The 1970 Campbell Memorial Lecture

The American Society for Metals

Perspectives on Corrosion of Materials

MARS G. FONTANA

P e r s p e c t i v e s on c o r r o s i o n l o o k s b a c k 10 y e a r s o r s o a n d i n t o t h e ' s e v e n t i e s . G e n e r a l i g n o r -
ance by many engineering disciplines and others and resultant costly failures are empha-
s i z e d . T h e s c o p e of t h e c o r r o s i o n p r o b l e m i s d e s c r i b e d . D i s c u s s e d a r e f o r m s of c o r r o s i o n
a n d m e t h o d s f o r c o m b a t t i n g ; s e c o n d a r y r e a c t i o n s ; e f f e c t s of m a t e r i a l s s t r u c t u r e ; a d v a n c e s
in techniques for measuring corrosion; important developments; and needs for the 1970's.
Need for involvement by metallurgists is emphasized.

MARS G. FONTANA received a bachelor's degree in Chemical Engi- IT i s i n d e e d a n h o n o r to b e s e l e c t e d b y t h e A m e r i c a n

neering in June 1931 and his master's, September 1932, and Ph.D.,
January 1935, in Metallurgical Engineering, all from the University of
Michigan. He was a research assistant in the Department of Engineering
Research 1929-1934. From October 1934 through October 1945, he
was a metallurgical engineer and supervisor, Engineering Department,
E. I. duPont de Nemours and Co., Wilmington, Del. In addition to cor-
rosion and other metallurgical problems, he pioneered industrial uses
of nylon, teflon, and other nonmetallics, and while associated with Du-
Pont, he developed patents on corrosion indicating, recording and
testing devices. He joined the staff at Ohio State in November 1945.
In addition to his position as Chairman of the Department of Metal-
lurgical Engineering he was named Ohio Regent's Professor in 1967,
Duriron Professor in 1970, and is Director of the Corrosion Center
which is the largest university effort in corrosion in the country. He
was president of the National Association of Corrosion Engineers in
1952 and N.A.C.E. presented him with the Frank Newman Speller
Award in Corrosion Engineering in 1956. He is editor of the journal
CORROSION since it started its new format in 1962. He was chairman
of the Corrosion Division of the Electrochemical Society in 1948. He
received the Distinguished Engineering Alumnus Citation in 1953 and
the Sesquicentennial Award in 1967 from the University of Michigan.
He was elected to the National Academy of Engineering in 1967. In
1969 he received honorary membership to the American Society for
Metals.
S o c i e t y f o r M e t a l s t o p r e s e n t t h e 1970 E d w a r d D e M i l l e
C a m p b e l l L e c t u r e w h i c h w a s e s t a b l i s h e d i n 1926. I
f e e l h u m b l e i n h a v i n g m y n a m e a d d e d t o t h i s l i s t of
d i s t i n g u i s h e d l e c t u r e r s . It i s a p r i v i l e g e t o p a y t r i b u t e
to P r o f e s s o r C a m p b e l l a n d t o r e c o g n i z e h i s p i o n e e r -
i n g e f f o r t s in e d u c a t i n g s t u d e n t s f o r w o r k i n t h e s t e e l
i n d u s t r y . It i s a l s o a p l e a s u r e to h o n o r a p r o f e s s o r of
my own alma mater. Unfortunately, I did not have the
o p p o r t u n i t y t o a s s o c i a t e w i t h h i m b e c a u s e h e d i e d on
S e p t e m b e r 19, 1 9 2 5 , a l m o s t 2 y e a r s t o t h e d a y b e f o r e
I a r r i v e d in A n n A r b o r a s a f r e s h m a n to a t t e n d t h e
U n i v e r s i t y of M i c h i g a n . W e w o r k e d in t h e s a m e b u i l d -
ing and I heard much about Professor Campbell from
my professors.
Professor Campbell's main interest was in the field
of s t e e l . He w a s b l i n d e d a t a g e 28 by a n e x p l o s i o n of
g l a s s w a r e w h i l e d i s s o l v i n g s t e e l in h y d r o c h l o r i c a c i d .
( H y d r o g e n i s a b y - p r o d u c t of c o r r o s i o n of i r o n . ) T h i s
serious handicap did not deter him from continuing a
fruitful career. What an inspiration he must have been
to h i s s t u d e n t s of m e t a l l u r g y l I w o n d e r w h a t h i s r e a c -
t i o n w o u l d b e to t h e c a m p u s u n r e s t of t o d a y . I ' m s u r e

METALLURGICAL TRANSACT|ONS VOLUME 1,DECEMBER 1970-3251

he e n j o y e d his 35 y e a r s at the u n i v e r s i t y and I can
s h a r e his delight in a s s o c i a t i n g with s t u d e n t s and in
noting t h e i r a c c o m p l i s h m e n t s a f t e r graduation. The
ASM a l s o r e c o g n i z e d his a c c o m p l i s h m e n t s in 1921 by
b e s t o w i n g on him H o n o r a r y M e m b e r s h i p p r e c e d e d only
by Sir R o b e r t Hadfield and H e n r y M a r i o n Howe.
At t h i s t i m e , I should like to acknowledge the i n s p i -
r a t i o n and t r a i n i n g r e c e i v e d f r o m P r o f e s s o r John
C h i p m a n , my Ph.D. a d v i s e r . The d i s s e r t a t i o n was in
the f i e l d of t h e r m o d y n a m i c s of s t e e l m a k i n g and p a r -
t i c u l a r l y f e r r o u s oxide in l i q u i d iron. The b a s i c r e a c -
tion s t u d i e d was:
Fe + H20 = FeO + H~ [1]
My p r o f e s s i o n a l c a r e e r , however, i s in the field of
c o r r o s i o n . A p e r s o n ' s i n t e r e s t s and viewpoints can
change. Looking back at this equation, I m i g h t now be
i n c l i n e d to d e s c r i b e it as the c o r r o s i o n of liquid i r o n
at 1600~ by w a t e r vapor!
As an e d u c a t o r in the field of c o r r o s i o n , I a m p l e a s e d
to p r e s e n t this l e c t u r e at this t i m e in t e c h n o l o g i c a l
h i s t o r y , b e c a u s e the c o r r o s i o n p r o b l e m n e e d s to be
b r o u g h t f o r c e f u l l y and vividly to the attention of e n -
g i n e e r s of all d i s c i p l i n e s and in a l l f i e l d s of e n d e a v o r .
P r o b a b l y the m o s t i m p o r t a n t s i n g l e p e r s p e c t i v e that
n e e d s e m p h a s i z i n g is that there is an overwhelming
need f o r education of m a t e r i a l s people and of a l l e n -
g i n e e r i n g d i s c i p l i n e s r e g a r d i n g the p e s t i l e n c e of c o r -
rosion.
A s u b s t a n t i a l p o r t i o n of g o v e r n m e n t and i n d u s t r i a l
funds f o r c o r r o s i o n should be a l l o c a t e d for well c o n -
ceived educative v e n t u r e s . The r e t u r n on this i n v e s t -
m e n t should be g r e a t . In m y y e a r s of e x p e r i e n c e I
have s e e n only a handful of f a i l u r e s due to c a u s e s
which r e q u i r e d new, as y e t u n d e v e l o p e d , m a t e r i a l s .
Virtually all premature corrosion failures these days
occur f o r reasons which w e r e already well known and
these failures can be prevented.
U n f o r t u n a t e l y , m a n y d e s i g n people and other e n g i -
n e e r s a r e woefully i g n o r a n t of c o r r o s i o n and its r a m i -
f i c a t i o n s and do not c o n s i d e r the c o r r o s i o n a s p e c t s
as they should. As a r e s u l t , m a n y unexpected and
c o s t l y f a i l u r e s o c c u r . Many v i o l a t e the m o s t s i m p l e
f u n d a m e n t a l s or a x i o m s of c o r r o s i o n . Changes d u r i n g
the d e s i g n stage a r e e a s i l y m a d e and this is "good
preventive m e d i c i n e . " I believe my major contribution
t o w a r d s c o m b a t t i n g c o r r o s i o n i s not c o r r o s i o n r e -
s e a r c h o r alloy d e v e l o p m e n t , but r a t h e r the t e a c h i n g
of a c o u r s e in c o r r o s i o n to h u n d r e d s of e n g i n e e r i n g
s t u d e n t s d u r i n g the p a s t 25 y e a r s . The a v e r a g e n u m -
b e r p e r y e a r has been about 75 d u r i n g r e c e n t y e a r s ,
i n c l u d i n g s t u d e n t s in p r a c t i c a l l y a l l b r a n c h e s of e n g i -
n e e r i n g . Some s p e c i a l i z e in c o r r o s i o n as a c a r e e r ,
but m o s t e l e c t this c o u r s e f o r g e n e r a l b a c k g r o u n d
p u r p o s e s . At l e a s t these young m e n and women will
r e c o g n i z e a c o r r o s i o n p r o b l e m when they e n c o u n t e r
one and have an idea how to solve it, i n s t e a d of m e r e l y
r e g a r d i n g c o r r o s i o n as a n e c e s s a r y evil.
The c o r r o s i o n of m a t e r i a l s i s a m a t t e r of t e c h n i c a l
c o n c e r n in t i m e s of peace as w e l l as war. It affects
the e c o n o m y , safety, r e l i a b i l i t y , and legal l i a b i l i t y of
c o n s u m e r goods and p e o p l e - o r i e n t e d a c t i v i t i e s (pollu-
tion c o n t r o l , s u r g i c a l i m p l a n t s , food p r o c e s s i n g , o c e a n
e n g i n e e r i n g ) . All fields of e n g i n e e r i n g should have a
m i n i m a l a p p r e c i a t i o n for p o s s i b l e c a u s e s of c o r r o s i o n -
3252-VOLUME 1, DECEMBER 1970
induced d e t e r i o r a t i o n of t h e i r r e s p e c t i v e p i e c e s of
e q u i p m e n t . A t t a c k i n g the c o r r o s i o n p r o b l e m r e q u i r e s
a t r u l y i n t e r d i s c i p l i n a r y effort. In fact, c o r r o s i o n of-
f e r s one of the r i c h e s t f i e l d s for i n t e r d i s c i p l i n a r y a c -
tivity. We should work together to e n c o u r a g e m o r e
and b r o a d e r i n v o l v e m e n t of v a r i o u s d i s c i p l i n e s in c o r -
rosion research.
S u p e r a l l o y s and s p e c i a l m a t e r i a l s m a y have sex ap-
peal to r e s e a r c h w o r k e r s , but the " a c t i o n " will always
be with l o w - c o s t m a t e r i a l s (i.e., c a r b o n steel). We
need to spend m o r e effort toward d e v i s i n g e c o n o m i c a l
and r e l i a b l e t e c h n i q u e s for u s i n g i n e x p e n s i v e m a t e r i -
a l s to slow the s p i r a l of c o r r o s i o n c o s t s . I have n e v e r
s e e n m o r e than a handful of c o r r o s i o n f a i l u r e s which
r e s u l t e d f r o m a defect in the m a n u f a c t u r e of the m a -
t e r i a l . Virtually all corrosion failures r e s u l t f r o m
carelessness on the part of the user or poor choice of
material or configuration by the designer.
The c o n s u m e r , u s e r , or c u s t o m e r g e n e r a l l y does
not p a r t i c u l a r l y c a r e which m a t e r i a l is u s e d to solve
his p r o b l e m or how it is produced, as long as it does
the job e c o n o m i c a l l y , r e l i a b l y , and s a f e l y . T h e r e f o r e ,
it is n e c e s s a r y f o r the c o r r o s i o n e n g i n e e r to be well
v e r s e d in the p r o p e r t i e s of a l l types of m a t e r i a l s of
c o n s t r u c t i o n . C o r r o s i o n c o n s i d e r a t i o n s a r e for m u c h
e n g i n e e r i n g e q u i p m e n t the l i m i t i n g f a c t o r to its l i f e -
time.
B e c a u s e of m y b a c k g r o u n d , it is i n t e r e s t i n g that
a p p a r e n t l y not one of the p r e v i o u s l e c t u r e s has c o n -
s i d e r e d solely the s u b j e c t of c o r r o s i o n . It s e e m s that
winning, f a b r i c a t i n g , and developing m a t e r i a l s a r e
only half the b a t t l e . The other half is k e e p i n g the m a -
t e r i a l intact during its operating lifetime--and this is
where corrosion becomes the dominating considera-
tion.
More metallurgists should become involved and
better informed in corrosion. For example, the metal-
lurgist through the u s e of s o p h i s t i c a t e d p h y s i c a l m e t -
a l l u r g y has d e v e l o p e d a l l o y s with t e n s i l e s t r e n g t h s of
300,000 to 400,000 p s i and then finds that they a r e
s u s c e p t i b l e to s t r e s s c o r r o s i o n when e x p o s e d to s e a
w a t e r or even to a b s o l u t e l y p u r e w a t e r ! C o r r o s i o n
p r o b l e m s will i n c r e a s e as we go to p r o c e s s e q u i p m e n t
o p e r a t i n g at h i g h e r t e m p e r a t u r e s and p r e s s u r e s and
as we f a r m o r o t h e r w i s e exploit the o c e a n s and a l s o
in the solving of our p r o b l e m s of p o l l u t i o n . The m e t -
a l l u r g i s t should be an equal p a r t n e r in the solution of
c o r r o s i o n p r o b l e m s . T h i s is one r e a s o n why I wel-
come this o p p o r t u n i t y to p r e s e n t a p i c t u r e of c o r r o -
sion to the A m e r i c a n Society for M e t a l s .
The ASM now i n c l u d e s n o n m e t a l s , which has been
c o m m o n in the c o r r o s i o n b u s i n e s s . U n d e r a p p r o p r i -
ate c i r c u m s t a n c e s n o n m e t a l s a r e s u b j e c t to s o m e of
the s a m e m o d e s of d e t e r i o r a t i o n as m e t a l s . F o r ex-
a m p l e , a c a s t epoxy r e s i n will c r a c k in a c a u s t i c so-
lution b e c a u s e of r e s i d u a l s t r e s s e s . If it is s t r e s s -
r e l i e v e d it does not c r a c k . If s t r e s s - r e l i e v e d and then
an e x t e r n a l s t r e s s applied, it will c r a c k . P o l y e t h y l e n e
also c r a c k s in c e r t a i n e n v i r o n m e n t s .
SCOPE O F THE CORROSION P R O B L E M
The f o r m a l d e f i n i t i o n of the t e r m " C o r r o s i o n " is
often confused, d e p e n d i n g on the s p e c i a l t y of the p e r -
son p r o v i d i n g the definition. It is, for e x a m p l e , c o m -
mon to think of c o r r o s i o n a s being only an e l e c t r o -
METALLURGICALTRANSACTIONS
c h e m i c a l p r o c e s s o r one a s s o c i a t e d only with aqueous
s o l u t i o n s . I b e l i e v e that c o r r o s i o n should be d e f i n e d
as the " d e g r a d a t i o n of a m a t e r i a l c a u s e d by an e n v i r -
o n m e n t . " T h e r e a r e a n u m b e r of n u a n c e s i m p l i e d by
this d e f i n i t i o n . F i r s t , the e n v i r o n m e n t need not be
w a t e r o r a i r ; it m a y be c a r b o n dioxide, o r g a n i c l i q -
u i d s , m o l t e n s a l t s , liquid m e t a l s , g a s e o u s s u l f u r , and
so forth. Somewhat l e s s obvious is that " c o r r o s i o n "
is c a u s e d by e n v i r o n m e n t s such a s n e u t r o n r a d i a t i o n ,
u l t r a v i o l e t light, f i s s i o n f r a g m e n t s , and g a m m a r a y s .
The a b l a t i o n p r o b l e m a s s o c i a t e d with high velocity r e -
entry is a corrosion problem.
With r e s p e c t to m a t e r i a l s , we m u s t be c o n c e r n e d
with a l l e n g i n e e r i n g s o l i d s : m e t a l s , p l a s t i c s , r u b b e r ,
ionic s o l i d s , c o v a l e n t s o l i d s , s u p e r c o o l e d liquids
( g l a s s e s ) , a g g r e g a t e s ( c o n c r e t e ) , wood, and c o m p o s i t e
materials.
The e x t e n t of the c o r r o s i o n p r o b l e m a s an e c o n o m i c
l i a b i l i t y is difficult to d e s c r i b e d e f i n i t i v e l y . V a r i o u s e s -
t i m a t e s have p l a c e d the a n n u a l n a t i o n a l cost of c o r r o -
sion in the r a n g e of 8 to 20 b i l l i o n d o l l a r s . T h i s cost
is b o r n e by i n d u s t r y , g o v e r n m e n t , and p r i v a t e i n d i v i d -
u a l s . However, it i s difficult to e s t i m a t e the cost of
lost p r o d u c t i o n o r d o w n - t i m e ($10,000 p e r day in one
c a s e i n v o l v i n g pitting) r e s u l t i n g f r o m c o r r o s i o n - i n -
duced f a i l u r e s , and the cost of l o s s of m a n y l i v e s r e -
s u l t i n g f r o m c a t a s t r o p h i c f a i l u r e s such a s the S i l v e r
Bridge f a i l u r e on the Ohio R i v e r . It is difficult also
to e s t i m a t e the cost p e n a l t y of c o r r o d e d m i l i t a r y
e q u i p m e n t which m a l f u n c t i o n s o r is not a v a i l a b l e at
c r i t i c a l t i m e s . In the NASA s p a c e p r o g r a m if a " f i x "
had not b e e n obtained on s t r e s s - c o r r o s i o n f a i l u r e s of
Ti6AI4V alloy t a n k s c o n t a i n i n g NzO4 (oxidizer), the
l u n a r l a n d i n g p r o g r a m could have b e e n d e l a y e d m a n y ,
many months.
C o r r o s i o n m a n y t i m e s is u s e f u l . P i c k l i n g of m e t a l s ,
e l e c t r o c h e m i c a l m a c h i n i n g , " b l u e i n g " of f i r e a r m s ,
e l e c t r o p o l i s h i n g of m e t a l s , the " d r y " cell b a t t e r y ,
and m e t a U o g r a p h i e a l etching a r e good e x a m p l e s of
c o n t r o l l e d c o r r o s i o n p r o c e s s e s . Knowledge of c o r r o -
sion p r o c e s s e s a l s o helps to u n d e r s t a n d c e r t a i n c o m -
p l e m e n t a r y e l e c t r o c h e m i c a l p r o c e s s e s , such a s e l e e -
t r o p l a t i n g and e l e c t r o w i n n i n g of m e t a l s which involve
the m e t a l d e p o s i t i o n p r o c e s s - - j u s t the opposite of the
corrosion process. Corrosive evaporation or dissolu-
tion a r e the opposite of a t o m i c and m o l e c u l a r c o n d e n -
sation o r p r e c i p i t a t i o n . G a s e o u s r e d u c t i o n of oxides is
the opposite of oxidation of m e t a l s .
C o r r o s i o n e n g i n e e r s and c o r r o s i o n s c i e n t i s t s have
gone t h e i r s e p a r a t e ways and do not c o m m u n i c a t e
well with each other, even though they should be c o m -
p l e m e n t a r y to each other. The u s e f u l p r i n c i p l e s of
e l e c t r o c h e m i s t r y so widely u s e d by s o m e c o r r o s i o n
s c i e n t i s t s a r e l i t t l e known and e v e n m o r e poorly u n -
d e r s t o o d by the c o r r o s i o n e n g i n e e r . A s c i e n t i s t and
e n g i n e e r a r e not a n t a g o n i s t i c ; they a r e s y n e r g i s t i c .
D i s c o v e r i e s and a t t a i n m e n t s in each field help and
fortify e a c h other. H each follows n a r r o w and widely
d i v e r g e n t paths o b l i v i o u s of e a c h other, t h e i r t r u e
p u r p o s e , which is to b e n e f i t m a n k i n d , will suffer.
C l o s e r c o o p e r a t i o n should r e s u l t in a r e d u c t i o n of the
t i m e lag between d i s c o v e r y and a c t u a l use. A good
e x a m p l e of this t i m e lag i n v o l v e s cathodic p r o t e c t i o n .
The p r i n c i p l e s w e r e d i s c o v e r e d by F a r a d a y about 150
y e a r s ago, but e x t e n s i v e u s e of cathodic p r o t e c t i o n
with i m p r e s s e d c u r r e n t s has t a k e n place only d u r i n g
METALLURGICALTRANSACTIONS
the p a s t 40 y e a r s . U t i l i z a t i o n in the c h e m i c a l i n d u s t r y
c o v e r s only about the p a s t 10 y e a r s . Yet h e r e i s one
of the m o s t e f f e c t i v e and l e a s t e x p e n s i v e m e t h o d s of
c o r r o s i o n c o n t r o l . An e x c e l l e n t e x a m p l e of a s h o r t e r
t i m e lag is anodic p r o t e c t i o n . In this c a s e c l o s e r co-
o p e r a t i o n b e t w e e n s c i e n t i s t s and e n g i n e e r s , and also
b e t t e r c o m m u n i c a t i o n s , r e s u l t e d in a p e r i o d of l e s s
than 10 y e a r s b e t w e e n d i s c o v e r y and corn'rhercial u t i -
lization.
The c o r r o s i o n e n g i n e e r m u s t keep i n f o r m e d on de-
v e l o p m e n t s in c o r r o s i o n s c i e n c e in o r d e r to m o r e ex-
p e d i t i o u s l y s o l v e h i s p r o b l e m . An i n t e r e s t i n g e x a m p l e
i n v o l v e s c a t a s t r o p h i c o x i d a t i o n ' of a high t e m p e r a t u r e
alloy c o n t a i n i n g m o l y b d e n u m . T h e s e a l l o y p a r t s had to
p a s s an a c c e p t a n c e t e s t c o n s i s t i n g of a s h o r t t i m e e x -
p o s u r e to a i r at l l 0 0 ~ d u r i n g which v e r y r a p i d oxida-
tion o c c u r r e d . I n v e s t i g a t i o n showed that a l l of the
oxide p r o d u c e d d u r i n g m a n u f a c t u r e was not r e m o v e d
p r i o r to the t e s t s . T h e s e s m a l l p a t c h e s of oxide t r i g -
g e r e d c a t a s t r o p h i c oxidation. An acid p i c k l i n g t r e a t -
m e n t r e m o v e d the p r o c e s s oxide and s o l v e d the p r o b -
lem.
THE EIGHT FORMS O F CORROSION AND THE
EIGHT METHODS FOR COMBATTING CORROSION
Many y e a r s ago I p r o p o s e d c l a s s i f y i n g the m a n y
m a n i f e s t a t i o n s of c o r r o s i o n into eight f o r m s . T h e s e
a r e : 1) uniform o r g e n e r a l c o r r o s i o n , 2) g a l v a n i c or
two-metal c o r r o s i o n , 3) crevice c o r r o s i o n (in s t a g -
n a n t a r e a s like at g a s k e t f a c e s or u n d e r d e p o s i t s ) ,
4) pitting, 5) intergranular c o r r o s i o n , 6) s e l e c t i v e
leaching (of one e l e m e n t of an alloy, such a s d e z i n c i f i -
cation), 7) erosion corrosion i n c l u d i n g f r e t t i n g and
cavitation, and 8) s t r e s s corrosion ( c r a c k i n g ) including
c o r r o s i o n fatigue. T h i s a r r a n g e m e n t of s u b j e c t s p r o -
v i d e s c l u e s to the m e c h a n i s m s involved and i n d i c a t e s
p o s s i b l e s o l u t i o n s to p a r t i c u l a r p r o b l e m s . F o r the
c o r r o s i o n e n g i n e e r it s e r v e s a s a " c h e c k o f f " list.
C a t e g o r i z a t i o n of this kind a l s o p r o v i d e s i n f o r m a t i o n
for r e s e a r c h and d e v e l o p m e n t . A d e t a i l e d d i s c u s s i o n
of t h e s e eight f o r m s is given in my text. 2
T a b l e I is the r e s u l t of a t w o - y e a r s u r v e y by the
DuPont Company ~ c o v e r i n g a total of 313 f a i l u r e s .
C o r r o s i o n f a i l u r e s w e r e s u b s t a n t i a l l y g r e a t e r than
those a t t r i b u t e d to s t r i c t l y m e c h a n i c a l effects. The
m o s t i m p o r t a n t c o r r o s i o n f a i l u r e s in o r d e r of f r e q u e n -
Table I. Metal Failure Frequency-1968, 1969 (313 Cases Corrosion
56.9 pct, Mechanical 43.1 pct)
CorrosionFailures
Form Percent
General 31.5
Cracking-StressCorrosion 21.6
-CorrosionFatigue 1.8 J 23.4
Pitting 15.7
Intergranular 10.2
ErosionCorrosion 7.4 ]
Cavitation 1.1 I 9.0
Fretting 0.5
Crevice 1.8
De(metal)ification 1.1
Two-Metal 0.0
(High temperature2.3 pet, WeldCorrosion2.3 pct, ColdWall1.8 pet, End
Grain 1.1 pct, Hot Wall0.5 pct, and HydrogenEmbrittlement0.5 pet.)
VOLUME I,DECEMBER 1970-3253
cy w e r e g e n e r a l , c r a c k i n g , p i t t i n g , i n t e r g r a n u l a r , and
e r o s i o n c o r r o s i o n . Most of the i t e m s l i s t e d in p a r e n -
t h e s i s could be included into the eight f o r m s . O b v i -
o u s l y t h i s company should expend m o s t of its R and D
effort in c o r r o s i o n on the f i r s t five i t e m s l i s t e d .
The p a t t e r n of c o r r o s i o n f a i l u r e s shown in T a b l e I
is p e r h a p s t y p i c a l of a l l c h e m i c a l c o m p a n i e s e x c e p t
that D u P o n t has well t r a i n e d people working on c o r r o -
sion p r o b l e m s . T h i s a c c o u n t s f o r the p r a c t i c a l l y z e r o
i n c i d e n c e of t w o - m e t a l f a i l u r e s . O t h e r c h e m i c a l c o m -
p a n i e s , p a r t i c u l a r l y the s m a l l ones, could show d i f f e r -
ent p a t t e r n s . Other i n d u s t r i e s would show widely d i -
v e r g e n t p a t t e r n s . The a u t o m o t i v e i n d u s t r y is m o s t l y
c o n c e r n e d with g e n e r a l c o r r o s i o n with s o m e i n t e r e s t
in p i t t i n g , s t r e s s c o r r o s i o n , and t w o - m e t a l c o r r o s i o n .
In the household and the b u i l d i n g i n d u s t r y , g e n e r a l ,
pitting, and t w o - m e t a l would c o v e r the v a s t m a j o r i t y
of p r o b l e m s .
With r e g a r d to adequate f u n d i n g for r e s e a r c h today,
only s t r e s s c o r r o s i o n and g e n e r a l c o r r o s i o n fall into
this c a t e g o r y . R e l a t i v e l y l i t t l e effort is p r e s e n t l y e x -
pended on the other f o r m s of c o r r o s i o n .
S i m i l a r to the check l i s t f o r f o r m s of c o r r o s i o n ,
the v a r i o u s m e t h o d s f o r p r e v e n t i n g c o r r o s i o n can be
c a t e g o r i z e d into eight types ~ as follows: 1) more r e -
sistant alloys including optimum heat treatment, 2)
cathodic and anodic protection, 3) metal purification,
4) nonmetallics, 5) alteration of environment (such as
i n h i b i t o r s ) , 6) design ( s a m e m a t e r i a l but o p t i m u m g e -
o m e t r i c configuration), 7) organic coatings (such as
p a i n t s ) , and 8) metallic and other inorganic coatings.
One m e t h o d or c o m b i n a t i o n s of these can be u s e d to
p r o v i d e the e c o n o m i c a l s o l u t i o n of a given p r o b l e m .
F o r e x a m p l e , types 1), 2), 5), 6), and 7) above a r e u t i -
l i z e d to p r o t e c t offshore p l a t f o r m s . Again, c a t e g o r i -
zation p r o v i d e s a handy " c h e c k off" list.
EIGHT SECONDARY INTERACTIONS
IN CORROSION
C o r r o s i o n p r o c e s s e s a r e known also for t h e i r u n u -
s u a l , nonobvious, and c o m p l e x i n t e r a c t i o n s . Many
t i m e s it i s in fact these " s e c o n d a r y " i n t e r a c t i o n s that
a r e l i m i t i n g c o n s i d e r a t i o n s in c o r r o s i o n . This l e c t u r e
g i v e s m e the chance to e m p h a s i z e the i n s i d i o u s n a t u r e
of t h e s e p r o c e s s e s and for the f i r s t t i m e to a r r a n g e
them in c a t e g o r i e s .
1) C o r r o s i v e Effects of Negative P o t e n t i a l s . While
l o w e r i n g the p o t e n t i a l i s the b a s i s for cathodic p r o t e c -
tion, t h i s s o m e t i m e s can i n d u c e u n d e s i r a b l e r e s u l t s .
A w e l l - k n o w n r e s u l t of l o w e r i n g the p o t e n t i a l is h y d r o -
gen e m b r i t t l e m e n t ; but l o w e r i n g the p o t e n t i a l will a l s o
c o r r o d e Fe3C by r e d u c i n g it to m e t h a n e a s has r e c e n t l y
been shown in our l a b o r a t o r y . In the case of a l u m i n u m ,
l o w e r i n g the potential a c c e l e r a t e s the f o r m a t i o n of
O H - w h i c h is v e r y c o r r o s i v e to a l u m i n u m .
The h i g h - t e m p e r a t u r e g a s e o u s e n v i r o n m e n t analogy
to cathodic p o t e n t i a l s in a q u e o u s s o l u t i o n s is a r e l a -
tively r e d u c i n g a t m o s p h e r e , such a s r e s u l t s f r o m the
i n c o m p l e t e c o m b u s t i o n of a c a r b o n a c e o u s g a s e o u s
fuel. In d r y CO2, F e - C r a l l o y s f o r m a n o n p r o t e c t i v e
wustite scale, excessive chromium carbides are p r e -
cipitated within the alloy m a t r i x , and e m b r i t t l e m e n t
r e s u l t s . (Carbon is soluble and m o b i l e in oxides.) At
s o m e t e m p e r a t u r e s , the a l l o y s w e r e t r a n s f o r m e d f r o m
f e r r i t e to a u s t e n i t e by the d i s s o l u t i o n of c a r b o n and
3254-VOLUME 1, DECEMBER 1970
the r e m o v a l of c h r o m i u m f r o m solution. P r o f u s e c a r -
bide p r e c i p i t a t i o n a l s o o c c u r s in a u s t e n i t i c s t a i n l e s s
s t e e l s s u b j e c t e d to m o l t e n alkali c a r b o n a t e s at 600~
B i n a r y F e - C r a l l o y s also fail to f o r m the p r o t e c t i v e
Cr203 s c a l e when oxidized in dilute (0.1 atm) H20 v a -
por. T h i s b e h a v i o r i s analogous to that of s t a i n l e s s
s t e e l s and o t h e r p a s s i v e a l l o y s in a q u e o u s s o l u t i o n s ,
w h e r e the a l l o y s a r e dependent upon a n o d i c p o t e n t i a l s
(highly oxidizing conditions) for the r e t e n t i o n of p r o -
tecttve p a s s i v e f i l m s .
2) D i s s o l u t i o n in the Solid and I n t e r n a l P r e c i p i t a t i o n
R e a c t i o n s . Z i r c o n i u m a l l o y s a r e widely u s e d in w a t e r
cooled n u c l e a r r e a c t o r s b e c a u s e of t h e i r e x c e l l e n t
c o r r o s i o n r e s i s t a n c e . The p r o t e c t i v e f i l m on these a l -
loys grows at a v e r y low r a t e and the oxidation p r o -
ceeds a c c o r d i n g to an o v e r a l l r e a c t i o n
Z r + 2H20 ~ ZrO2 + 2H2 [2]
If this r e a c t i o n w e r e the only one o c c u r r i n g , z i r c o n i u m
clad n u c l e a r fuel would have a l m o s t i n f i n i t e c o r r o s i o n
life. However, a s i g n i f i c a n t f r a c t i o n (5 to 40 pct d e -
pending on the alloy and the e n v i r o n m e n t ) of the h y d r o -
gen p r o d u c e d in r e a c t i o n [2] e n t e r s the m e t a l to f o r m
h y d r i d e s a c c o r d i n g to the r e a c t i o n
2 Z r + 3H = Zr2H3 [3]
The h y d r i d e s thus f o r m e d e v e n t u a l l y e m b r i t t l e the
cladding m a t e r i a l by the f o r m a t i o n of a p l a t e - l i k e hy-
d r i d e and m a k e it u n s u i t a b l e for u s e when the a b s o r b e d
hydrogen c o r r e s p o n d s to about 400 ppm.
S i m i l a r u n d e s i r a b l e d i s s o l u t i o n of oxygen o c c u r s in
r e f r a c t o r y m e t a l s . In addition to the c a s e for hydride
f o r m a t i o n , t h e r e i s the hydrogen pickup of s t e e l s
(where no h y d r i d e s a r e formed) m e n t i o n e d e a r l i e r .
3) Unwanted R e a c t i o n P r o d u c t s . It often happens
that the c o r r o s i o n r a t e of m a t e r i a l s i s r e l a t i v e l y low
but the p r o d u c t s of r e a c t i o n s t i l l p r o d u c e l i m i t i n g c o n -
d i t i o n s in the s y s t e m .
In w a t e r - c o o l e d n u c l e a r r e a c t o r s y s t e m s the c o r r o -
sion of s t a i n l e s s s t e e l p r o d u c e s Fe, C r , and Ni (and a
s m a l l a m o u n t of Co) d i s s o l v e d in the coolant. While
these e l e m e n t s r e s i d e in the r e a c t o r they a r e activated
by ( n , ~ ) r e a c t i o n s which have high e n e r g y g a m m a r a y s
and r e l a t i v e l y long half l i v e s . T h e s e a c t i v a t e d p r o d -
u c t s along with t h e i r n o n a c t i v a t e d b r e t h r e n often d e -
p o s i t at s t a g n a n t a r e a s in the cooling s y s t e m which
a r e f a r r e m o v e d f r o m the r e a c t o r ; the r e s u l t i n g a c -
c u m u l a t i o n c a u s e s a point of high r a d i o a c t i v i t y outside
the r e a c t o r s h i e l d i n g and c a u s e s p e r s o n n e l h a z a r d s
even when the r e a c t o r shuts down.
A second u n w a n t e d p r o d u c t is e p i t o m i z e d by the cop-
p e r s o l u b i l i z a t i o n p r o b l e m in heat e x c h a n g i n g s y s t e m s .
Copper often i s d i s s o l v e d f r o m copper alloy heat e x -
c h a n g e r s in o t h e r p a r t s of the s y s t e m . T h i s copper
will then d e p o s i t on s i t e s of r e l a t i v e l y l o w e r e l e c t r o -
c h e m i c a l p o t e n t i a l , e s p e c i a l l y a l u m i n u m , to cause a c -
c e l e r a t e d pitting. Copper e x e r t s this effect through
c a t a l y t i c a l l y a c c e l e r a t i n g the r e d u c t i o n of w a t e r m o l e -
c u l e s o r hydrogen ions and s i m u l t a n e o u s l y stifling
anodic p r o c e s s e s w h e r e it has deposited.
T h i r d , the l e t h a l effects of d i s s o l v e d lead and m e r -
c u r y a r e well known. The d e c l i n e and f a l l of the R o m a n
E m p i r e has b e e n a t t r i b u t e d to lead p o i s o n i n g r e s u l t i n g
f r o m the s t o r a g e of w i n e s in lead vats. The p a t r i c i a n s
METALLURGICALTRANSACTIONS
who c o n s u m e d such wines w e r e s y s t e m a t i c a l l y poi-
soned and the c o u n t r y d r a i n e d of its t a l e n t e d l e a d e r s .
F o u r t h , c o r r o s i o n p r o d u c t s can c o n t a m i n a t e or d e -
grade the commodity involved and cause u n d e s i r a b l e
or i n f e r i o r p r o d u c t when p u r i t y is i m p o r t a n t .
Fifth, in liquid m e t a l cooled s y s t e m s the p h e n o m e -
non of t e m p e r a t u r e g r a d i e n t m a s s t r a n s f e r can c a u s e
p r e m a t u r e plugging of tubing. H e r e , the piping s u r -
f a c e s d i s s o l v e to a l i m i t e d e x t e n t at a higher t e m p e r -
a t u r e -- p r e s u m a b l y in the hot leg of a heat t r a n s f e r
loop. The d i s s o l v e d m a t e r i a l then p r e c i p i t a t e s in the
cold leg where the solubility is l e s s .
4) Volatile Oxides. The f o r m a t i o n of volatile oxide
and h y d r a t e d oxide m o l e c u l e s r e p r e s e n t s a s e r i o u s
h i n d r a n c e to the r e t e n t i o n of p r o t e c t i v e , diffusion-
b a r r i e r oxide s c a l e s in h i g h - t e m p e r a t u r e g a s e o u s e n -
v i r o n m e n t s . E m p i r i c a l l y , it is well a p p r e c i a t e d that
the oxides of W, Mo, 1 and Cr a r e volatile in oxidizing
a t m o s p h e r e s , while SiO2 e x p e r i e n c e s vapor l o s s e s in
r e d u c i n g a t m o s p h e r e s . T h e o r e t i c a l l y , this b e h a v i o r
is a l s o w e l l u n d e r s t o o d .
5) M i s s a p p l i c a t i o n of I n h i b i t o r s . V a r i o u s i n h i b i t o r s
can be added to stifle anodic and cathodic p r o c e s s e s
and t h e r e b y r e d u c e the c o r r o s i o n r a t e . However, the
m i s a p p l i c a t i o n of such i n h i b i t o r s can a c c e l e r a t e c o r -
r o s i o n . F o r e x a m p l e , u s e of a cathodic i n h i b i t o r (one
which i n t e r f e r e s with, for e x a m p l e , the r e a c t i o n 2e
+ 2H* - - H2) can a c c e l e r a t e c o r r o s i o n by r e t a r d i n g
the cathodic k i n e t i c s and p r o d u c i n g an i n t e r s e c t i o n
with a s u b m e r g e d anodic peak of an a c t i v e - p a s s i v e
material.
The addition of c h r o m a t e s to stifle the anodic p r o c -
e s s m a y have d e l e t e r i o u s e f f e c t s if added to a solution
of the wrong pH. At p H ' s below about 3, c h r o m a t e s
r e d u c e to Cr and at higher pH the c h r o m a t e s r e d u c e
to c h r o m i u m oxides or h y d r o x i d e s a c c o r d i n g to the
reactions
6e' + Cr20~ + 7H + 7OH- (acidrange)
6e' + Cr20~ + 4H + 4OH- (less acid)
Producing Cr ~3 provides an additional reduction reac-
tion and accelerates corrosion; producing Cr203 sti-
fles further anodic reactions, raises the potential,
and reduces the corrosion.
6) Concentration of Reactants. In certain concen-
trations various species in solution are not only in-
nocuous but beneficial. For example, the corrosion
resistance of iron is improved by raising the pH to
the range of 8 to II, dependingon the desired results,
using additions of LiOH or NaOH. These additions pro-
duce substantial improvements unless the system ex-
periences wetting and drying, for example on heat
transfer surfaces where boiling occurs. The resulting
concentrating processes may then produce a very high
pH and lead to caustic stress corrosion or simply ac-
celerated general corrosion owing to the instability of
protective films relative to caustic soluble species
such as FeO~.
A similar effect occurs in the case of chloride con-
centration. Many times the residual chloride concen-
tration in the environment is sufficiently low as to
preclude premature stress corrosion cracking. How-
ever, a local boiling sit~lationor one simply of wetting
followed by evaporation to dryness in the ambient will
METALLURGICALTRANSACTIONS
cause c o n c e n t r a t i o n s s u f f i c i e n t to p r o m o t e s t r e s s -
c o r r o s i o n c r a c k i n g of s t a i n l e s s s t e e l s .
C r a c k i n g of a u s t e n i t i c s t a i n l e s s s t e e l p l a n t equip-
m e n t f r o m the o u t s i d e s u r f a c e (non p r o c e s s s t r e a m
side) b e c a u s e of, for e x a m p l e , leaching (and c o n c e n -
tration) of c h l o r i d e s in i n s u l a t i n g m a t e r i a l s h a s been
o b s e r v e d . F r e q u e n c y of this type of f a i l u r e is so g r e a t
it has been t e r m e d e x t e r n a l s t r e s s - c o r r o s i o n c r a c k i n g
(ESCC).
7) F o r c e s E x e r t e d by C o r r o s i o n P r o d u c t s . The c o r -
r o s i o n p r o d u c t s p r o d u c e d d u r i n g the c o r r o s i o n r e a c -
tion can be as d e s t r u c t i v e as the c o r r o s i o n p r o c e s s
itself. C r a c k s in c o n c r e t e s t r u c t u r e s due to the c o r -
r o s i o n p r o d u c t s f r o m imbedded a l u m i n u m p i e c e s are
well known; the s e l f - p r o p a g a t i n g of s t r e s s - c o r r o s i o n
c r a c k s due to s t r e s s e s p r o d u c e d by c o r r o s i o n p r o d -
u c t s was o b s e r v e d by P i c k e r i n g , Beck, and Fontana. 4
In this paper the actual f o r c e s e x e r t e d by the c o r r o -
sion p r o d u c t s w e r e actually m e a s u r e d .
C o r r o s i o n p r o d u c t s e x e r t epitaxial s t r e s s e s also.
C h i r i g o s 5 has o u t l i n e d p o s s i b l e effects of c o r r o s i o n
p r o d u c t s in a c c e l e r a t i n g the c o r r o s i o n of u r a n i u m and
z i r c o n i u m b a s e a l l o y s . Such effects p r o b a b l y account
for the l i n e a r oxidation k i n e t i c s o b s e r v e d for many
alloys.
In the high t e m p e r a t u r e oxidation of t a n t a l u m , it has
been shown that m e t a s t a b l e suboxide p l a t e l e t s a r e
f o r m e d on {100} habit p l a n e s in the m e t a l b e n e a t h the
scale. These p l a t e l e t s act as c r a c k p a t h s in the scale
and u l t i m a t e l y c a u s e an o r i e n t a t i o n d e p e n d e n c e in the
k i n e t i c s of t a n t a l u m oxidation.
8) R e s i d u a l S u r f a c e I m p u r i t i e s . R e s i d u a l fluoride on
z i r c o n i u m alloys (due to poor r i n s e a f t e r an HF-HNO3
pickle) g r e a t l y a c c e l e r a t e s c o r r o s i o n in hot water.
R a t h e r than gaining weight at a m o d e s t r a t e , the z i r -
conium loses weight.
A high t e m p e r a t u r e analog to this effect o c c u r s in
the case of " c a t a s t r o p h i c o x i d a t i o n " m e n t i o n e d e a r l i e r
[4] when some v a n a d i u m oxide, sodium sulfate, o r sodium
c a r b o n a t e is left on the m e t a l s u r f a c e b e f o r e exposing
[ 5]
to t e m p e r a t u r e in the l l 0 0 ~ range. 1'6 S t r e s s c o r r o -
sion c r a c k i n g i n d u c e d d u r i n g s e r v i c e by r e s i d u a l m a -
chining l u b r i c a n t c o n t a i n i n g chloride has been o b s e r v e d .
T h e r e is no s u b s t i t u t e for c a r e f u l p r i o r c l e a n i n g of
p a r t s where i m p u r i t y effects a r e s u s p e c t e d . Special
c a r e m u s t be taken when the s u r f a c e would have slight
i n t e r g r a n u l a r p e n e t r a t i o n s ( r e s u l t i n g f r o m n i t r i c acid
pickling of s e n s i t i z e d s t a i n l e s s s t e e d w h e r e i m p u r i -
ties might lodge and r e m a i n after s u b s e q u e n t washing.
EFFECTS OF MATERIALS STRUCTURE ON
CORROSION PROCESSES
Since the ASM is primarily a materials society, it
is appropriate to consider the influence of materials--
their structure and their chemistry--on c o r r o s i o n
p r o c e s s e s . The m e t a l l u r g y of m e t a l l i c c o r r o s i o n is
as i m p o r t a n t as the e l e c t r o c h e m i s t r y . Since the s t r u c -
t u r a l effects of o t h e r e n g i n e e r i n g solids on t h e i r c o r -
r o s i o n b e h a v i o r has been l e s s e x t e n s i v e l y i n v e s t i g a t e d ,
the m e t a l s wilt be d i s c u s s e d p r i m a r i l y but with the
i m p l i c a t i o n that the s a m e p r o c e s s e s might, as well,
o p e r a t e to some d e g r e e in other m a t e r i a l s .
The i m p o r t a n t m e t a l l u r g i c a l c o n s i d e r a t i o n s in c o r -
r o s i o n a r e s u m m a r i z e d as follows:
1) Basic M e t a l - E n v i r o n m e n t C o m p a t a b i l i t y . Aside
VOLUME I,DECEMBER 1970-3255
f r o m the obvious p e r f o r m a n c e c r i t e r i a of p h y s i c a l for s e l e c t i o n of the p r o t e c t i v e film r e l a t e s p r i m a r i l y
and m e c h a n i c a l p r o p e r t i e s , the f i r s t m e t a l l u r g i c a l to the point defect c o n c e n t r a t i o n and m o b i l i t y in the
c o n s i d e r a t i o n in c o r r o s i o n r e s i s t a n c e is the e s s e n t i a l p r o t e c t i v e film and a d h e r e n c e of the s c a l e . As long as
c h e m i c a l compatability. the p r o t e c t i v e f i l m m a i n t a i n s its m e c h a n i c a l i n t e g r i t y
In the s i m p l e s t view, one m a y a p p r o a c h this f r o m and as long a s the t r a n s p o r t of ions in the l a t t i c e is
the point of view of e i t h e r the 1) r e l a t i v e nobility of sufficiently slow, the oxidation r a t e will be low. The
the alloy with r e s p e c t to the e n v i r o n m e n t , or 2) q u a l i t y d e t a i l e d b a s i s f o r the f o r m a t i o n of p r o t e c t i v e oxide
of the p r o t e c t i v e film. The n o b i l i t y approach, g e n e r a l l y , f i l m s i s c o m p l e x for e n g i n e e r i n g a l l o y s . An e x c e l l e n t
does not e m b r a c e a l a r g e n u m b e r of p r a c t i c a l l y s i g - m o n o g r a p h by Kofstad ~ and an a r t i c l e by Rapp a s u m -
n i f i c a n t m a t e r i a l s in e i t h e r a q u e o u s or g a s e o u s e n - m a r i z e s i g n i f i c a n t c o n s i d e r a t i o n s in the oxidation of
v i r o n m e n t s . T h e r e f o r e , the s e c o n d c r i t e r i o n , the s t a - pure m e t a l s and alloys.
bility of p r o t e c t i v e f i l m s , m u s t be e x a m i n e d m o r e 2) I m p u r i t y E f f e c t s and I n c l u s i o n s . I m p u r i t i e s in a l -
closely. loys e x e r t v a r i o u s effects depending upon the p a r t i c u -
In a q u e o u s e n v i r o n m e n t s , the m o s t s i g n i f i c a n t c o n - l a r m e c h a n i s m involved and whether the i m p u r i t y is
s i d e r a t i o n is the pH d e p e n d e n c e of the stability of the p r e s e n t as a p r e c i p i t a t e o r in solid s o l u t i o n .
f i l m s . Fig. 1 s u m m a r i z e s the r a n g e of stability of ox- Nitrogen, for e x a m p l e , a c c e l e r a t e s the s t r e s s c o r -
ides on v a r i o u s p u r e m e t a l s a s affected by the pH at r o s i o n c r a c k i n g of s t a i n l e s s s t e e l in s o m e c h l o r i d e
25~ T h i s c o m p a r i s o n shows why zinc is not so c o r - s o l u t i o n s as shown by Uhlig and Sava. 9 I r o n i m p u r i t y
r o s i o n r e s i s t a n t w h e r e a s tin (as in tin plate) p r o v i d e s in t i t a n i u m is r e s p o n s i b l e for its poor c o r r o s i o n r e -
e x c e l l e n t c o r r o s i o n r e s i s t a n c e ; this d i a g r a m a l s o s i s t a n c e in c e r t a i n aqueous s o l u t i o n s . I r o n i m p u r i t i e s
shows why g l a s s (SiO2) is so s t a b l e in the acid r a n g e in a l u m i n u m p r o m o t e pitting. Nitrogen c o n t a m i n a t i o n
and e t c h e s so e a s i l y in the c a u s t i c range. in p u r e z i r c o n i u m has been well known to a c c e l e r a t e
In addition to the c a l c u l a t e d t h e r m o d y n a m i c s t a b i l i t y its c o r r o s i o n in high hydrogen w a t e r and s t e a m e n v i r -
of f i l m s , kinetic s t u d i e s show that p r o t e c t i v e f i l m s o n m e n t s . U n f o r t u n a t e l y , the b a s i s for m a n y of these
e x i s t in r e g i o n s of pH where bulk f i l m s a r e not s t a b l e . i m p u r i t y effects is not c l e a r .
In g a s e o u s e n v i r o n m e n t s (e.g., oxygen), the b a s i s I n c l u s i o n s a r e f r e q u e n t l y as d e l e t e r i o u s to the c o r -
r o s i o n b e h a v i o r a s they a r e to f r a c t u r e . Sulfide i n c l u -
s i o n s in Type 403 s t a i n l e s s s t e e l have b e e n shown by
I [ I I I I I
2.1 -- F o n t a n a 1~ to be n u c l e i for s t r e s s c o r r o s i o n c r a c k i n g
owing to t h e i r r a p i d c o r r o s i o n and the h y d r o g e n uptake
1.8-- Ni which r e s u l t s . Hydrogen b l i s t e r i n g of s t e e l s is f a v o r e d
I by the p r e s e n c e of i n c l u s i o n s - - e s p e c i a l l y if the i n c l u -
1.5-- I
Pb ~ " - Co s i o n s a r e s t r u n g out d u r i n g f a b r i c a t i o n .
1.2--
The p r e s e n c e of m i n o r " i m p u r i t i e s " i s not always
d e l e t e r i o u s . F o r at l e a s t 40 y e a r s , m i n o r additions
09-- Fe (1 pct and l e s s ) of r a r e e a r t h and a l k a l i e a r t h m e t a l s
i have been made to h i g h - t e m p e r a t u r e a l l o y s for i m -
o.6- p r o v i n g p r o t e c t i v e n e s s of s c a l e s and a d h e r e n c e u n d e r
Mn
I o s c i l l a t i n g t e m p e r a t u r e condition~. C o n v i n c i n g e v i -
03i-- Sn /--Cu
Ij I I dence for the m e c h a n i s m involved with t h e s e alloy
dopants is not y e t a v a i l a b l e , although m a n y g r o u p s a r e
o- I Iw
p r e s e n t l y studying this effect. The m o r e r e c e n t l y de-
> Mo
I I Cr
~ -0.3:-- I veloped s u p e r a l l o y s have i n c o r p o r a t e d such additions
Cd into t h e i r c o m p o s i t i o n s . The d e v e l o p m e n t of a new L a -
Ti I I
-0.6 -- Nb-.~j containing, C o - b a s e sheet s u p e r a l l o y has allowed the
I %-Io r e d e s i g n of the b u r n e r c a n s (allowing h i g h e r t e m p e r a -
-0.9 -- Si I
Zn t u r e s ) for t u r b i n e a i r c r a f t e n g i n e s , such that a d r a s t i c
r e d u c t i o n in v i s i b l e e x h a u s t e m i s s i o n s has been
-I.2 --
achieved.
- 1 5 -- 3) Multiple P h a s e M a t e r i a l s . Single p h a s e pure m e t -
Zr
I I a l s p o s s e s s few m e c h a n i c a l p r o p e r t i e s of e n g i n e e r i n g
I I
-1.8 -- '%-AI i n t e r e s t ; f u r t h e r alloying to achieve d e s i r e d p r o p e r -
Be ties r e s u l t s in m a t e r i a l s of complex s t r u c t u r e s . The
I
-2.1 -- Th s i m p l e s t of t h e s e m a t e r i a l s a r e t w o - p h a s e e q u i l i b r i u m
-2P, -- s t r u c t u r e s which m a y have s u b s t a n t i a l l y d i f f e r e n t
Mg
p r o p e r t i e s - - o r m a y n o t - - d e p e n d i n g on the c o m p o s i t i o n s
-2.7 -- of the r e s p e c t i v e p h a s e s . The c o r r o s i o n b e h a v i o r of
p e a r l i t e has been studied by Cron, P a y e r , and Staehle 1'
-3C I I I I I I I I I
u n d e r c o n d i t i o n s of v a r i o u s pH, applied p o t e n t i a l , and
-2 0 2 4 6 8 I0 12 14 16
specific a n i o n s . Depending upon these c o n d i t i o n s , the
pH~ f e r r i t e , the c a r b i d e , or the i n t e r f a c e between them
Fig. 1--Maximum range of stability of protective oxides on may d i s s o l v e p r e f e r e n t i a l l y . Fig. 2 shows t h e s e p o s -
some pure metals as a function of pH at 25~ according to s i b i l i t i e s as o b s e r v e d in thin foil s p e c i m e n s exposed
Pourbaix. 32 These ranges defined by equilibrium concentra-
tion of 10-4 molar soluble ions. The lines are arranged such to an applied p o t e n t i a l at 25~ in an a q u e o u s solution
that the horizontal line of maximum width of stability is lo- and s u b s e q u e n t l y e x a m i n e d in the t r a n s m i s s i o n e l e c -
cated at the minimum potential where it intersects pH7. tron m i c r o s c o p e (TEM). It is c l e a r f r o m Fig. 2 that

3256 VOLUME I,DECEMBER 1970 METALLURGICALTRANSACTIONS

 Ferr/le Dissolution b) solute e n r i c h m e n t , and c) p r e f e r e n t i a l p r e c i p i t a t i o n .
Original /:-oH
The p r e f e r e n t i a l oxidation, s u l f i d i z a t i o n , h y d r o g e n a -
tion, and c a r b u r i z a t i o n of g r a i n b o u n d a r i e s i s well
known. The w e a k e n i n g of the m a t e r i a l which o c c u r s
t h e r e f r o m may cause premature failure.
P r e f e r e n t i a l p r e c i p i t a t i o n at g r a i n b o u n d a r i e s as a
s o u r c e of p r e m a t u r e f a i l u r e is p r o b a b l y b e s t known in
the c a s e s of a l u m i n u m a l l o y s and s t a i n l e s s s t e e l s .
F o r m i n g the p r e c i p i t a t e at the b o u n d a r y p r o d u c e s d e -
pletion of a s p e c i e s a d j a c e n t to the p r e c i p i t a t e . In a l u -
m i n u m a l l o y s this s t a t e of a f f a i r s is p r o d u c e d as a
p a r t of the heat t r e a t i n g p r o c e d u r e r e q u i r e d to obtain
high s t r e n g t h .
One of the m o r e s e v e r e types of i n t e r g r a n u l a r c o r -
r o s i o n in a l u m i n u m alloys is exfoliation. E xfoliation
i s abetted a) by the fact that the g r a i n s in r o i l e d a l u -
II~ Ip,rn
m i n u m sheet a r e f l a t t e n e d out in " p a n c a k e " f o r m so
that c o r r o s i o n along the r o l l i n g d i r e c t i o n is g r e a t l y
f a v o r e d and b) by the l a r g e volume i n c r e a s e of the
(a) {b)
c o r r o s i o n p r o d u c t s . This p a r t i c u l a r p r o b l e m has
Fe-Od5w/. C Alloy phi 4 c a u s e d g r e a t d i f f i c u l t i e s at r i v e t h o l e s in a i r c r a f t
As Forged, O I N N a O H - O I M KHCeH~O 4 sheet material.
The i n t e r g r a n u l a r c o r r o s i o n and i n t e r g r a n u l a r
Pearl/tic Structure - 2 9 0 m V , lOm/n. s t r e s s c o r r o s i o n p r o b l e m in s t a i n l e s s s t e e l s which
r e s u l t s from s e n s i t i z i n g heat t r e a t m e n t s is one of
Carbide Dissolution Interface Dissolution the m a j o r p r o b l e m s in the application of a u s t e n i t i c
s t a i n l e s s s t e e l s . 12 In this case we a r e c o n c e r n e d
about the c o r r o s i o n of the p r e c i p i t a t e - f r e e zone which
is depleted in c h r o m i u m .
In the high t e m p e r a t u r e oxidation of b i n a r y N i - C r
a l l o y s with about 14 to 25 pct Cr, the p r e f e r e n t i a l
f o r m a t i o n of Cr203 g r a i n b o u n d a r y f i l m s has been
shown to be i m p o r t a n t to the a d h e r e n c e of p r o t e c t i v e
Cr203 s u r f a c e s c a l e s and for the " h e a l i n g " of r u p -
t u r e d s c a l e s . B e c a u s e of this f a v o r a b l e effect of g r a i n
b o u n d a r i e s , the oxidation k i n e t i c s for N i - C r a l l o y s of
t h e s e i n t e r m e d i a t e Cr c o n t e n t s is l o w e r for s p e c i m e n s
with f i n e r g r a i n s i z e . U n f o r t u n a t e l y f r o m the e c o n o m i c
and a v a i l a b i l i t y standpoint, and for an a p p a r e n t l y u n -
known r e a s o n , the p r e f e r e n t i a l g r a i n b o u n d a r y f i l m s
do not f o r m in a s i m i l a r m a n n e r on c o m p a r a b l e F e - C r
a l l o y s , so that the a d h e r e n c e and h e a l i n g of Cr203
s c a l e s on F e - C r a l l o y s is i n f e r i o r c o m p a r e d to N i - C r
(r (d) alloys.
5) P r e f e r r e d O r i e n t a t i o n . P r o b a b l y the m o s t well
pH4 pH4 known influence of p r e f e r r e d o r i e n t a t i o n is that on the
HC ~ Acetic Acid s t r e s s c o r r o s i o n of a l u m i n u m alloys. Here s t r e s s c o r -
r o s i o n s u s c e p t i b i l i t y for s t r e s s e s a p p l i e d in the short
+ l O O m V,GOmln -215m V, I0 rain. transverse d i r e c t i o n o c c u r s at about 20 pct of the y i e l d
Fig. 2--Modes of dissolution of ferrite and iron carbide in s t r e n g t h w h e r e a s for s t r e s s e s applied in the r o l l i n g
thin foils of pearlite exposed to various potentials, pH's, and d i r e c t i o n t h e r e is h a r d l y any i n c r e a s e in s u s c e p t i b i l i t y .
anions at 25~ Specimens examined by the electron micro-
scope subsequent to exposure in solution. An a p p r o x i m a t e l y s i m i l a r situation o c c u r s in t i t a n i u m
alloys.
The p r e f e r r e d o r i e n t a t i o n effects s e e m to r e l a t e to:
n e i t h e r phase is "anodic" o r " c a t h o d i c " but that they 1) p r e f e r e n t i a l a t t a c k along g r a i n b o u n d a r i e s which
v a r y in r e a c t i o n r a t e depending upon the e n v i r o n m e n t a l a r e elongated in the r o l l i n g p r o c e s s so that the c o r r o -
conditions. sion can p r o c e e d e a s i l y along a contiguous path; 2 ) f o r -
4) G r a i n B o u n d a r i e s , S t r a i n E n e r g y , Solute E n r i c h - m a t i o n of r e a c t i o n p r o d u c t s produced along c e r t a i n
m e n t , and P r e c i p i t a t e s . P u r e g r a i n b o u n d a r i e s do not c r y s t a l l o g r a p h i c p l a n e s (e. g., hydride p l a t e l e t s ) ; 3)
a p p e a r to c o n t r i b u t e s i g n i f i c a n t l y to the r e a c t i v i t y of p r e f e r r e d r e a c t i o n s or lack thereof along c e r t a i n c r y s -
m e t a l s in aqueous e n v i r o n m e n t s . S t r a i n e n e r g y alone tal f a c e s ; or 4) c o r r o s i o n p r o c e s s e s which follow a
does not a p p e a r to c o n t r i b u t e s i g n i f i c a n t l y to r e a c t i v i - slip c o n t r o l l e d d i r e c t i o n .
ty beyond some c o n t r i b u t i o n which leads to g r a i n In the h i g h - t e m p e r a t u r e oxidation of m a n y d i f f e r e n t
b o u n d a r y grooving. m e t a l s (Cu, Fe, Ni, Co, Ta, Hf, and o t h e r s ) to form
The p r i m a r y c o n t r i b u t i o n of g r a i n b o u n d a r i e s to r e - oxide s c a l e s with d r a s t i c a l l y differing point defect and
activity i s a s s o c i a t e d with t h e i r a) higher diffusivity, t r a n s p o r t p r o p e r t i e s , a dependence of oxidation k i n e -

METALLURGICAL TRANSACTIONS VOLUME I , D E C E M B E R 1 9 7 0 - 3 2 5 7

 {a)
Fig. 3--Dissolution along slip step traces as shown by the transmission electron microscope examination of thin foils, TEM of
oxide replica, and SEM examination of the surface. Materials all stainless steels exposed to chloride solutions. (a) Thin foil by
TEM, (b) oxide replica by TEM, (c) bulk surface by SEM.
t i c s on c r y s t a l l i n e o r i e n t a t i o n has been found. The r a -
t i o n a l i z a t i o n of this b e h a v i o r d i f f e r s for each of the
d i f f e r e n t m e t a l s m e n t i o n e d b e c a u s e of m o r p h o l o g i c a l
and m e c h a n i s t i c d i f f e r e n c e s in the oxidation p r o c e s s e s .
6) Slip Behavior. An i m p o r t a n t c o n t r i b u t i o n to u n -
d e r s t a n d i n g s t r e s s c o r r o s i o n b e h a v i o r was made by
Swann and Nutting 13 who s u g g e s t e d that c o p l a n a r i t y of
slip m a y be a c r u c i a l f a c t o r in s t r e s s c o r r o s i o n c r a c k -
ing. The b a s i s for this s u g g e s t i o n is that the i m p l i e d
a b s e n c e of c r o s s slip p e r m i t s a) s h a r p e r slip s t e p s on
the s u r f a c e (e. g., a m o r e e a s i l y broken p r o t e c t i v e
film) or b) a higher s t r e s s on i n t e r n a l b a r r i e r s . T h e s e
t e n d e n c i e s then favor the o n s e t of s t r e s s c o r r o s i o n
c r a c k i n g . Such t e n d e n c i e s t o w a r d s m o r e c o p l a n a r s l i p
have been c o r r e l a t e d with l o w e r e d s t a c k i n g fault e n e r -
gy, s h o r t r a n g e o r d e r , and long r a n g e o r d e r . While
the c u r r e n t s t a t u s of s t r e s s c o r r o s i o n c r a c k i n g r e l a -
tive to the c o p l a n a r a r g u m e n t is not well defined, t h e r e
is c e r t a i n l y r e a s o n a b l e e v i d e n c e for its p a r t i a l i m p o r -
tance in a l u m i n u m , t i t a n i u m , and copper alloys.
7) Static and Moving D i s l o c a t i o n s . While t h e r e is
little e v i d e n c e for e x t e n s i v e p r e f e r e n t i a l d i s s o l u t i o n - -
a s i d e f r o m etch p i t t i n g - - o f p u r e d i s l o c a t i o n s , P i c k e r -
ing 14 h a s shown that solute s e g r e g a t i o n is n e c e s s a r y
for p r e f e r e n t i a l d i s s o l u t i o n in i r o n - s i l i c o n alloys.
D i s s o l u t i o n of m e t a l o c c u r s w h e r e moving disloca-
tions break the protective surface f i l m . This p h e n o m e -
non was f i r s t r e p o r t e d by Swann and E m b u r y . '~ P r e f e r -
e n t i a l d i s s o l u t i o n at m o v i n g d i s l o c a t i o n s as shown by
TEM of a m e t a l foil, TEM of an oxide r e p l i c a , and
s c a n n i n g e l e c t r o n m i c r o s c o p y (SEM) of a m e t a l s u r -
face, a r e c o m p a r e d in Fig. 3.
8) Surface S t r u c t u r e and S u r f a c e T r e a t m e n t s . S u r -
face p r e p a r a t i o n g r e a t l y i n f l u e n c e s c o r r o s i o n b e h a v -
ior. Oxidation by water at 300~ is a c c e l e r a t e d by
e l e c t r o p o l i s h i n g r e l a t i v e to m e c h a n i c a l p r e p a r a t i o n .
3258-VOLUME 1,DECEMBER 1970
(b) (c)
S t r e s s c o r r o s i o n of s t a i n l e s s s t e e l s is a c c e l e r a t e d by
r o u g h e n i n g the s u r f a c e - - c h e m i c a l l y o r m e c h a n i c a l l y .
The c o r r o s i o n b e h a v i o r of z i r c o n i u m a l l o y s in hot
w a t e r and s t e a m is g r e a t l y affected by the u s e of s h a r p
or dull tools.
In the oxidation of N i - C r a l l o y s with i n t e r m e d i a t e
Cr c o n t e n t s , G i g g o n s and P e t t i t TM found t h a t p r i o r s u r -
face p r e p a r a t i o n by g r i t b l a s t i n g in o r d e r to p r o v i d e
s e v e r e s u r f a c e d e f o r m a t i o n would i n s u r e the f o r m a -
tion of p r o t e c t i v e Cr203 s c a l e s . They showed that the
d e f o r m e d s u r f a c e r e c r y s t a l l i z e d to f o r m s m a l l s u r -
face g r a i n s when the s p e c i m e n s w e r e h e a t e d to the
e l e v a t e d oxidation t e m p e r a t u r e . U n d e r t h e s e conditions,
the helpful f o r m a t i o n of g r a i n b o u n d a r y f i l m s (loops)
of Cr203 c a u s e d the s p e c i m e n to follow the slow oxi-
dation k i n e t i c s found for e x t r e m e l y f i n e - g r a i n e d s p e c i -
mens.
IMPORTANT ADVANCES IN TECHNIQUES FOR
MEASURING CORROSION PHENOMENA
The c o r r o s i o n e n g i n e e r is i n t e r e s t e d p r i m a r i l y in
the l i f e t i m e of e n g i n e e r i n g e q u i p m e n t ; for t h e s e p u r -
p o s e s weight c h a n g e , v i s u a l o b s e r v a t i o n , t i m e to fail,
and optical m e t a l l o g r a p h y a r e g e n e r a l l y adequate tools.
The m i s s i o n of the c o r r o s i o n s c i e n t i s t is to e s t a b l i s h
p r e d i c t a b i l i t y f o r the p e r f o r m a n c e of a l l o y - e n v i r o n -
m e n t c o m b i n a t i o n s ; here he n e e d s p r i m a r i l y to study
the f o r m a t i o n and b r e a k d o w n of p r o t e c t i v e l a y e r s for
which he wants to know the growth laws, c r y s t a l s t r u c -
t u r e , c h e m i c a l c o m p o s i t i o n , defect s t r u c t u r e , and
morphology.
U n d e r s t a n d i n g the v a r i o u s t e c h n i q u e s a v a i l a b l e for
c o r r o s i o n r e s e a r c h has r e c e n t l y been g r e a t l y f a c i l i -
tated by the p u b l i c a t i o n of Techniques of Metals R e -
search edited by Bunshah. 17 The ten v o l u m e s of this
METALLURGICALTRANSACTIONS
 ] ! I I I I I~ I I I " I / ; A "

20%si
~) MOOOC-IHr J J / (b)
..~ .IB % Si
30 //" I / / 1 6 % Si 12%Si 650~ 6 5 Hr /....~ / /
./ ../I Z./~,4% Si ...~ ~...~z.(_-,O% Si IC-- ~ / / / / I Fe- 2.O.3 c r - O '2 ~176
c -
_."j_~C..---~'J-~*--e% s, I~ I I / I ~ ,o~ H, so.
20 ~/"~'_~'~..~-~'~'~"-~'~ --~Mild Steel i/ k~/ / / 1 Alloys Anneoled ot
~__~__-- V I / I I J~di~otedTemperoture
l ~ I I Io.d Ti~e ~nd Wote~

-, 0 J ' ~ J ~ l I~ I / ~ ~ I -05 I I I
0 I00 200 300 400 500 600 I0 -4 I0- 3 I0- z Io-' I0
Current Density, mA / crn 2 (All Doto at 25~ Current Density, rnA/cm z

........ I ........ I ........ I ....... I .... ''"1 '

(c)
IN HzSO~ Type 2OI Stoinless Steel I
,.51 -02
_o.iiL ........ l ....... iron
withI [nAdditions
Phenylthiourec
IN HzSO
' '4of' i '''I(~)

,o

~E I N H2SO 4 + 0.5 M Noel ~ -03 /No Addition

~ ~ ~ ~ ,/ * I0 -e MPHTU
%k C . . . . . .J.~ "~ I N HzSO4 0 7 5 M Noel

Q._i.=.=_ . . . . ,.,De,
0 -05 ~ ~ ~ ~ ~ -

-0~6
-0-5-- T ,~,,T,fT ~ ttt,tttl ........ f ........ f z i ...... ; , , t tt,t~tl ~ t t IIIIII l t I Jltljl
I0-3 ~0-2 lO ~ I JO I0a I01 I02 IOs I04
Current Density, mA/cm z Current Density, m A / c m z
Fig. 4--Polarization curves showing effects of (a) alloying, Fe-S[ alloys from work of Omurtag and Doruk; 35 (b) heat treatment,
F e - C r alloys from work of Heumann and Roekel; 36 (c) chloride ion additions, from work of Walker and Rowe; s7and (d) inhibition
by phenylthiourea, from work of Beth, Cavellaro, Trabanelli. 38

s e r i e s should be c a r e f u l l y s c r u t i n i z e d by c o r r o s i o n - f e a t u r e s of p o l a r i z a t i o n c u r v e s for a v a r i e t y of a l l o y s
i s t s to find u s e f u l t e c h n i q u e s - - a s well as t h e i r l i m i t a - a r e being a n a l y z e d s t a t i s t i c a l l y to o p t i m i z e c o m p o s i -
t i o n s . T e c h n i q u e s for e n g i n e e r i n g s t u d i e s have been t i o n s of d e v e l o p m e n t a l a l l o y s .
s u m m a r i z e d by F o n t a n a and G r e e n e , 2 by Champion, le 2) L i n e a r P o l a r i z a t i o n . One may q u i c k l y note that
and o t h e r s . A very u s e f u l r e v i e w of t e c h n i q u e s for d e t e r m i n i n g p o l a r i z a t i o n c u r v e s i n v o l v e s , in s o m e
f u n d a m e n t a l c o r r o s i o n r e s e a r c h in aqueous e n v i r o n - c a s e s , c o n s i d e r a b l e effort and also i n f o r m a t i o n is
m e n t s has been p r e p a r e d by K r u g e r and F r a n k e n t h a l obtained which m a y not be valuable to the c o r r o s i o n
in vol. IV of Techniques o f Metals Research. e n g i n e e r . A s i m p l e r e l e c t r o c h e m i c a l t e c h n i q u e is
Only s i g n i f i c a n t a d v a n c e s in applying t e c h n i q u e s to called linear polarization. Its d e v e l o p m e n t and popu-
c o r r o s i o n s t u d i e s will be c o n s i d e r e d . T h e r e a r e a l a r i z a t i o n a r e due to the work of S t e r n and his a s s o -
g r e a t m a n y t e c h n i q u e s a v a i l a b l e which have been u s e d c i a t e s . 19'2~ T h i s t e c h n i q u e is one of the v e r y i m p o r t a n t
in s u p p o r t of c o r r o s i o n s t u d i e s but not to m a k e direct c o n t r i b u t i o n s of c o r r o s i o n s c i e n c e to c o r r o s i o n e n -
m e a s u r e m e n t s of c o r r o s i o n p h e n o m e n a . g i n e e r i n g . Here the s p e c i m e n is p o l a r i z e d a few m i l -
Two d e v e l o p m e n t s that will p r o b a b l y be u s e d in l i v o l t s a n o d i c a l l y a n d / o r c a t h o d i c a l l y and the c o r r e -
c o r r o s i o n r e s e a r c h soon a r e e l e c t r o n s p e c t r o c h e m i - sponding c u r r e n t is m e a s u r e d . This i n f o r m a t i o n g i v e s
ca/ a n a l y s i s (ESCA) and A u g e r s p e c t r o s c o p y . F i e l d a slope which, b e c a u s e of its u n i t s , i s c a l l e d the po-
ion and field e l e c t r o n e m i s s i o n should find g r e a t e r larization r e s i s t a n c e and is r e l a t e d d i r e c t l y to the
application. i n s t a n t a n e o u s c o r r o s i o n r a t e . The t e c h n i q u e p e r m i t s
The d i s a d v a n t a g e s of the c o m p l e x e q u i p m e n t de- m e a s u r i n g c o r r o s i o n p r o c e s s e s to be m e a s u r e d in
s c r i b e d below a r e high c a p i t a l c o s t s and expensive vivo for biomedical purposes, permits continuous
m a i n t e n a n c e . T h i s is t r u l y a " p r i c e of p r o g r e s s . " monitoring of corrosion rates in the process streams
1) Anodic and Cathodic P o l a r i z a t i o n Studies. I l l u s - of chemical industries, and is used in surveying the
t r a t i v e of the application of anodic and cathodic po- effects of large n p m b e r s of environmental perturba-
l a r i z a t i o n a r e p o l a r i z a t i o n c u r v e s in Fig. 4 showing, tions in a short time--/, e., evaluating inhibitors.
r e s p e c t i v e l y , the effect of a l l o y i n g a), heat t r e a t m e n t 3) Strain Electrometry. T. P. Hoar first advocated
b), c h l o r i d e breakdown of p a s s i v i t y c), and cathodic and verified 2. that a straining specimen might have
i n h i b i t o r d). At n u m e r o u s i n d u s t r i a l l a b o r a t o r i e s , the similar electrochemical behavior to the tip of an ad-

METALLURGICAL TRANSACTIONS VOLUME 1,DECEMBER 1970-3259

 5c

4C +800mY

3C +600 mV

~. ~V
2C

oov

o i i ,i,,,,I , , ,J,J,,,i
i io 1oo
TIME ( m m )

(b)

~)
Fig. 5--(a) View of ellipsometer with appropriate electrochemical instrumentation. (b) Growth of protective films on a Fe-10
Cr-10 Ni alloy in pH6 sulfate solution at room temperature for various applied potentials (Goswami, unpublished results).

v a n c i n g s t r e s s c o r r o s i o n c r a c k . T h i s technique to-
g e t h e r with m o d i f i c a t i o n s h a s b e e n used by n u m e r o u s
9
i n v e s t i g a t o r s i n c l u d i n g P a r k i n s and H u m p h r i e s . 22
4) E l e v a t e d T e m p e r a t u r e E l e c t r o c h e m i s t r y . V i r t u - 8
ally all f u n d a m e n t a l e l e c t r o c h e m i c a l work of i n t e r e s t
to c o r r o s i o n has been conducted below 100~ but a v a -
r i e t y of s i g n i f i c a n t m a t e r i a l s a p p l i c a t i o n s (steam pow-
e r , c h e m i c a l p r o c e s s i n g , d e s a l i n a t i o n ) o p e r a t e at
higher t e m p e r a t u r e s in the r a n g e f r o m 100~ to the
,~
7

6
I
c r i t i c a l point of w a t e r . F u n d a m e n t a l work here has
been slowed by p r o b l e m s a s s o c i a t e d with higher p r e s -
sures, reference electrodes, and contaminants. Re-
cently a n u m b e r of works in the USA, G r e a t B r i t a i n ,
Sweden, and R u s s i a have d e v e l o p e d u s e f u l e l e c t r o c h e m - 1200 A

ical t e c h n i q u e s for studying this h i g h e r r a n g e of t e m -

p e r a t u r e . Work to date has b e e n r e v i e w e d by M a s t e r s o n
and J o n e s . z3 Work by Cowan and Staehte 24 shows that
the p a s s i v i t y of n i c k e l b r e a k s down above 100~ i n d i -
cating that r o o m t e m p e r a t u r e d a t a m u s t be applied
only with g r e a t caution at h i g h e r t e m p e r a t u r e s .
5) E l l i p s o m e t r y . P r o b a b l y the m o s t exciting o p t i c a l
technique to find u s e in c o r r o s i o n r e c e n t l y is an old
t e c h n i q u e - - e U i p s o m e t r y . The t e r m " e l l i p s o m e t r y "
was c o i n e d in 1944 by A l e x a n d r e Rothen but b a c k g r o u n d
work on the technique had b e e n u n d e r w a y s i n c e the l a t e
1800's. T h e r e have been two r e c e n t s y m p o s i a on the
subject.Zs'z6
The technique i n v o l v e s d i r e c t i n g a b e a m of light a t
a s p e c i m e n s u r f a c e while c o r r o d i n g in s i t u (gaseous
o r aqueous) and d e t e r m i n i n g the t h i c k n e s s of the p r o -
t e c t i v e f i l m . This is p o s s i b l e b e c a u s e the p r o t e c t i v e
f i l m p o s s e s s e s d i f f e r e n t o p t i c a l p r o p e r t i e s than the
s u b s t r a t e . The i n t e r a c t i o n of the i n c o m i n g m o n o c h r o -
m a t i c a l l y p o l a r i z e d light with t h i s p r o t e c t i v e f i l m
p r o v i d e s i n f o r m a t i o n which i s u s e d to obtain its t h i c k -
n e s s . E l l i p s o m e t r i c m e a s u r e m e n t s a r e s e n s i t i v e to
a v e r a g e f i l m t h i c k n e s s e s in the r a n g e of 1A; s o m e
c l a i m s e n s i t i v i t e s in the 0.1,~ r a n g e . L e a d e r s in ap-
plying t h i s technique to c o r r o s i o n a r e K r u g e r of the
National B u r e a u of S t a n d a r d s and B o c k r i s of the U n i -
v e r s i t y of P e n n s y l v a n i a . An e x a m p l e of data o b t a i n e d
0 I I I
0 300 6OO i200
Depth 1~)
Fig. 6--Intensity for 31p vs film depth for Ta205 films on tan-
talum after anodizing in 0.9M H3PO4 (after Evans and Pem-
sler). 28
f r o m e l l i p s o m e t r i c m e a s u r e m e n t s is shown in Fig. 5.
6) E l e c t r o n - M o r p h o l o g i c a l . C o n t r i b u t i o n s of the
t r a n s m i s s i o n e l e c t r o n m i c r o s c o p e and the s c a n n i n g
e l e c t r o n m i c r o s c o p e to c o r r o s i o n s t u d i e s have been
s i g n i f i c a n t in u n d e r s t a n d i n g m i c r o m o r p h o l o g i c a l a s -
p e c t s of c o r r o s i o n p r o c e s s e s . F i g s . 2 and 3 e p i t o m i z e
the value of t h e s e two t e c h n i q u e s . The w o r k on d i s l o -
cation c o p l a n a r i t y by Swann and o t h e r s r e l a t i v e to
s t r e s s c o r r o s i o n h a s been p r e v i o u s l y m e n t i o n e d . F r a c -
tographic s t u d i e s of s t r e s s c o r r o s i o n c r a c k i n g u s i n g
both TEM r e p l i c a and SEM a r e in w i d e s p r e a d u s e d e -
spite t h e i r r e l a t i v e l y r e c e n t advent.
7) D i f f r a c t i o n T e c h n i q u e s . Low e n e r g y e l e c t r o n dif-
f r a c t i o n (LEED) mad r e f l e c t i o n e l e c t r o n d i f f r a c t i o n
(RED) t e c h n i q u e s a r e v a l u a b l e for defining t w o - d i m e n -
s i o n a l and bulk s u r f a c e s t r u c t u r e s , r e s p e c t i v e l y .
T h e s e t e c h n i q u e s a r e adequately e v a l u a t e d in the l i t -
e r a t u r e . One of the m o s t i m p o r t a n t d e v e l o p m e n t s in

3260-VOLUME I.DECEMBER 1970 METALLURGICALTRANSACTIONS

 (=) (b)
400
FQet Fracture
Fig. 7--(a) Stress intensity vs time for Type
300 ~-~K~r b 4340 steel exposed to 3 1/2 pct NaC1 solution.
Locations
.
of Kl_L : and Kls~noted.
LL,
(b) Schematic
200
of loci for mean stress vs crack depth for
~o Klc and Klscc showing region of design and
regions to be avoided.
IO0 I =r162

NO Breok~
00 I I
200 400 600 800 I000
Time to Fracture,mtn ( Crock Depth)89 ~ -

a p p l y i n g RED to c o r r o s i o n s t u d i e s has b e e n due to 4O

Sewell and Cohen where they c o m b i n e d RED and X - r a y
e m i s s i o n a n a l y s i s to study c o m p o s i t i o n s of s u r f a c e CF -_8M
f i l m s of m o n o l a y e r i c t h i c k n e s s . 27
8) Ion M i c r o p r o b e M a s s S p e c t r o m e t r y . P e m s l e r and
3O
E v a n s have r e c e n t l y applied the ion m i c r o p r o b e 28 to
the c h e m i c a l a n a l y s i s of p r o t e c t i v e f i l m s on m e t a l s . o
Fig. 6 shows the d i s t r i b u t i o n of 31p in Ta205 f i l m s o
which w e r e anodized in 14M H3PO4. Such a capacity
for o b t a i n i n g d i s t r i b u t i o n on this kind of a s c a l e r e p -
2o
r e s e n t s a g r e a t advance in u n d e r s t a n d i n g the c h e m i s t r y C~
of p r o t e c t i v e f i l m s .
9) A p p l i c a t i o n of F r a c t u r e M e c h a n i c s to S t r e s s C a r -
r o s i o n Studies. Significant a p p l i c a t i o n of f r a c t u r e m e -
c h a n i c s a n a l y s i s to e x p e r i m e n t a t i o n in s t r e s s c o r r o s i o n IO
c r a c k i n g was begun by B. F. Brown of the Naval R e -
s e a r c h L a b o r a t o r y . z9 Such a n a l y s i s is now a s t a n d a r d
tool for s t r e s s c o r r o s i o n s t u d i e s e s p e c i a l l y for high
s t r e n g t h a l l o y s of steel, a l u m i n u m and t i t a n i u m . Its
m a i n v a l u e is in defining the s t r e s s field in the r e g i o n o I I I I I I I I
of the c r a c k tip. The f r a c t u r e m e c h a n i c s approach 0 5 I0 15 20 25 30 35 40
p r o v i d e s the f i r s t u s e f u l and q u a n t i t a t i v e tool which Ferrite, Vol. %
the d e s i g n e r can u s e d i r e c t l y for i n c o r p o r a t i n g i n f o r -
Fig. 8--Effect of ferrite on stress required to induce stress
m a t i o n f r o m s t r e s s c o r r o s i o n t e s t s into design. Fig. corrosion of cast "18-8" type alloys.
7(a) shows the m o s t widely u s e d type of plot for p r e -
s e n t i n g i n f o r m a t i o n obtained for s p e c i m e n s d e s i g n e d
for this a n a l y s i s . The c r i t i c a l p a r a m e t e r s of KIc" and
c h l o r i d e - w a t e r e n v i r o n m e n t on t h r e e a l l o y s . T h e i r
KISCC define the c r i t e r i a for the o n s e t of f a s t f r a c t u r e wrought c o u n t e r p a r t s Type 316 (CF-8M), 304 (CF-8),
and sl0w (SCC) c r a c k growth, r e s p e c t i v e l y . Since K
and 304L (CF-3) show e s s e n t i a l l y the s a m e r e s i s t a n c e
has the g e n e r a l f o r m K = adb--, w h e r e a i s the m e a n
a s the c a s t a l l o y s with no f e r r i t e . W r o u g h t a l l o y s c a n -
s t r e s s and " a " the c r a c k depth, the l i n e s of Fig. 7(b)
not take full a d v a n t a g e of t h i s effect b e c a u s e of diffi-
define the loci of all c o n d i t i o n s u n d e r which both slow
culty in r o l l i n g high f e r r i t e duplex s t r u c t u r e s . F e r r i t e
growth and fast f r a c t u r e a r e expected; s i n c e fast f r a c -
c o n t r o l is a good e x a m p l e of an i m p r o v e m e n t b a s e d
t u r e is i m m i n e n t once KIscc is exceeded, the d e s i g n e r a l m o s t e n t i r e l y on m e t a l l u r g i c a l c o n s i d e r a t i o n s . This
m u s t u s e this a s his l i m i t .
d e v e l o p m e n t i s b a s e d on w o r k at The Ohio State Uni-
v e r s i t y u n d e r the s p o n s o r s h i p of the Alloy C a s t i n g
IMPORTANT D E V E L O P M E N T S
Institute.
The p r e v i o u s s e c t i o n d e a l t with a d v a n c e s in t e c h - 2) Anodic P r o t e c t i o n . C o m p a r e d to cathodic p r o t e c -
n i q u e s for studying c o r r o s i o n and these a r e i m p o r t a n t tion anodic p r o t e c t i o n is r e l a t i v e l y new and c o m m e r -
d e v e l o p m e n t s . O t h e r s a r e d e s c r i b e d below. cial a p p l i c a t i o n s extend back only a few y e a r s . This
1) F e r r i t e Control. C o n t r o l of the f e r r i t e / a u s t e n i t e p r o t e c t i o n is b a s e d on the f o r m a t i o n of a p r o t e c t i v e
r a t i o in a u s t e n i t i c c a s t s t a i n l e s s a l l o y s is now p r a c - film by e x t e r n a l l y applied anodic c u r r e n t s . T h i s oc-
ticed on a s u b s t a n t i a l scale. The p e r c e n t a g e of f e r r i t e c u r s with m e t a l s e x h i b i t i n g a c t i v e - p a s s i v e t r a n s i t i o n s
in the a u s t e n i t i c m a t r i x can be c o n t r o l l e d by a d j u s t i n g such a s iron, n i c k e l , c h r o m i u m , t i t a n i u m and t h e i r
the a u s t e n i t e and f e r r i t e f o r m i n g e l e m e n t s within the alloys. The d e v e l o p m e n t of p o t e n t i o s t a t s at r e a s o n a b l e
p a r t i c u l a r alloy c o m p o s i t i o n s p e c i f i c a t i o n s . I n c r e a s e d p r i c e s helped m a k e this method f e a s i b l e . Some r e s i s -
t e n s i l e s t r e n g t h in the o r d e r of 20 pct or m o r e r e s u l t s , tance to the u t i l i z a t i o n of anodic p r o t e c t i o n is due to
thus p e r m i t t i n g t h i n n e r s e c t i o n s and l e s s weight. In the fact that the c u r r e n t flow is d i r e c t l y opposite to
addition, r e s i s t a n c e to all f o r m s of c o r r o s i o n i s i n - the d i r e c t i o n of flow in cathodic p r o t e c t i o n . If i m p r o p -
c r e a s e d in m a n y c a s e s , p a r t i c u l a r l y s t r e s s c o r r o s i o n . e r l y applied, c o r r o s i o n is a c c e l e r a t e d by this r e v e r s e d
Fig. 8 shows s t r e s s r e q u i r e d to c a u s e c r a c k i n g by a flow.

METALLURGICALTRANSACTIONS VOLUME 1,DECEMBER 1970-3261

 3) T i t a n i u m . T i t a n i u m and i t s a l l o y s a r e r e l a t i v e plug valves have g r e a t l y i m p r o v e d the p e r f o r m a n c e
n e w c o m e r s in the c o r r o s i o n field but they make a s u b - and c o s t s of this type of e q u i p m e n t . T e f l o n - l i n e d pipe
s t a n t i a l c o n t r i b u t i o n b e c a u s e they exhibit u n u s u a l c o r - and v a l v e s have been widely used in s e r v i c e s too c o r -
r o s i o n r e s i s t a n c e a s c o m p a r e d to older m e t a l s and r o s i v e for m e t a l s . Fig. 9 shows a 12-in. valve with a
a l l o y s . T i t a n i u m was d e l i v e r e d by Dr. W. J. K r o l l in Teflon c o v e r e d d i s k and a l i n e d body. P l a s t i c s , i n c l u d -
the ' f o r t i e s , r e a r e d by the A r m e d S e r v i c e s in the 'fif- ing c o a t i n g s , a r e b e i n g u t i l i z e d m o r e and m o r e for c o r -
t i e s , then suffered a r e l a p s e but was n u r t u r e d by the
c h e m i c a l i n d u s t r y , and then r e c e i v e d a shot in the a r m
by the SST in the ' s i x t i e s .
R e c e n t l y an e x c e l l e n t book has been p u b l i s h e d which
b r i n g s the e n t i r e t i t a n i u m field up to date. Edited by
P r o m i s e l and Jaffee, ~~ this book c o v e r s the p r o c e e d -
i n g s of an i n t e r n a t i o n a l c o n f e r e n c e held in London in
1968.
In 1948 the P o s t p r e d i c t e d u s e of t i t a n i u m , b e c a u s e
of i t s light weight and c o r r o s i o n r e s i s t a n c e , for e v e r y -
thing f r o m b r i d g e t a b l e s to b a t t l e s h i p s and I was quoted
by a W e s t Coast p a p e r as s a y i n g t i t a n i u m would go to
the moon. D u r i n g the late ' f o r t i e s only four o r g a n i z a -
t i o n s w e r e working with this new m e t a l - - B u r e a u of
M i n e s , DuPont, Battelle, and Ohio State. Many c o m p a -
n i e s e n t e r e d the field l a t e r but m o s t dropped out e v e n -
tually. A f t e r all these ups and downs and s u b s t a n t i a l
p r i c e r e d u c t i o n s , t i t a n i u m and its alloys a r e now i m -
portant commercial materials.
Titanium possesses three outstanding characteris-
tics which account for much of its application in c o r -
r o s i v e s e r v i c e s . T h e s e a r e r e s i s t a n c e to 1) s e a w a t e r
and o t h e r c h l o r i d e s a l t s o l u t i o n s , 2) hypochlorite and
wet c h l o r i n e , and 3) n i t r i c acid i n c l u d i n g f u m i n g a c i d s .
Salts such a s FeCI3 and CuClz, which tend to pit m o s t
o t h e r m e t a l s and a l l o y s , a c t u a l l y inhibit c o r r o s i o n of
t i t a n i u m . It s e e m s that the m o r e heavily c o n t a m i n a t e d
the e n v i r o n m e n t , the b e t t e r the r e s i s t a n c e of t i t a n i u m .
A l a r g e i n s t a l l a t i o n of t i t a n i u m heat e x c h a n g e r t u b i n g Fig. 9--Teflon lined butterfly valve (courtesy, The Duriron
handling hot chloride s o l u t i o n s i s p r a c t i c a l l y u n a f f e c t e d Co.).
a f t e r five y e a r s , w h e r e a s 10-gage Type 316 pitted
through in 10 days. However, t i t a n i u m shows poor r e -
2000 --
s i s t a n c e in some e n v i r o n m e n t s so knowledge of i t s
p r o p e r t i e s is n e c e s s a r y to avoid e x p e n s i v e f a i l u r e s .
4) T i t a n i u m with Noble Metal Additions. One of the
g r e a t t r i u m p h s of c o r r o s i o n s c i e n c e is the d e v e l o p m e n t
of t i t a n i u m alloys c o n t a i n i n g noble m e t a l a d d i t i o n s f '
The m e c h a n i s m for this effect i s b a s e d on the noble
m e t a l additions r a i s i n g the e x c h a n g e c u r r e n t . T h i s a c -
tion r a i s e s the c o r r o s i o n p o t e n t i a l into the region of
i m p r o v e d p a s s i v i t y f 2 R e c e n t e x p e r i m e n t a l work has
g:
shown, as expected, that n i c k e l additions will a c c o m -
p l i s h the s a m e r e s u l t - - f o r the s a m e r e a s o n . This b e n -
e f i c i a l effect on g e n e r a l c o r r o s i o n may have an a c c e l - o I000-
e r a t i n g effect on any a n o d i c a l l y c o n t r o l l e d s t r e s s 0

c o r r o s i o n . T h e s e a l l o y s s o m e t i m e s show b e t t e r r e s i s - ._~
t a n c e to c r e v i c e c o r r o s i o n but not always. Thus s p e c i a l UJ
c a r e should be taken in applying these alloys.
5) T e f l o n , the " n o b l e m e t a l " of the p l a s t i c s , is f i n d -
ing an i n c r e a s i n g n u m b e r of u s e s p a r t i c u l a r l y for 500 --

handling s e v e r e c o r r o s i v e s . One of the m o s t i n t e r e s t -

ing and u n u s u a l d e v e l o p m e n t s i n v o l v e s Teflon tubing
for heat e x c h a n g e r s . It is u n u s u a l in that a m a t e r i a l
with good heat i n s u l a t i n g p r o p e r t i e s can show heat
t r a n s f e r c h a r a c t e r i s t i c s c o m p a r a b l e to m e t a l s !
T e f l o n ' s " n o n - s t i c k " p r o p e r t i e s and its complete i n - 0 6 12 18 24
e r t n e s s to m o s t e n v i r o n m e n t s keep its s u r f a c e c l e a n Peripherol Velocity
and s c a l e s , c o r r o s i o n p r o d u c t s , and d e p o s i t s do not
( los )
f o r m like they do on m e t a l s and thus i n t e r f e r e with Fig. 10--Erosion corrosion of some cast stainless alloys by
heat t r a n s f e r . Teflon s l e e v e s ( i n s t e a d of l u b r i c a n t s ) in 96 pct H2SO4 containing 20 vol pct A120s.

3262-VOLUME I,DECEMBER 1970 METALLURGICALTRANSACTIONS

 ~ G
9 | @ |( ~ IAnion Species ]
,on ..Conc.=o.,on,.-,,
ICotion Species I
~k~ lend Concentration [CY I
Gaseous Species ~ Q~.. ~ ~.~
and Concentrotion(G2) ~ @ ~ (Az-') ~ ComplexSpecies ]
' 9 ' ~k~..,/'~ [ -- ~ G(.~] land Concentration (MX'+}]
9d ~ ~ X ,~ / High Temperature WeakenedFilm or
....................... ~"~'~k ~ Q , ,,[Tronsport ProcessesI Crystal,ine Film .. . -
Dissolved
I n af'ter 7'~N'~==zz=~ ~ m = z ~ r ~ \ / / "
Reg'o ' " ~ r ~aturelly
..... /hii3 I-ilm
Breakthrough ~ " '

/ / / / / / ~ [DepletedRegio~

rystols
s I

I Reactions J x~ L.Grein Boundary Segregation[

/
I Adsorption Reactions J

Fig. l l - - P a n o r a m i c consideration of possible c r i t i c a l p r o c e s s e s operating which may influence s t r e s s corrosion.

r o s i o n c o n t r o l in r e c e n t y e a r s . F o r e x a m p l e , l a r g e
t a n k s a r e c o n s t r u c t e d of f i b e r r e i n f o r c e d p l a s t i c s , t h u s
invading a field formerly reserved for steels.
6) C a s t S t a i n l e s s Alloy CD 4M Cu. T h i s f e r r o u s a l -
loy d e v e l o p e d u n d e r the s p o n s o r s h i p of the Alloy C a s t -
ing I n s t i t u t e , c o n s i s t s of 25 C r , 5 Ni, 3 Cu, 2 Mo, and
0.03 C and i s a d u p l e x ( f e r r i t e - a u s t e n i t e ) m a t e r i a l . It
s h o w s e x c e l l e n t r e s i s t a n c e to g e n e r a l c o r r o s i o n , e r o -
s i o n c o r r o s i o n , Fig. 10, and s t r e s s c o r r o s i o n m u c h
b e t t e r than the c o m m o n s t a i n l e s s s t e e l s and i t a l s o
h a s b e t t e r s t r e n g t h . N o m i n a l v a l u e s a r e 105,000 p s i
t e n s i l e , 85,000 p s i y i e l d , 20 p c t e l o n g a t i o n , and 240
B r i n e l l in the a n n e a l e d c o n d i t i o n with h i g h e r s t r e n g t h s
when a g e d . Its a p p l i c a t i o n i s i n c r e a s i n g r a p i d l y p a r -
t i c u l a r l y f o r r a t h e r a g g r e s s i v e e n v i r o n m e n t s in the
c h e m i c a l i n d u s t r y and a l s o in p o l l u t i o n c o n t r o l e q u i p -
m e n t . The low n i c k e l content of CD 4M Cu i s a d v a n t a -
g e o u s d u r i n g c r i t i c a l s h o r t a g e s of n i c k e l .
7) High S i l i c o n I r o n A n o d e s f o r C a t h o d i c P r o t e c t i o n .
T h e s e a n o d e s , with e x t e r n a l l y a p p l i e d c u r r e n t s , have
e n t e r e d t h i s f i e l d which had b e e n d o m i n a t e d p r e d o m i -
nantly b y c a r b o n and p l a t i n u m . D u r i c h l o r 51, a r e g u l a r
high s i l i c o n i r o n (14.5 p c t Si) with c h r o m i u m a d d i -
t i o n s , i s the l a t e s t e n t r y . Low c o n s u m p t i o n r a t e s and
long l i f e have r e s u l t e d in e x t e n s i v e u s e of D u r i c h l o r 51
a n o d e s in n u m e r o u s e n v i r o n m e n t s .
8) High P u r i t y F e r r i t i c S t a i n l e s s S t e e l s . With the
a d v e n t of high c a p a c i t y e l e c t r o n b e a m m e l t i n g it i s
p o s s i b l e to d e v e l o p f e r r i t i c s t a i n l e s s s t e e l s which a r e
free from embrittling impurities. These alloys are
r e s i s t a n t to c h l o r i d e SCC and s o m e have e x c e l l e n t p i t -
ting r e s i s t a n c e . A s p r o c e s s i n g c o s t s c o m e down and
a p p l i c a t i o n s i n c r e a s e , t h e s e a l l o y s w i l l find m o r e u s e .
The o p t i m i z a t i o n of t h e s e a l l o y s in m a n y l a b o r a t o r i e s
is b e i n g c o n d u c i e d e l e c t r o c h e m i c a l l y .
9) The N o n s p e c i f i c N a t u r e of S t r e s s C o r r o s i o n
C r a c k i n g . F o r m a n y y e a r s the s t r e s s c o r r o s i o n c r a c k -
ing p h e n o m e n o n w a s thought to be c a u s e d only by s p e -
c i f i c ions. T h i s i s no l o n g e r t r u e . S t r e s s c o r r o s i o n i s
v e r y c o m p l i c a t e d 33 a s shown in F i g . 11. I n c o n e l 600
c r a c k s in a b s o l u t e l y p u r e w a t e r ; s e n s i t i z e d and non-
s e n s i t i z e d 18-8 s t a i n l e s s s t e e l will c r a c k in w a t e r with
oxygen c o n c e n t r a t i o n s in the r a n g e of 1 p p m at 300~
t i t a n i u m a l l o y s w i l l c r a c k in N~O4, c h l o r i d e - w a t e r s ,
and in m e t h a n o l - N a C I - H 2 0 e n v i r o n m e n t s ~4 a s shown
in F i g . 12; c a r b o n s t e e l s c r a c k in l i q u i d a n h y d r o u s
a m m o n i a ; c a r b o n s t e e l s a l s o c r a c k in c e r t a i n m o i s t
m i x t u r e s of CO/CO2 at r o o m t e m p e r a t u r e . The old b e -
l i e f of p u r e m e t a l s not c r a c k i n g a p p e a r s to have b e e n
d e s t r o y e d by P u g h ( p r i v a t e c o m m u n i c a t i o n ) who has
d e m o n s t r a t e d t h a t 99.999 p c t p u r e c o p p e r i s s u b j e c t
to s t r e s s c o r r o s i o n c r a c k i n g u n d e r c e r t a i n c o n d i t i o n s .
10) W e a t h e r i n g S t e e l s . The d e v e l o p m e n t of a r c h i -
tectural facing alloys such as Corten has been a major
i m p r o v e m e n t in the c o r r o s i o n r e s i s t a n c e of low a l l o y
s t e e l s . T h e s e a l l o y s a r e now widely u s e d f o r b u i l d i n g s
and o t h e r s t r u c t u r e s without the m a j o r c o s t s of e x -
t e r i o r painting.
11) D i s p e r s i o n H a r d e n e d N i c k e l A l l o y s . TDNi and
T D N i C r a l l o y s a r e r e c e n t d e v e l o p m e n t s of high
s t r e n g t h and o x i d a t i o n r e s i s t a n t m a t e r i a l s f o r e l e v a t e d
t e m p e r a t u r e s e r v i c e . P r i c e s m u s t be r e d u c e d b e f o r e
they will be a d o p t e d c o m m e r c i a l l y on a w i d e s c a l e .
THE 'SEVENTIES
AS a final perspective in this lecture I wish to enu-
merate what needs to be done during the next decade.
i) Education. The need for education of designers,
materials people, management, and government as to

METALLURG[CALTRANSACTIONS VOLUME I,DECEMBER 1970-3263

the r a v a g e s and s u b t l e t i e s of c o r r o s i o n is today the
m o s t p r e s s i n g need in c o r r o s i o n . These effects should
not be left to the "faithful f e w " but should r e c e i v e
s u p p o r t f r o m g o v e r n m e n t and i n d u s t r y .
2) I n f o r m a t i o n C e n t e r . A complete i n f o r m a t i o n c e n -
t e r p a t t e r n e d a f t e r the Defense M e t a l s I n f o r m a t i o n
C e n t e r at B a t t e l l e i s badly needed. T h e r e i s s u f f i c i e n t
i n f o r m a t i o n a l r e a d y a v a i l a b l e today to p r e v e n t m a n y
f a i l u r e s . This would not be j u s t a data b a n k but the

II
c e n t e r would a c t i v e l y d i s s e m i n a t e i n f o r m a t i o n and ap-
p r i s e a p p r o p r i a t e d i s c i p l i n e s of r e l e v a n t i n f o r m a t i o n .

I1
,

]
\
\\

x
O05N NoCI ~

".. ~///
/
/ /
I

(I]
I
(I)
3) T e c h n i c a l C r i t i c a l i t y . A group o r s y s t e m approach
in r e s e a r c h in u n i v e r s i t i e s and other l a b o r a t o r i e s is
often helpful to p r o v i d e b e t t e r r e t u r n for the d o l l a r s
spent. S e v e r a l d i s c i p l i n e s can be b r o u g h t to b e a r with
f r u i t f u l r e s u l t s . F o r e x a m p l e , at Ohio State, g r a d u a t e
100(3 s t u d e n t s and other r e s e a r c h e r s a r e t a c k l i n g s t r e s s
corrosion from different "angles" including electro-
chemistry, mechanical metallurgy, physical metallurgy,
OlONuCl s u r f a c e c h e m i s t r y , and m e t a l p h y s i c s . S p e c i m e n s of
~No Faikwe
9, ODSN NaCl high p u r i t y m e t a l s and alloys, along with c o m m e r c i a l
= o O.ION NaO
== 9 0.i95N NoCl (Soturatod)
m a t e r i a l s , a r e u s e d . Also, p u r e and c o n t r o l l e d i m p u r i t y
E e n v i r o n m e n t s . The s t u d e n t s " r u b s h o u l d e r s " and d i s -
== 100 (I), c u s s t h e i r work a s it p r o g r e s s e s i n s t e a d of waiting for
..g= the l i t e r a t u r e which i s often delayed. In o t h e r words,
one l a r g e p r o j e c t on a c o n t i n u i n g b a s i s a t one site
o
could be m o r e f r u i t f u l p e r d o l l a r as c o m p a r e d to s m a l l
I--
s h o r t - t i m e p r o j e c t s with single a p p r o a c h e s on widely
d i f f e r e n t m a t e r i a l s . (This is not m e a n t to d i s c o u r a g e
the individual r e s e a r c h e r . ) This concept could be
10 t e r m e d " t e c h n i c a l c r i t i c a l i t y . " It should be m o r e
widely adopted.
Additional a d v a n t a g e s to the group a p p r o a c h o c c u r
when a l a r g e g r o u p is involved working on a wide v a r i -
ety of a r e a s i n c l u d i n g the solution of a c t u a l e n g i n e e r i n g
p r o b l e m s . Students a r e exposed to a wide r a n g e of phe-
I I i
n o m e n a and t h e i r b a c k g r o u n d s a r e e n h a n c e d through
0.10 0.20 0.50 0.4.0 ' % u l l " s e s s i o n s , s e m i n a r s , and d i s c u s s i o n s with v i s i -
P~rc~at Weter t o r s who a r e e x p e r t s in specific fields of c o r r o s i o n . D i s -
Fig. 12--Time-to-failure of Ti 8A1 1Mo 1V stressed to 90 pct c u s s i o n s of i n d u s t r i a l p r o b l e m s i n c l u d i n g f a i l u r e a n a l y -
of Y.S. in methanol containing varying amounts of NaC1 and
H20. s e s give the s t u d e n t s a feel for the r e a l w o r l d and what

T L _ _

Fig. 13--Upper two diagrams show schematic

relationship between binary equilibrium di- Time
agrams and TTT curve. Lower two diagrams
show relationship between Pourbaix diagrams
and polarization curve.
a Solution pH

- -
L
-- Eo(X ~ ~ ' ~ ~ E~o~
E o { ~ icl~

pH log i

3264-VOLUME 1, DECEMBER 1970 METALLURGICALTRANSACTIONS

the u l t i m a t e goal of c o r r o s i o n r e s e a r c h is all about,
n a m e l y , s a f e and r e l i a b l e d e s i g n p r e d i c t a b i l i t y .
4) P a s s i v i t y in Aqueous E n v i r o n m e n t s . T h e r e is
g r e a t i n c e n t i v e to develop a g r e a t l y i m p r o v e d u n d e r -
s t a n d i n g of p a s s i v i t y in aqueous e n v i r o n m e n t s . The
e m p h a s i s should be on a q u a n t i t a t i v e u n d e r s t a n d i n g .
Obtaining a q u a n t i t a t i v e p r e d i c t a b i l i t y for s t r e s s c o r -
r o s i o n c r a c k i n g , pitting, and c r e v i c e c o r r o s i o n as well
as a t m o s p h e r i c c o r r o s i o n d e p e n d s on a b e t t e r u n d e r -
s t a n d i n g of p a s s i v i t y .
5) E l e v a t e d T e m p e r a t u r e E l e c t r o c h e m i s t r y . Most
f u n d a m e n t a l e l e c t r o c h e m i c a l s t u d i e s a r e done at r o o m
t e m p e r a t u r e and a g r e a t m a n y i m p o r t a n t a p p l i c a t i o n s
a r e in the 100 ~ to 350~ r a n g e . S u b s t a n t i a l e m p h a s i s
on developing t e c h n i q u e s and conducting f u n d a m e n t a l
e l e c t r o c h e m i c a l r e s e a r c h in t h i s higher t e m p e r a t u r e
r a n g e is needed.
6) Hydrogen in Metals. D i s s o l v e d hydrogen in s t e e l s
and h y d r i d e p r e c i p i t a t e s in m a t e r i a l s like t i t a n i u m a r e
a m a j o r cause of c o r r o s i v e d e g r a d a t i o n . We need to
u n d e r s t a n d on a m o r e q u a n t i t a t i v e b a s i s both the e n t r y
of h y d r o g e n into the m e t a l and the i n t e r a c t i o n with hy-
drogen and the lattice.
7) I n c o r p o r a t e C o r r o s i o n L i m i t a t i o n s in Design M a n -
uals. Listing environmental (e.g., stress corrosion
cracking) l i m i t a t i o n s in d e s i g n m a n u a l s which o r d i -
n a r i l y give only s t r e n g t h data would p r e v e n t a g r e a t
many premature failures.
8) P a s s i v i t y in High T e m p e r a t u r e Oxidation. F o r
high t e m p e r a t u r e oxides we need to u n d e r s t a n d m o r e
about the f o r m a t i o n of second p h a s e s in the oxides,
m o r e about high t e m p e r a t u r e m e c h a n i c a l p r o p e r t i e s of
the oxides, and m o r e about i n t e r a c t i o n of i m p u r i t y
f r o m both the alloy and the e n v i r o n m e n t . F u r t h e r , a
m a j o r effort should be u n d e r t a k e n to u n d e r s t a n d the
f u n d a m e n t a l b e h a v i o r of s u l f u r i z a t i o n , c a r b u r i z a t i o n ,
and n i t r i d i n g .
9) C o r r o s i o n of C o m p o s i t e s . Composite m a t e r i a l s
a p p e a r to offer a n a t u r a l site for a c c e l e r a t e d c o r r o -
sion b e c a u s e of the different c h e m i c a l p r o p e r t i e s of
the c o m p o n e n t s involved b e c a u s e , in g e n e r a l , c o r r o -
sion p r o c e s s e s a r e a c c e l e r a t e d by d i f f e r e n c e s . C o m -
p o s i t e s m a y e x p e r i e n c e the s a m e p r o b l e m s as n o r m a l l y
found with elongated s t r i n g e r s . The volume of the c o r -
r o s i o n p r o d u c t s may play a m a j o r role as would a c -
c e l e r a t i n g c r e v i c e effects.
10) T u r b i n e M a t e r i a l s for A i r c r a f t and Automotive
A p p l i c a t i o n s . In the a i r c r a f t i n d u s t r y s t r e n g t h was
once the b o t t l e n e c k - - n o w it i s oxidation r e s i s t a n c e .
A d v a n c e s a r e now needed in this a r e a . In the a u t o m o -
tive i n d u s t r y , the application of t u r b i n e s is l i m i t e d by
cost. C h e a p e r t u r b i n e alloys for automotive a p p l i c a -
t i o n s is an a r e a needing g r e a t e r e m p h a s i s . I n e x p e n s i v e
high t e m p e r a t u r e m a t e r i a l s to p e r m i t lowering of h a r m -
ful e x h a u s t e m i s s i o n s f r o m a u t o m o b i l e s is a high p r i -
ority must.
11) G r e a t e r E m p h a s i s on M e t a l l u r g i c a l Aspects.
F i n e d e t a i l s of s t r u c t u r e and alloy composition need a
much b e t t e r definition. F o r e x a m p l e , the c o m p o s i t i o n
of g r a i n b o u n d a r i e s in the p r e s e n c e and a b s e n c e of
p r e c i p i t a t i o n n e e d s a v e r y g r e a t i m p r o v e m e n t in defi-
nition. We need to study m o r e c a r e f u l l y the c h e m i c a l
s t a b i l i t y of p r e c i p i t a t e s such as c a r b i d e s , sulfides,
and v a r i o u s i n t e r m e t a l l i c s .
It should be i n t e r e s t i n g to m e t a l l u r g i s t s to note the
METALLURGICALTRANSACTIONS
t h e r m o d y n a m i c and kinetic s i m i l a r i t i e s in e l e c t r o -
c h e m i s t r y and m e t a l l u r g y . Fig. 13 c o m p a r e s the
boundary c o n d i t i o n s i m p o s e d by b i n a r y e q u i l i b r i u m
d i a g r a m s on T T T c u r v e s with s i m i l a r b o u n d a r y con-
d i t i o n s i m p o s e d by P o u r b a i x d i a g r a m s on p o l a r i z a t i o n
curves.
12) S t a n d a r d i z a t i o n of P r o c e d u r e s . We need to con-
tinue our e f f o r t s in the d i r e c t i o n of s t a n d a r d i z i n g
t e s t i n g p r o c e d u r e s and n o m e n c l a t u r e . Both NACE and
ASTM have m a j o r e f f o r t s in this d i r e c t i o n ; these ef-
f o r t s should be e n c o u r a g e d and continued.
13) C r e v i c e Effects. We need a g r e a t e r e m p h a s i s
on u n d e r s t a n d i n g the c o r r o s i o n p r o c e s s e s in r e s t r i c t e d
g e o m e t r i e s as they affect pitting, c r e v i c e c o r r o s i o n ,
i n t e r g r a n u l a r c o r r o s i o n , and SCC. H e r e , equal e m p h a -
s i s n e e d s to be p l a c e d on r e f i n e d c a l c u l a t i o n a l tech-
n i q u e s and m i c r o e x p e r i m e n t a l t e c h n i q u e s .
14) Legal L i a b i l i t y for C o r r o s i o n Induced F a i l u r e s .
T h e r e is a d i s t u r b i n g t r e n d in this c o u n t r y which is
p l a c i n g m o r e l i a b i l i t y on the p r o d u c e r as opposed to
the u s e r in the c a s e of c o r r o s i o n induced f a i l u r e s .
P r o d u c e r s should f a m i l i a r i z e t h e m s e l v e s with the l e -
gal i m p l i c a t i o n s r e l a t i v e to i m p r o v e d m a t e r i a l s and
a p p r o p r i a t e p r e c a u t i o n s provided c u s t o m e r s . Better
quality c o n t r o l is m a n d a t o r y .
15) P r e d i c t i v e Capability for S t r e s s C o r r o s i o n
Cracking. While a t r e m e n d o u s a m o u n t of work has
been done on SCC in r e c e n t y e a r s , the m e c h a n i s t i c
and p r e d i c t i v e p i c t u r e is s t i l l o b s c u r e . We need
g r e a t e r e m p h a s i s on studying the unit p r o c e s s e s :
t r a n s i e n t anodic k i n e t i c s and d i s l o c a t i o n - s u r f a c e in-
t e r a c t i o n , as well a s the p a s s i v i t y at l o c a l g e o m e t r y
a r e a s m e n t i o n e d above.
16) B i o m e d i c a l M a t e r i a l s . B e t t e r m a t e r i a l s and
education a r e n e e d e d for m e d i c a l m e t a l s for s u r g i c a l
i m p l a n t s . I g n o r a n c e in this a r e a is e x e m p l i f i e d by a
p a p e r r e p o r t i n g r e s u l t s of t e s t s on s p e c i m e n s of a
v a r i e t y of m e t a l s and alloys i m p l a n t e d in r a b b i t s .
This p a p e r r e p o r t e d d i f f e r e n t r e s u l t s for c o l u m b i u m
and n i o b i u m ! l
ACKNOWLEDGMENTS
I wish to acknowledge the support and e n c o u r a g e m e n t
by many p e r s o n s and o r g a n i z a t i o n s : My c o l l e a g u e s at
Ohio State, P r o f e s s o r s Beck, Rapp, and Staehle. M e s s r s .
Burte, K i r k p a t r i c k , Lovelace, Lynch, and Standifer of
the A i r F o r c e M a t e r i a l s L a b o r a t o r y ; S i m m o n s , Singer,
and Van Echo of AEC; and Deutsch and R a r i n g of NASA;
The Alloy C a s t i n g I n s t i t u t e and the A m e r i c a n Iron and
Steel Institute; Dr. K r a m e r of ONR who s t a r t e d c o r r o -
sion work at Ohio State in 1946 with a g r a n t for funda-
m e n t a l c o r r o s i o n r e s e a r c h , and also Dr. P. A. C l a r k i n .
F i n a l l y , h u n d r e d s of other f r i e n d s engaged in the bat-
tie a g a i n s t c o r r o s i o n .
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VOLUME 1,DECEMBER 1970-3265
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3266-VOLUME 1, D E C E M B E R 1970
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METALLURGICAL TRANSACTIONS