J. Electrochem. Soc., Vol. 137, No. 2, February 1990 9 The Electrochemical Society, Inc.

411

dX = (D1)X {1} modulation frequency, Hz

t2 disk rotation frequency, Hz
d Y = (D1)Y

where dX, and dY are the vectors consisting of the pseudo- REFERENCES
spectral approximations to the first derivatives of the func- 1. J. Macdonald and J. A. Garber, This Journal, 124, 1022
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2. W. H. Smyrl, Abstract 689, p. 1099, The Electrochemi-
LIST OF SYMBOLS cal Society Extended Abstracts, Vol. 82-1, Montreal,
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A amplitude of time varying concentration perturba- 3. W. H. Smyrl, This Journal, 132, 1551 (1985).
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Co steady-state concentration mol/liter 7. E. Levart and D. Schuhmann, J. Electroanal. Chem.,
C electrical double layer capacitance, F 53, 77 (1974).
D diffusion coefficient, cm/s 8. P. S. Tyler, Private communication (1984).
Imi measured value of the imaginary part of the total 9. C. S. Lin, E.B. Denton, H. S. Gaskill, and G. L. Put-
impedance, t~ nam, Ind. Eng. Chem., 43, 2136 (1951).
(hIm)i difference between measured and theoretically de- 10. J. R. Selman and C. W. Tobias, Adv. Chem. Eng., 10,
termined imaginary part of the total impedance at 211 (1978).
j ~S_~t i ' t 2 11. A. C. Riddiford, "Advances in Electrochemistry and
Electrochemical Engineering," Vol. 4, p. 47, C.W.
K dimensionless frequency Tobias and P. Delahay, Editors, Interscience, New
Rs ohmic resistance in electrolyte, t~ York (1966).
Re~ measured value of the real part of the total imped- 12. C. Ho, I. D. Raistrick, and R. A. Huggins, This Journal,
ance, 127, 343 (1980).
(ARe)~ difference between measured and theoretically de- 13. J. E. B. Randles, Discuss. Faraday Soc., 1, 11 (1947).
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t2 (1974).
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Vz velocity in direction of disk axis, cm/s 127, 2603 (1980).
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cm 18. C. Deslouis, C. Gabrielli, and B. Tribollet, ibid., 130,
~f convective Warburg impedance at zero frequency, 2044 (1983).
19. W. G. Cochran, Proc. Cambridge Phil. Soc., 30, 365
Zw convective Warburg impedance, t~ (1934).
Zto~ total complex impedance for system, t~ 20. B. Tribollet, J. Newman, and W. H. Smyrl, To be pub-
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A Modified Double Loop EPR Technique for Detection of

Sensitization in Cast Stainless Steel
David L. Reichert* and Glenn E. Stoner*
Center for Electrochemical Science and Engineering, Department of Materials Science, University of Virginia,
Charlottesville, Virginia 22901

ABSTRACT
The double loop electrochemical potentiodynamic reactivation technique was developed to detect sensitization in
wrought stainless steel. Because cast stainless steel has a different microstructure than wrought stainless steel, neither the
double loop nor the single loop EPR technique has the selectivity required to detect sensitization. By using a modified
double loop EPR technique in which the peak potential is raised to 450 mV vs. SCE, the sweep rate is slowed to 3 V/h, and
the KSCN concentration is increased to 0.02M, sensitization can be detected in cast stainless steel.

Cast stainless steel is widely used in the nuclear industry
for valves, pumps, and plenums. Because these pieces are
welded into place and may have repair welds performed
on them, there is a danger of carbide formation resulting in
a chromium-depleted region adjacent to the carbides. This
region is susceptible to severe localized corrosion. This ef-
fect is called sensitization. For reasons of both safety and
economics, a reliable, nondestructive test method for de-
tecting sensitization in cast stainless steel is needed.
Both the single loop (1) and the double loop (2, 3) electro-
chemical potentiodynamic reactivation (EPR) techniques
* Electrochemical Society Active Member.
have been shown to be able to determine the degree of sen-
sitization in wrought stainless steel. The austenite-ferrite
duplex nature of cast stainless steel, however, means
stronger passivation characteristics for the CF-8, the cast
equivalent of wrought 304, than for the austenitic 304 (4).
The result of this is that neither the single loop nor the
double loop test methods have the selectivity required for
the detection of sensitization in cast stainless steel.
By modifying the test parameters of the double loop
method, a modified double loop EPR test was developed
that can determine the degree of sensitization in cast stain-
less steel.

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 412 J. Electrochem. Soc., Vol. 137, No. 2, F e b r u a r y 1990 9 The Electrochemical Society, Inc.

Development of Modified EPR Technique Modified Double Loop EPR

T h e d o u b l e loop E P R t e s t c o n s i s t s of a n a n o d i c s w e e p
f r o m t h e c o r r o s i o n p o t e n t i a l to a p e a k p o t e n t i a l in t h e pas- + 450 rnV

sive r e g i o n f o l l o w e d b y a r e a c t i v a t i o n s c a n f r o m t h e p e a k
p o t e n t i a l b a c k to t h e c o r r o s i o n p o t e n t i a l . I n s t a n d a r d dou-
b l e l o o p E P R tests, t h e s w e e p r a t e is 6 V/h, t h e p e a k p o t e n -
tial is 300 m V (vs. SCE), a n d t h e e l e c t r o l y t e is 0.5M H2SO4 +
t
POTENTIAL
ocSCAN
0.01M K S C N . T h e d e g r e e of s e n s i t i z a t i o n is t h e n deter-
m i n e d f r o m t h e ratio of t h e m a x i m u m c u r r e n t in t h e reac-
t i v a t i o n s c a n d i v i d e d b y t h e m a x i m u m c u r r e n t in t h e
a n o d i c scan, or Ir/I~. T h e g r e a t e r t h e r a t i o or, b e c a u s e I a is
a p p r o x i m a t e l y c o n s t a n t for a g i v e n m a t e r i a l (5), t h e g r e a t e r COBB I I
Ir Ia
t h e r e a c t i v a t i o n c u r r e n t Ir, t h e g r e a t e r t h e d e g r e e o f sensiti-
LOG CURRENT }1.
zation.
I n o r d e r for t h e E P R t e s t to b e s e l e c t i v e t h e r e m u s t b e 1) Electrolyte is 0.5M H2SO 4 + 0.02M KSCN
s i g n i f i c a n t i n c r e a s e s in t h e Ir/I~ v a l u e c o r r e s p o n d i n g to in-
c r e a s e s i n t h e level of s e n s i t i z a t i o n i n t h e m a t e r i a l . T h e 2) Start Ar~odic Scan at E CORR
s t a n d a r d d o u b l e loop E P R t e s t w a s n o t s e l e c t i v e b e c a u s e
the natural scatter in the experimental results was larger 3) Sweep at 3 V/Hr
t h a n t h e d i f f e r e n c e s b e t w e e n t h e a v e r a g e Ir/Ia v a l u e s for
m a t e r i a l s w i t h d i f f e r e n t levels of s e n s i t i z a t i o n . 4) Reverse Direction at 450 mV
T h e r e f o r e , t h e s w e e p rate, t h e electrolyte, a n d t h e p e a k
p o t e n t i a l p a r a m e t e r s w e r e e x a m i n e d to d e t e r m i n e c h a n g e s Fig. 1. Schematic of the modified double loop EPR test
t h a t w o u l d m a k e t h e t e s t m o r e selective. T h e s e l e c t i o n of
t h e s c a n rate w a s a c o m p r o m i s e b e t w e e n low r a t e s t h a t led
to a l e n g t h y t e s t a n d c a u s e d m o r e g e n e r a l c o r r o s i o n a n d H2SO4 + 0.02M K S C N e l e c t r o l y t e m u s t b e m a d e f r e s h e a c h
pitting, and high rates which provided a shorter test time d a y b u t c a n b e u s e d r e p e a t e d l y . A s t r o n g s m e l l of H2S indi-
b u t led to a loss of s e l e c t i v i t y (3, 6). I t w a s f o u n d , t h r o u g h c a t e s t h a t t h e s o l u t i o n s h o u l d b e replaced. A r g o n w a s b u b -
e x p e r i m e n t a t i o n , t h a t t h e s t a n d a r d s w e e p r a t e w a s too fast b l e d t h r o u g h t h e e l e c t r o l y t e e v e n t h o u g h it w a s deter-
a n d t h a t s l o w i n g t h e s w e e p r a t e i n h a l f to 3 V/h i m p r o v e d m i n e d t h a t p u r g i n g w a s u n n e c e s s a r y for t h e E P R t e s t (10).
t h e s e l e c t i v i t y of t h e test. It w a s f o u n d t h a t t h i s i m p r o v e d t h e l o n g e v i t y o f t h e elec-
trolyte. T h e s a m p l e s w e r e 1.27 • 1.27 c m CF-8 p l a t e s
I n o r d e r to f u r t h e r i m p r o v e t h e selectivity, t h e electro-
m o u n t e d i n M a r a g l a s I w i t h a s t a i n l e s s steel w i r e s p o t
lyte c o m p o s i t i o n w a s also e x a m i n e d . It w a s f o u n d t h a t
d o u b l i n g t h e c o n c e n t r a t i o n of t h e H2SO4 to 1.0M l o w e r e d w e l d e d to t h e i r b a c k side. T h e w i r e w a s s e a l e d in a glass
t h e p H f r o m 0.29 to -0.005 a n d i n c r e a s e d b o t h Ia a n d Ir. T h e t u b e t h a t e x t e n d e d o u t s i d e t h e cell; t h e c o u n t e r e l e c t r o d e
w a s p l a t i n u m a n d t h e r e f e r e n c e e l e c t r o d e w a s a n SCE. T h e
result was a surface that had undergone greater attack
S C E w a s i n a t u b e filled w i t h s a t u r a t e d KC1 a n d s e p a r a t e d
w i t h n o i m p r o v e m e n t in selectivity. H a l v i n g t h e H2SO4
c o n c e n t r a t i o n to 0.25M a n d a p H of 0.58, d e c r e a s e d t h e ag- 1 ACME, Division Allied Products, New Haven, Connecticut
g r e s s i v e n e s s of t h e e l e c t r o l y t e to t h e p o i n t w h e r e it w a s too 06505.
b e n i g n to b e useful. T h u s , c h a n g i n g t h e H2SO4 c o n c e n t r a -
t i o n f r o m 0.5M d i d n o t i m p r o v e t h e test. A l t e r a t i o n s of t h e
K S C N c o n c e n t r a t i o n , h o w e v e r , p r o v e d useful. K S C N acts
as a n a c t i v a t o r b y p r o m o t i n g t h e b r e a k d o w n o f t h e p a s s i v e
film. D u r i n g t h e a n o d i c scan, t h e K S C N i n s u r e d t h a t t h e
a i r - f o r m e d p a s s i v e film w a s b r o k e n d o w n a n d t h a t t h e en-
tire s u r f a c e w a s a c t i v e (3). D u r i n g t h e r e a c t i v a t i o n scan, t h e
K S C N s e r v e d to a c t i v a t e localized r e g i o n s t h a t h a d a less
r e s i s t a n t p a s s i v e film. T h e s e r e g i o n s m a y b e g r a i n or p h a s e
b o u n d a r i e s w h o s e p a s s i v e film was less r e s i s t a n t d u e to
c o m p o s i t i o n g r a d i e n t s or t h e y m a y b e r e g i o n s o f low re~
s i s t a n c e d u e to c h r o m i u m d e p l e t i o n (7). I f t h e K S C N con-
c e n t r a t i o n w a s too h i g h , g e n e r a l c o r r o s i o n o c c u r r e d d u r i n g
t h e r e a c t i v a t i o n s c a n a n d t h e r e p r o d u c i b i l i t y of t h e t e s t re-
s u l t s w e r e d e c r e a s e d . I f t h e c o n c e n t r a t i o n w a s too low, o n e
o b t a i n e d i n s u f f i c i e n t r e a c t i v a t i o n c u r r e n t s (6, 8, 9). It w a s
f o u n d t h a t d o u b l i n g t h e c o n c e n t r a t i o n to 0.02M K S C N w a s
a g o o d b a l a n c e b e t w e e n sufficiently a g g r e s s i v e a t t a c k a n d
reproducibility.
T h e s l o w i n g of t h e s c a n rate a n d t h e d o u b l i n g of t h e
K S C N c o n c e n t r a t i o n m a d e t h e t e s t m o r e aggressive. Be-
c a u s e t h e p a s s i v e c u r r e n t s h o w e d little c h a n g e b e t w e e n
300 a n d 450 m V (vs. SCE) a n d n o n e w r e a c t i o n s w e r e intro-
d u c e d , t h e s i m p l e s t w a y to give t h e s a m p l e m o r e t i m e to
f o r m its p a s s i v e film w a s to raise t h e p e a k potential. Rais-
i n g t h e p e a k p o t e n t i a l f r o m 300 to 450 m V a l l o w e d n o n s e n -
sitized s a m p l e s to w i t h s t a n d t h e m o r e a g g r e s s i v e t e s t con-
d i t i o n s a n d m a i n t a i n a l o w Ir/I~ v a l u e w h i l e t h e s e n s i t i z e d
s a m p l e s s h o w e d s i g n i f i c a n t i n c r e a s e s i n I~/I~ a c c o r d i n g to
t h e i r level o f s e n s i t i z a t i o n . W h e n all o f t h e s e c h a n g e s w e r e
c o m b i n e d i n t o a m o d i f i e d d o u b l e loop E P R test, it p r o v e d
to b e s e l e c t i v e a n d r e p r o d u c i b l e in d e t e c t i n g s e n s i t i z a t i o n
i n c a s t s t a i n l e s s steel. F i g u r e 1 s h o w s a s c h e m a t i c of t h e
m o d i f i e d d o u b l e loop E P R test.

Experimental
A P A R M o d e l 273 p o t e n t i o s t a t a n d 351 p r o g r a m m e r
w e r e u s e d to c o n t r o l t h e E P R tests, a n d a w a t e r b a t h w a s
u s e d to m a i n t a i n a c o n s t a n t 30~ t e m p e r a t u r e . T h e 0.5M Fig. 2. Optical micrographsof CF-8 heat-treated at 700~

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 J. Electrochem. Soc., Vol. 137, No. 2, February 1990 9 The Electrochemical Society, Inc. 413

DL EPR AT 3V/Hr; 450mY PEAK POTENTIAL Table I. Degree of sensitization values

0.02M KSCN + 0.5M HES04
175
<-- 15 H O U R Heat-treatment Time 99% confidence
......
: 800~
700oc D.O.S. = 396 temperature (h) lr/Ia • 10-4 interval (+/-)
150 ---s--- 600oc
Annealed -- 0.9 0.1
N
125 Annealed -- 0.7 0.2
E~ 800~ 0.1 12.3 5.4
~ 1oo 1.0 19.2 7.9
5.0 7.5 4.1
15 4.2 1.3
100 0.7 0.3
300 4.6 4.4
~ 50
700~ 0.1 3.3 1.5
0.5 43.8 5.7
/
1.0 103 13
~ 25 .9 / -. 2.0 135 18
5.0 35.8 10.9
15 11.2 3.2
100 7.6 1.6
A 0.1 0.5 1.0 2.0 5.0 15 100 300 300 7.0 1.2
HEAT TREATHENTTIME (HOURS) 600~ 0.5 3.6 0.8
A = ANNEALED CONDITION 1.0 15.1 7.7
2.0 11.1 1.9
Fig. 3. Plot of degree of sensitization values 5.0 30.1 4.5
15 396 95

f r o m t h e b u l k electrolyte w i t h a glass frit and a capillary

tube. The samples w e r e p o l i s h e d to 600 grit to allow obser-
v a t i o n w i t h an optical m i c r o s c o p e after the E P R test was
p e r f o r m e d . T h e least a m o u n t of e x p e r i m e n t a l scatter was
o b t a i n e d w h e n the samples w e r e tested 3-6 m i n after b e i n g
polished. The s w e e p rate was 3 V/h and the p e a k potential
was 450 m V (vs. SCE).
P r i o r to p e r f o r m i n g the E P R tests, t h e samples, w h i c h
w e r e r e c e i v e d in the a n n e a l e d condition, w e r e heat-
treated. T h e samples w e r e e n c a p s u l a t e d with a backfill of
1/2 a t m o s p h e r e e r g o n to p r e v e n t decarburization d u r i n g
h e a t - t r e a t m e n t I s o t h e r m a l h e a t - t r e a t m e n t s at three differ-
ent t e m p e r a t u r e s w e r e used: at 800~ for 0.1, 1.0, 5.0, 15,
100, and 300h; at 700~ for 0.1, 0.5, 1.0, 2.0, 5.0, 15, 100, and
300h; and at 600~ for 0.5, 1.0, 2.0, 5.0, and 15h. T h e s e tem-
p e r a t u r e s and t i m e s g a v e a w i d e range of levels of sensiti-
zation.
Optical m i c r o s c o p y was p e r f o r m e d to correlate the mi-
c r o s t r u c t u r e to t h e h e a t - t r e a t m e n t S a m p l e s w e r e m o u n t e d
in e p o x y and p o l i s h e d w i t h d i a m o n d paste to a 1 ~m sur-
face finish before b e i n g e t c h e d w i t h diluted a q u a regia
(15 m l HC1 + 5 m l HNO3 + 30 m l H 2 0 ) followed with
M u r a k a m i ' s etch (10g K3Fe(CN)6 + 10g K O H + 100 ml
H20). This c o m b i n a t i o n stains the ferrite yellow/brown,
the carbides dark, and the sigma phase blue.
peratures, healing occurs v e r y rapidly allowing only low
levels of sensitization to develop. At low t e m p e r a t u r e s , but
a b o v e 500~ the Cr can diffuse fast e n o u g h to f o r m the car-
bides but not fast e n o u g h to p r e v e n t the region a d j a c e n t to
the carbides f r o m b e c o m i n g d e p l e t e d of Cr (12), and t h e
material can b e c o m e severely sensitized.
T h e s e effects are seen in Fig. 3. At 800~ healing is v e r y
rapid and the peak level of sensitization is low. At 700~ it
takes longer for the sensitization to develop, but t h e onset
of healing is delayed e v e n further. The result of this is a
m u c h h i g h e r degree of sensitization after 2h and a slower
rate of healing that finally reduces the d e g r e e of sensitiza-
tion to the level of the 800~ tests after 300h. At 600~ the
o n s e t of sensitization is significantly delayed, but after 15h
there is no indication of healing and the d e g r e e of sensiti-
zation value, Ir/I~, has a p p r o a c h e d 400 • 10 -4. The results
f r o m t h e s e three h e a t - t r e a t m e n t t e m p e r a t u r e s clearly
s h o w that the modified d o u b l e loop E P R t e c h n i q u e can be
u s e d to detect sensitization in cast stainless steel.
Acknowledgment
This w o r k was s u p p o r t e d by E. I. du P o n t de N e m o u r s ,
Incorporated, W e s t i n g h o u s e - S a v a n n a h R i v e r P l a n t and
t h e C e n t e r for I n n o v a t i v e Technology.

Results and Conclusions M a n u s c r i p t s u b m i t t e d May 3, 1989; revised m a n u s c r i p t

The optical m i c r o g r a p h s seen in Fig. 2 s h o w the progres-
sion of carbide and s i g m a phase formation. F i g u r e 2a is of
a s a m p l e that has b e e n h e a t e d for 0.1h at 700~ D a r k e r col-
ored ferrite pools in austenite are evident, but there are no
c a r b i d e s visible at 1000 t i m e s magnification. Figures 2b, c,
d, and e, w h i c h w e r e h e a t e d for 0.5, 1.0, 2.0, and 5.0h, re-
spectively, s h o w the b u i l d u p of carbides, the small, v e r y
dark particles, along the phase boundaries. S i g m a phase
appears in Fig. 2f (15h at 700~ as small particles intermin-
gled w i t h the carbides. In Fig. 2g and h, w h i c h s h o w the
100 and 300h h e a t - t r e a t m e n t s at 700~ the sigma p h a s e can
be seen to h a v e g r o w n and c o n s u m e d increasing a m o u n t s
of the ferrite phase. T h e s e m i c r o g r a p h s s h o w that a range
of m i c r o s t r u c t u r e s h a v e b e e n p r o d u c e d that can be u s e d to
m o d i f y the E P R test for use on cast stainless steel.
T h r e e samples of each h e a t - t r e a t m e n t w e r e tested five
t i m e s each and the average d e g r e e of sensitization was
plotted vs. h e a t - t r e a t m e n t in Fig. 3. T h e s e values and the
m a g n i t u d e s of t h e 99% confidence intervals are listed in
T a b l e I.
Stainless steel is capable of a process called healing
w h e r e Cr diffuses into the d e p l e t e d zones from the b u l k
raising the Cr level and curing the sensitized region (11). At
h i g h t e m p e r a t u r e s (above 825~ the Cr can diffuse fast
e n o u g h to p r e v e n t Cr d e p l e t i o n a d j a c e n t to t h e carbides
t h e r e b y p r e v e n t i n g sensitization. A t slightly lower tern-
r e c e i v e d Aug. 7, 1989. This was P a p e r 45 p r e s e n t e d at the
Los Angeles, CA, M e e t i n g of the Society, May 7-12, 1989.
The University of Virginia assisted in meeting the publi-
cation costs of this article.
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