollutant in
hydrogen charging through Reactions 6, 7, and I 1 on the sur- seawater results in a significant ductility loss and reduction in
face of the Cu-Ni alloy. In this study, where hydrogen coexists fracture strain. The ductility given by the elongation percent
through Reactions 6, 7, and 11 with the causative agents of was reduced from 30% when the concentration was 100 ppm to
SCC (sulfide ions and oxidation products, e.g., HS-), interpre- 15% when the concentration increased to 1000 ppm. The true
tation of results must be made carefully. Table 2 shows the em- fracture strain is a sensitive measure for SCC susceptibility.
Figures 8(c) and (d) show the true fracture strain versus the sul-
fide concentration.
90 ,.,I,,.I,,.I,.,I,.. I,
Specimen elongation is directly related to the time of failure
because a constant cross head extension is imposed during the
~" 80- slow strain rate test, and the load decreases and drops to zero at
t..,
failure. Figure 9 shows a sharp decrease in the time to failure
o
with increasing sulfide concentration. This further substanti-
70- ates the embrittling effects of sulfide ion and its byproducts.
From the previous results, it can be concluded that in slow
strain tests on 90Cu-10Ni in sulfide polluted seawater, the frac-
ture strain and the time to failure provide a strict criterion for
SCC susceptibility. The strain prior to crack initiation is also
determined by electrochemical monitoring of the specimen
,o during the test.
Figure 10 shows the electrochemical monitoring of the open
circuit potential, El=o. It was found that a similar trend exists in
1
this case when compared to the unstrained conditions shown
0 200 400 600 800 I000 1200 earlier in Fig. 3. A sharp systematic potential shift in the active
Sulfide Concentration (ppm) direction was observed in the strained conditions with increas-
ing sulfide concentration. This shift in potential is directly re-
Fig. 9 The embrittling effect of sulfide concentration during lated to the reaction occurring on the surface of the alloy as
slow strain rate testing (SSRT) for the 90Cu-10Ni alloy in outlined earlier. This active shift in potential results in hydro-
seawater. (a) Time to failure (linear plot). (b) Time to failure gen evolution via Reactions 6, 7, and 11, which become a pos-
sible cathodic partial process supporting the earlier predictions
that the sulfide also plays an indirect role in inducing hydrogen
-0.2 cracking. It appears that this effect becomes more pronounced
with increasing sulfide levels. The time dependent effects of
."~-0.3 sulfide on potential and mode of failure are broken down into
two opposing effects: high levels of sulfide (_>300 ppm) and
~_., -0.4 low levels of sulfide (_<100 ppm).
In the presence of high concentrations of sulfide (>300
"~ -0.5 ppm), the potential continues to increase from its initial active
values, which indicates a mild increase in crack velocity. Early
~ -0.6 crack initiation and propagation causes a shift in potential in
the noble direction indicative of a mild increase in propagating
o velocity of the crack. At high levels of sulfide, this effect is in-
"~ -0.7'
dependent of its concentration. The premature failure of the
specimen in these environments can easily be attributed to the
-0.8 -
significant increase in hydrogen charging and the associated
embrittling effect. This effect overwhelms the direct sulfide
-0.9 I I I I I
stress cracking contributed by sulfide and its byproducts. Thus,
0 0.1 0.2 0.3 0.4 0.5
for high levels of sulfide, the nature of the fracture is dominated
T i m e (106 S) by hydrogen embrittlement, and the role of sulfide stress crack-
Fig. 10 Open circuit potential diagram for the 90Cu-10Ni al- ing is minimized.
loy in sulfide polluted seawater during slow strain rate testing For environments of low sulfide pollutant (_<100 ppm), an
(SSRT) initial shift in the active direction is directly related to material

54if--Volume 6(4) August 1997 Journal of Materials Engineering and Performance

response to sulfide and, at later stages, crack initiation fol-
lowed by crack propagation occurs. The contribution of hydro-
gen in this case is minimal, and significant crack propagation
occurs through the action o f sulfide and its oxidation products.
The initial continued potential drop appears to be the result of
a film rupture process and the creation of an active surface at
the slip steps. Figure 10 shows this type of behavior for the case
o f a 100 ppm sulfide polluted environment. A metastable re-
gion o f potential occurs at about 90 x 103 s, which can be ex-
plained by pseudoequilibrium effects of the film free surface
including the newly formed crack and the repassivation proc-
ess due to sulfide and oxidation products. A large potential in-
crease occurs, apparently due to crack formation in the final
stage of the test. Figure 10 shows this type of potential rise. The
electrode potential reaches a maximum, and the specimen
breaks. It is expected that the fractured specimen will mainly
show sulfide stress cracking, and the contribution of hydrogen
is minimal. The total time to failure can also be determined
from the data (Fig. 10) for the low sulfide levels, which are
equal to 350 x 103 s (97 h). This is consistent with the failure
time of the SST.

3.2 Morphology of Fracture

Metallography or fractography is always used to verify the
presence of SCC after SSRT and can provide both quantitative
and qualitative descriptions of SCC severity. Both optical and
scanning electron microscopes were used to examine the failed
specimens. The presence of secondary cracks on the surface of
the tested material is a good indication of the severity o f SCC.
Table 2 shows the stereo microscopic observations with in-

Table 2 Toughness of the 90Cu-10Ni alloy measured by

the area under the o-~ curve as a function of sulfide
pollutant concentration

Sulfide environment,
ppm Observations o-e area, MJim3
0 Ductilematerial 106.19
100 Few secondarystress-corrosion 82.34
cracksin the necked region
300 Increasedsecondarystress- 57.47
corrosioncracks in the necked
region
500 Furtherincreasein secondary 47.35
stress-corrosioncracks in the
neckedregion
Fig. 11 Longitudinal cross section of a tensile gage region 1000 Secondarystress-corrosion 28.53
cracksover a large regionof
showing secondary stress-corrosion crack for the 90Cu-10Ni gage length
alloy in 300 ppm sulfide (200x)

(a) (b)

Fig. 12 (a) A photomicrograph of the 90Cu-10Ni alloy in 500 ppm sulfide (1100x) showing the embrittled region of fracture. (b) A photo-
micrograph of the 90Cu-10Ni alloy in 300 ppm sulfide (1500x) showing the ductile dimple type failure in the necked region

Journal of Materials Engineering and Performance Volume 6(4) August 1997--541

 Fig. 13 A photomicrograph of the 90Cu-10Ni alloy in 300 ppm
sulfide (700x) showing the intergranular crack propagation
(a)
Fig. 15 A photomicrograph of the 90Cu-10Ni alloy in 500 ppm sulfide (4500x) showing the intergranular decohesive fracture with slight
transgranular cracking
creasing sulfide concentrations. Clearly, SCC of alloys is envi-
ronment specific and is promoted by critical ranges of concen-
trations of the culprit ions. Shallow penetrations under
stress-corrosion circumstances indicate borderline conditions
between regions of severe SCC and pitting corrosion.
Laboratory observations showed that increasing the con-
centration of sulfide always increased the general corrosion
and the deposits of corrosion byproducts. The specimen was
encrusted with dark brown, loosely adhered scales. A range of
features from severe general corrosion, pitting, and secondary
stress corrosion cracks in the necked region were observed
upon examining the longitudinal cross section of the tensile
gage region (Fig 11). In general, secondary corrosion cracks on
the surface were increased upon increasing the sulfide concen-
tration, which increased the corrosivity of the environment
(Table 2). Figures 12(a) and (b) show typical fractographic fea-
tures of failed specimens.
542--Volume 6(4) August 1997
Fig. 14 A photomicrograph of the 90Cu- 10Ni alloy in 500 ppm
sulfide (7500x) showing the intergranular crack propagation region
(b)
The transition from brittle, intergranular propagation in
the SCC region (Fig. 12a) to ductile, dimple propagation in
the mechanical region at the bottom of the micrograph is shown
in Fig. 12(b). The secondary cracks were completely inter-
granular and oriented perpendicular to the direction of the ap-
plied stress.
The features were typical of what would be expected in nor-
mal SCC failure. Figure 13 shows extensive intergranular
cracking where transgranular cracking was less prominent.
The hydrogen ions resulting from Reactions 6, 7, and 11 are ad-
sorbed and diffuse into the alloy, resulting in the production of
localized cracking. The region of the alloy exposed at the crack
tip as the crack propagates by virtue of hydrogen embrittlement
and the applied stress are anodic to the oxidized sides of the
crack and the adjacent surface of the material, which results in
the continuation of the electrochemical attack and the further
evolution and absorption of hydrogen. The triaxial state of
Journal of Materials Engineering and Performance
 (a)
Fig. 16 A photomicrograph of the 90Cu- 10Ni alloy in 1000 ppm sulfide showing microcracks of intergranular type. (a) 2500x. (b) 4500x
stress, and the stress concentration at the crack tip accelerate
hydrogen embrittlement and provide a driving force for crack
propagation.
Figures 14 to 16 clearly show the view by SEM of the inter-
granular decohesion resulting from cracking. The crack
branching clearly indicates a constant crack growth rate over a
range of applied stress intensities.
4. Conclusions
The severity and type of SCC depends on the sulfide con-
centration in the seawater. The severity of SCC increases as the
sulfide concentration increases. It was found that 90Cu- 10Ni is
susceptible to sulfide cracking and hydrogen embrittlement.
The hydrogen embrittlement is predominant at higher concen-
trations of sulfide. The hydrogen attack is an indirect conse-
quence of a series of electrochemical reactions in this
sulfide-cupronickel alloy system. The stresses result in the rup-
ture of the corrosion product film, thus enhancing sulfide stress
cracking associated with the anodic dissolution in the low sul-
fide concentration range and hydrogen embrittlement dominat-
ing in the high sulfide concentration range. It was found that a
synergism exists between sulfide and stress, which enhances
the effect of the latter.
Acknowledgment
The partial support of this work by the Kuwait University
Research Administration is gratefully acknowledged.
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