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90Cu-10Ni Alloy To SCC in Seawater
90Cu-10Ni Alloy To SCC in Seawater
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.
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:
0.8
Ttta~ 1
elecCro~e 0.6
_-: :
~ 0.4
"N
R~bloer
I- -- -- -XA t
cork
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
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
"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
Fig. 6 Cyclic potentiodynamic diagrams for the unstrained 90Cu-10Ni alloy in sulfide polluted seawater
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)
~
30- e~
25- ~0
15
, , , i . . . t . . . I . . . i . . . ! . . i
10 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)
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
(a) (b)
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- The transition from brittle, intergranular propagation in
ronment specific and is promoted by critical ranges of concen- the SCC region (Fig. 12a) to ductile, dimple propagation in
trations of the culprit ions. Shallow penetrations under the mechanical region at the bottom of the micrograph is shown
stress-corrosion circumstances indicate borderline conditions in Fig. 12(b). The secondary cracks were completely inter-
between regions of severe SCC and pitting corrosion. granular and oriented perpendicular to the direction of the ap-
Laboratory observations showed that increasing the con- plied stress.
centration of sulfide always increased the general corrosion The features were typical of what would be expected in nor-
and the deposits of corrosion byproducts. The specimen was mal SCC failure. Figure 13 shows extensive intergranular
encrusted with dark brown, loosely adhered scales. A range of cracking where transgranular cracking was less prominent.
features from severe general corrosion, pitting, and secondary The hydrogen ions resulting from Reactions 6, 7, and 11 are ad-
stress corrosion cracks in the necked region were observed sorbed and diffuse into the alloy, resulting in the production of
upon examining the longitudinal cross section of the tensile localized cracking. The region of the alloy exposed at the crack
gage region (Fig 11). In general, secondary corrosion cracks on tip as the crack propagates by virtue of hydrogen embrittlement
the surface were increased upon increasing the sulfide concen- and the applied stress are anodic to the oxidized sides of the
tration, which increased the corrosivity of the environment crack and the adjacent surface of the material, which results in
(Table 2). Figures 12(a) and (b) show typical fractographic fea- the continuation of the electrochemical attack and the further
tures of failed specimens. evolution and absorption of hydrogen. The triaxial state of
stress, and the stress concentration at the crack tip accelerate 3. R.N. Parkins, Slow Strain Rate Testing--25 Years Experience,
hydrogen embrittlement and provide a driving force for crack Slow Strain Rate Testingfor the Evaluation of Environmentally In-
propagation. duced Cracking: Research and Engineering Applications, ASTM
STP 1210, R.D. Kane, Ed., ASTM, 1993, p 7-21
Figures 14 to 16 clearly show the view by SEM of the inter-
4. L.E. Eiselstein, B.C. Syrett, S.S. Wing, and R.D. Caligiuri, Cor-
granular decohesion resulting from cracking. The crack ros. Sci., Vol 23 (No. 3), 1993, p 223-239
branching clearly indicates a constant crack growth rate over a 5. A.M. Beccaria, G. Poggi, P. Traverso, and M. Giazza, Corros.
range of applied stress intensities. Sci., Vol 32 (No. 11), 1991, p 1263-1275
6. J.N. Alhajji and M.R. Reda, Corros. Sci., Vol 34 (No. 1), 1993,
p 163-177
4. Conclusions 7. J.N. Alhajji and M.R. Reda, Corros. Sci., Vo149, 1993, p 809
8. J.N. Alhajji and M.R. Reda, "The Effects of Some Common
The severity and type of SCC depends on the sulfide con- Pollutants on the Corrosion of Copper-Nickel Alloys in Seawa-
centration in the seawater. The severity of SCC increases as the ter," The First UAB Symposium on Materials Science: Corro-
sion and Corrosion Protection, United Arab Emirates, Dec 12-
sulfide concentration increases. It was found that 90Cu- 10Ni is 14, 1993
susceptible to sulfide cracking and hydrogen embrittlement. 9. M.R. Reda and J.N. Alhajji, "The Effect of Complexing Agents
The hydrogen embrittlement is predominant at higher concen- on the Corrosion of Copper/Nickel Alloys in Sulfide Polluted
trations of sulfide. The hydrogen attack is an indirect conse- Seawater under Impingement Attack," 12th International Corro-
quence of a series of electrochemical reactions in this sion Congress (Houston, TX), National Association of Corrosion
sulfide-cupronickel alloy system. The stresses result in the rup- Engineers, 1993
ture of the corrosion product film, thus enhancing sulfide stress 10. M.R. Reda and J.N. Alhajji, Br. Corros. J., Vo130 (No. 1), 1995,
cracking associated with the anodic dissolution in the low sul- p 56-62
fide concentration range and hydrogen embrittlement dominat- 11. J.N. Alhajji and M.R. Reda, J. Electrochem. Soc., Vol 141 (No.
6), 1994, p 1432
ing in the high sulfide concentration range. It was found that a
12. D. Thompson, Material Research Study, Vol 1, 1961, p 108
synergism exists between sulfide and stress, which enhances
13. J. Popplewell and T. Gearing, Corrosion, Vol 8, 1975, p 279-286
the effect of the latter.
14. K. Habib and A. Husain, Stress Corrosion Cracking of Copper-
Nickel Alloys in Sulfide Polluted Natural Seawater at Moderate
Acknowledgment Temperature, Desalination, Vol 97, 1994, p 29-34
The partial support of this work by the Kuwait University 15. B.C. Syrett, Corros. Sci., Vol 21 (No. 3), 1981, p 187-209
Research Administration is gratefully acknowledged. 16. C. Kato, H.W. Pickering, and J.E. Castle, J. Electrochem. Soc.,
Vol 3 (No. 6), 1984, p 1225
17. R. Francis, Br. Corr. J., Vol 20 (No. 4), 1985, p 175
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