294 JOURNAL OF THE ELECTROCHEMICAL SOCIETY A p r i l 1959

are i n t e r p o s e d b e t w e e n it a n d t h e n i t r o group. I t is A n y discussion of this paper will appear i n a Discus-

also seen t h a t the a d d i t i o n of successive chloro or
n i t r o g r o u p s to a p r i m a r y n i t r o c a r b o n a t o m i n -
creases the p o t e n t i a l of t h e p a r e n t n i t r o a l k a n e c o m -
p o u n d w i t h each s u c c e e d i n g a d d i t i o n of the e l e c t r o n
a t t r a c t i n g group.
2. C o u l o m e t r i c s t u d i e s i n a MgBr2 e l e c t r o l y t e i n -
dicate e l e c t r o d e efficiencies of 3 6 - 5 2 % c a n be o b -
t a i n e d f r o m a n u m b e r of solid n i t r o a l k a n e c o m -
p o u n d s , a s s u m i n g a 6 - e l e c t r o n c h a n g e per n i t r o
group. T h e l a t t e r a s s u m p t i o n is i n d o u b t , h o w e v e r ,
since t h e r e d u c t i o n m e c h a n i s m is n o t k n o w n .
3. M a g n e s i u m - n i t r o a l k a n e d r y cells h a v e b e e n
a s s e m b l e d , a n d t h e p e r f o r m a n c e c h a r a c t e r i s t i c s of
these cells i n d i c a t e t h a t n i t r o a l k a n e c o m p o u n d s show
p r o m i s e for use as cathodes i n p r i m a r y cells.
Acknowledgment
The a u t h o r s w i s h to e x p r e s s t h e i r a p p r e c i a t i o n to
Mr. A. M. Cooke a n d Dr. R. S. E g l y of C o m m e r c i a l
S o l v e n t s C o r p o r a t i o n a n d Dr. M. H. Gold of A e r o j e t -
G e n e r a l C o r p o r a t i o n for s u p p l y i n g m a n y of the
c h e m i c a l s u s e d i n this i n v e s t i g a t i o n . T h a n k s are d u e
also to Mr. G. R. G a n g e s of this l a b o r a t o r y for as-
s e m b l i n g a n d t e s t i n g t h e d r y cells.
Manuscript received J u l y 7, 1958. This paper was
presented before the Ottawa Meeting, Sept. 28-Oct. 2,
1958.
sion Section to be published in the December 1959
JOURNAL.
REFERENCES
1. C. K. Morehouse and R. Glicksman, This Journal,
104, 467 (1957).
2. R. Glicksman and C. K. Morehouse, ibid., 1@5, 299
(1958).
3. R. Glicksman and C. K. Morehouse, ibid., 105, 613
(1958).
4. C. K. Morehouse and R. Glicksman, ibid., 105, 306
(1958).
5. C. K. Morehouse and R. Glicksman, ibid., 105, 619
(1958).
6. C. K. Morehouse and R. Glicksman, ibid., 103, 94
(1956).
7. R. Glicksman and C. K. Morehouse, ibid., 102, 273
(1955).
8. I. M. Kolthoff and J. J. Lingane, "Polarography,"
Vol. II, Chapter XLII, Interscience Publishers,
New York (1952).
9. L. F. Fieser and M. Fieser, "Organic Chemistry,"
3rd ed., pp. 162-164, Reinhold P u b l i s h i n g Corp.,
New York (1956).
10. C. R. Noller, "Chemistry of Organic Compounds,"
p. 430, W. B. Saunders Co., Philadelphia (1951).
11. H. B. Hass and E. F. Riley, Chem. Revs., 32, 373
(1943).
12. H. B. Hass, E. F. Riley, and H. Schechter, "The Sci-
ence of Petroleum," Oxford Univ. Press, Vol. V.
pt II.
13. N. Levy, and J. D. Rose, Quart. Rev., 2, 358 (1948).
14. R. C. Kirk, P. F. George, and A. B. Fry, This Jour-
nal, 99, 323 (1952).

Oxidation Studies on the Iron-Chromium-Aluminum Heater Alloys

Earl A. Gulbransen and Kenneth F. Andrew

Research Laboratories, Westinghouse Electric Corporation, Pittsburgh, Pennsylvania

ABSTRACT
The oxidation behavior of three i r o n - c h r o m i u m - a l u m i n u m alloys was
studied using sensitive weight gain techniques. I n addition, x - r a y diffraction
methods were used to d e t e r m i n e the crystal structure and composition of the
oxide films. The adhesion characteristics of the oxide film to the metal were
tested by i n t r o d u c i n g strains into the metal oxide system d u r i n g oxidation.
Rate studies show a change in rate for the three alloys n e a r 900~ Between
900 ~ to 1050~ the rate of oxidation r e m a i n e d n e a r l y constant; above 1050~
it increased again. X - r a y diffraction studies suggest that a crystal structure
,transformation was occurring i n the oxide. At 1050~ a-A120~ was the m a i n
oxide i n the scale.
The parabolic rate law was used to i n t e r p r e t the rate data. Deviations oc-
curred d u r i n g the initial reaction period as a result of crystal structure t r a n s -
formations i n the film. Heats of activation of 76 to 77 k c a l / m o l e were cal-
culated for the range 700~176
S t r a i n oxidation studies showed the oxide scale on the high a l u m i n u m
alloy to be less susceptible to damage t h a n the lower a l u m i n u m content alloys.
These studies were correlated directly with practical performance tests.
T h e r m o d y n a m i c analyses of the several types of solid-solid and solid-gas
reactions were used to i n t e r p r e t the rate and structure studies. P r e l i m i n a r y de-
sign principles were proposed for heat resistant alloys.

H e a t e r alloys h a v e b e e n c h a r a c t e r i z e d b y t h r e e 4 - 6 % A1, b a l a n c e Fe. Both a l l o y s y s t e m s consist of a

i m p o r t a n t p r o p e r t i e s : (a) high m e l t i n g point, ( b )
h i g h r e s i s t a n c e to o x i d a t i o n , a n d (c) good m e c h a n -
ical p r o p e r t i e s . F o r e x t r e m e service conditions, t w o
t y p e s of alloys h a v e b e e n used: (a) N i - C r alloys of
n o m i n a l c o m p o s i t i o n 80% Ni a n d 20% Cr, a n d (b)
F e - C r - A 1 alloys of n o m i n a l c o m p o s i t i o n 20-25% Cr,
s i n g l e p h a s e w i t h t h e N i - C r alloys h a v i n g t h e a u s -
t e n i t i c s t r u c t u r e a n d the F e - C r - A 1 alloys t h e f e r -
ritic s t r u c t u r e .
T h e m a x i m u m o p e r a t i n g t e m p e r a t u r e i n t h e final
a n a l y s i s is l i m i t e d b y t h e a l l o y ' s solidus point. This
is a b o u t 1440~ for the F e - C r - A 1 alloys a n d 1380~

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 V o l . 106, N o . 4 OXIDATION STUDIES
for t h e N i - C r alloys. N e i t h e r s e r i e s of a l l o y s c a n b e
u s e d a t t e m p e r a t u r e s n e a r t h e i r s o l i d u s p o i n t as t h e
r a t e of o x i d a t i o n a n d s c a l i n g b e c o m e s e x c e s s i v e l y
h i g h a n d t h e m e c h a n i c a l p r o p e r t i e s b e c o m e poor. A t
e x t r e m e t e m p e r a t u r e s t h e o x i d a t i o n r e s i s t a n c e of t h e
a l l o y d e t e r m i n e s , in p a r t , t h e u s e f u l n e s s of t h e a l l o y
as a h i g h - t e m p e r a t u r e m a t e r i a l .
T h e o x i d a t i o n r e s i s t a n c e of m e t a l s h a s b e e n r e l a t e d
to t h e f o r m a t i o n of l a t t i c e d e f e c t s a n d t h e d i f f u s i o n
of cations, anions, a n d e l e c t r o n s t h r o u g h t h e s e d e -
fects (1,2). T h i s p i c t u r e , b a s e d on a u n i f o r m o x i d e
film, is p r o b a b l y too s i m p l e as h a s b e e n s h o w n b y t h e
f o r m a t i o n of o x i d e n e e d l e s , w h i s k e r s , a n d p l a t e l e t s
(3, 4) on t h e scale. T h e s e s u g g e s t t h a t c e r t a i n a r e a s
of t h e m e t a l a r e m u c h m o r e r e a c t i v e t h a n t h e r e s t
of t h e s u r f a c e .
If t h e m e t a l is o x i d i z e d u n d e r p e r i o d i c t e m p e r a -
t u r e c y c l e s or w h e n s u b j e c t e d to s t r e s s e s o r to a
strain, the oxide-metal interface may be damaged
( 5 ) . A s a r e s u l t , t h e r a t e of o x i d a t i o n i n c r e a s e s . T h e
o x i d a t i o n r e s i s t a n c e of t h e a l l o y for t h e s e c o n d i t i o n s
is g o v e r n e d n o t o n l y b y d i f f u s i o n p r o c e s s e s b u t also
b y t h e c h e m i c a l a n d p h y s i c a l p r o p e r t i e s of t h e o x i d e ,
alloy, a n d o x i d e - a l l o y i n t e r f a c e .
T h e o b j e c t i v e s of t h i s s t u d y a r e : ( a ) to d e t e r m i n e
t h e k i n e t i c s of t h e o x i d a t i o n of t h r e e F e - C r - A 1 a l l o y s
as a f u n c t i o n of t i m e , t e m p e r a t u r e , a n d a l l o y c o m -
p o s i t i o n , ( b ) to d e t e r m i n e t h e effect of s t r a i n on t h e
o x i d a t i o n process, (c) to d e t e r m i n e t h e c r y s t a l s t r u c -
t u r e of t h e o x i d e scales, a n d ( d ) to i n t e r p r e t f r o m
the experimental observations and thermodynamic
a n a l y s i s t h e h i g h h e a t r e s i s t a n c e of t h e F e - C r - A 1
alloys.
L i t e r a t u r e . - - v o n K a n t z o w (6) first o b s e r v e d t h a t
t h e h e a t r e s i s t a n c e of s t e e l s w a s i m p r o v e d b y a l l o y -
i n g w i t h a l u m i n u m . A s e r i e s of a l l o y s of F e - C r a n d
A1 w e r e d e v e l o p e d a n d p a t e n t e d . S i n c e 1932 t h e s e
a l l o y s h a v e b e e n m a n u f a c t u r e d u n d e r t h e n a m e of
Kanthal 1alloys.
T h e h e a t r e s i s t a n c e of F e - A 1 a n d F e - C r a l l o y s h a s
been studied by several groups (7-12). Hauttman
(7) s h o w e d t h e s t r o n g effect of i n c r e a s i n g t h e A1
c o n t e n t b e t w e e n 4 a n d 9% at 1000~ AI~O, w a s
f o u n d in t h e o x i d e l a y e r on a 9.44% A1 alloy. S c h e i l
a n d S c h u l z (8) in a s t u d y of C r - A 1 steels at 1200~
showed that the most oxidation resistant alloys were
c o v e r e d w i t h a w h i t e a l u m i n u m o x i d e scale. A t t e m -
p e r a t u r e s a b o v e 1000~ a n A1 c o n t e n t of g r e a t e r
t h a n 4% w a s n e c e s s a r y to g e t a h i g h d e g r e e of o x i -
dation resistance. The high oxidation resistance
properties and high electrical resistance suggested
t h e u s e of A 1 - C r steels for h e a t e r alloys. Z i e g l e r (9)
a n d P o r t e v i n , P r e t e t , a n d J o l i v e t (10) also n o t e d t h e
b e n e f i c i a l affect of a d d i n g A1 to i m p r o v e t h e o x i d a -
t i o n r e s i s t a n c e of steels.
T h e n a t u r e of t h e s c a l i n g p r o c e s s in t h e o x i d a t i o n
of steels c o n t a i n i n g Ni, Cr, a n d A1 h a s b e e n d i s c u s s e d
b y K r a i n e r , W e t t e r n i k , a n d C a r i u s (11). T h e loss b y
s c a l i n g w a s l o w e s t f o r s t e e l c o n t a i n i n g 24% C r a n d
5 % A1 a n d h a v i n g a s c a l e of AI~O~. H o w e v e r , t h e r e -
s i s t a n c e of t h e l a y e r to s c a l i n g w i t h t e m p e r a t u r e
f l u c t u a t i o n s w a s b e s t f o r a Cr20, scale a n d p o o r e s t f o r
a n AI~O, scale.
1 K a n t h a l is a p r o p r i e t o r y n a m e f o r a s e r i e s of h e a t e r a l l o y s m a n -
ufactured by Kanthal Corp., Stamford, Conn.
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ON Fe-Cr-A1 ALLOYS 295
T h e s e g r e g a t i o n of a l u m i n u m a t o m s in A 1 - C r - F e
a l l o y s t o w a r d t h e p e r i p h e r y is d i s c u s s e d b y S e k t o v a
(12). S e k t o v a also n o t e d t h e s t r o n g effect of A1 to
i m p r o v e t h e o x i d a t i o n r e s i s t a n c e of t h e s e alloys.
Experimental
The vacuum microbalance method has been de-
s c r i b e d ( 1 3 - 1 5 ) . I n t h i s s t u d y a m i c r o b a l a n c e of l o w
s e n s i t i v i t y , 4.39~g/0.001 e m deflection, w a s used. A
t o t a l w e i g h t c h a n g e of a b o u t 7 m g c o u l d b e m e a s u r e d
w i t h a s e n s i t i v i t y of 1.10 X 10 -~ g. This l o w s e n s i -
t i v i t y m i c r o b a l a n c e t o g e t h e r w i t h t h e u s e of s m a l l e r
s p e c i m e n s i n c r e a s e d t h e r a n g e of t h e m e a s u r i n g
s y s t e m b y a f a c t o r of 25.
A vacuum grade mullite furnace tube contained
t h e s a m p l e . I t w a s s e a l e d d i r e c t l y to t h e P y r e x glass
s y s t e m . W i t h t h e s p e c i m e n in t h e f u r n a c e t u b e at
1100~ a M c L e o d g a u g e p r e s s u r e of 3 X 10 ~ m m H g
w a s r e a d i l y o b t a i n e d in t h e s y s t e m . T h e v a c u u m s y s -
t e m a n d gas p r e p a r a t i o n s y s t e m h a v e b e e n d e -
s c r i b e d (15).
T h e f u r n a c e t e m p e r a t u r e w a s c o n t r o l l e d to a b o u t
--1.5~ T h e r e w a s no e v i d e n c e of a t e m p e r a t u r e
gradient along the 2.25-cm specimen during oxida-
tion.
Weight changes occurring during the reaction
w e r e f o l l o w e d in a s e m i c o n t i n u o u s m a n n e r b y o b -
s e r v i n g a p o i n t e r on a b a l a n c e b e a m u s i n g a m i c r o -
m e t e r m i c r o s c o p e . R e a d i n g s of t h e b a l a n c e w e r e
t a k e n i n v a c u o b e f o r e r e a c t i o n at t e m p e r a t u r e , d u r -
i n g t h e r e a c t i o n in o x y g e n , a n d a f t e r r e a c t i o n i n
vacuo. W e i g h t c h a n g e s d u e to r e a c t i o n of c a r b o n in
t h e m e t a l w i t h t h e s u r f a c e o x i d e a n d to v a p o r i z a t i o n
of m e t a l l i c e l e m e n t s f r o m t h e a l l o y w e r e s m a l l .
S p e c i m e n s u s e d i n t h i s s t u d y w e r e t h r e e t y p e s of
commercial heater alloys obtained from the Kanthal
Corporation. Table I shows the approximate and
s p e c t r o s c o p i c a n a l y s i s of t h e a l l o y s a n d t h e i r r a t i n g s
as h e a t e r alloys. T h e 0.025-cm t h i c k s p e c i m e n s w e r e
p r e p a r e d f r o m 0.63 c m w i d e s t r i p s a n d h a d s u r f a c e
a r e a s of a b o u t 2.25 c m ~. S a m p l e w e i g h t w a s a b o u t
0.1886 g. S e c t i o n s of t h e s t r i p w e r e a b r a d e d s t a r t i n g
w i t h No. 1 p o l i s h i n g p a p e r a n d finishing t h r o u g h 4 / 0
p a p e r . To a v o i d o x i d a t i o n , t h e l a s t s t a g e w a s c a r r i e d
out under purified kerosene. After abrading, the
samples were cleaned with soap and water, distilled
w a t e r , p e t r o l e u m e t h e r , a n d a b s o l u t e alcohol, a n d
s t o r e d in a d e s i c c a t o r .
S t r a i n o x i d a t i o n . - - E a r l i e r s t u d i e s of t h e N i - C r s e r i e s
of a l l o y s (5) a n d t h e s t u d i e s of K r a i n e r . W e t t e r n i k ,
a n d C a r i u s (11) h a v e s h o w n t h a t c o n s t a n t t e m p e r a -
t u r e s t u d i e s c a n n o t b e u s e d a l o n e to e v a l u a t e t h e
p r o t e c t i v e c h a r a c t e r i s t i c s of a p a r t i c u l a r a l l o y if
t h e a l l o y is s u b j e c t e d to s t r e s s o r to a s t r a i n in its
use. To g i v e a m o r e c o m p l e t e p i c t u r e of t h e p h y s i c a l
a n d c h e m i c a l f a c t o r s i n v o l v e d in h i g h - t e m p e r a t u r e
oxidation, a new test method called .strain oxidation
w a s d e v e l o p e d . I n t h i s m e t h o d t h e m e t a l is o x i d i z e d
to a g i v e n w e i g h t gain, r e m o v e d f r o m t h e b a l a n c e
s y s t e m a n d s t r a i n e d 1 - 4 % in a t e n s i l e m a c h i n e . A f t e r
c u t t i n g a s m a l l e r s e c t i o n of t h e s a m p l e f r e e f r o m g r i p
m a r k s , t h e s p e c i m e n w a s p l a c e d in t h e b a l a n c e s y s -
tem and re-oxidized. Rate calculations before and
a f t e r s t r a i n w e r e m a d e on a 1 c m ~ basis. To a c h i e v e
 296 JOURNAL OF THE ELECTROCHEMICAL SOCIETY April 1959
Table I. a. Approximate composition* Fe-Cr-A[ alloys (Kanthal Corporation)
Weight per cent

Relative useful
Alloy C Si Mn Cr A1 Co Fe l i f e a t 1200~

1 0.07 0.65 0.26 23.0 5.7 0.57 Balance 175

2 0.06 0.74 0.27 22.4 5.1 0.59 Balance 150
3 0.07 0.65 0.22 21.7 4.5 0.58 Balance 100

b. Spectroscopic analyses~ (Westinghouse)

Weight per cent

Alloy Mo Ni Cu Zr Pb$ Sn Mg V Ca

1 <0.01 <0.I ~0.01 0.01-0.05 <0.01 <0.05 <0.001 <0.01 <0.01

2 0.5-0.9 0.1-0.5 ~--0.01 Not detected <0.03 <0.05 <0.001 <0.01 <0.01
3 <0.01 <0.I -.,0.01 Not detected <0.01 <0.05 <0.001 <0.01 <0.01

* T r a c e s o f o t h e r e l e m e n t s to i m p r o v e o x i d a t i o n r e s i s t a n c e .
f T e s t e d f o r b u t n o t d e t e c t e d : N b , T a , Ti, a n d Ce.
Erratic segregation.

a s t r a i n of 1% a stress c o r r e s p o n d i n g to t h e y i e l d t i m e o f 2 hr. W e i g h t g a i n d u r i n g r e a c t i o n w a s cal-

p o i n t or g r e a t e r was i m p o s e d o n the s a m p l e . c u l a t e d i n u n i t s of m i c r o g r a m s p e r s q u a r e c e n t i m e t e r .
X-ray di]yraction method.--Filtered Cr K~ r a d i a t i o n X - r a y diffraction a n a l y s i s s u g g e s t e d t h a t the
w a s used w i t h a fine focus x - r a y d i f f r a c t i o n tube. T h e oxides w e r e l a r g e l y a-AI~O~ a n d Cr~O+. A s s u m i n g
diffraction p a t t e r n s w e r e m a d e at r o o m t e m p e r a t u r e a-ALO~ a n d a s u r f a c e r o u g h n e s s r a t i o of u n i t y , a
u s i n g a 9 cm U n i c a m c a m e r a . v a l u e of 54 was c a l c u l a t e d for the r e l a t i o n b e t w e e n
O x i d e s a m p l e s w e r e r e m o v e d f r o m the alloy b y t h e oxide t h i c k n e s s i n a n g s t r o m s a n d t h e w e i g h t
e l e c t r o c h e m i c a l s t r i p p i n g (16). A f t e r w a s h i n g s e v - gain in micrograms per square centimeter.
era1 t i m e s i n d i s t i l l e d w a t e r , the oxide films w e r e Time and temperature.--Figures 1-3 show o x i d a -
r o l l e d o n to s m a l l glass c a p i l l a r y t u b e s for m o u n t i n g t i o n c u r v e s for the t h r e e alloys i n the r a n g e 800 ~
in the x - r a y camera. ll00~ There was a rapid initial reaction rate in all
curves, w i t h t h e r a t e d e c r e a s i n g as t h e o x i d e film
Results
grows. No e v i d e n c e w a s f o u n d for a l i n e a r r a t e l a w
T h e t h r e e alloys w e r e oxidized at 6 0 0 ~ 1 7 6 for the t i m e s studied. A l l of t h e oxides w e r e g r a y i s h -
u s i n g a n o x y g e n p r e s s u r e of 7.6 c m Hg for a r e a c t i o n b l a c k a n d w e r e a d h e r e n t to the a l l o y w h e n cooled to
room temperature.
,6o I B e l o w 900~ t h e o x i d a t i o n c u r v e s show a s t r o n g
~'~ / A II00~ d e p e n d e n c e on t h e t e m p e r a t u r e . H o w e v e r , b e t w e e n
900 ~ a n d 1050~ the r a t e w a s n e a r l y c o n s t a n t for
~ .---o--- C 1000~ each of the alloys. A b o v e 1050~ it i n c r e a s e d a g a i n
=L 80 ~:::~ "'~"~ ~ I with temperature.
~_ 8 1050~
This n e a r l y c o n s t a n t r a t e of r e a c t i o n b e t w e e n 950 ~
40 ~ E 900% a n d 1050~ is of g r e a t i n t e r e s t a n d suggests t h a t
.o..o-o'- F 850~ m a j o r s t r u c t u r a l c h a n g e s w e r e o c c u r r i n g i n t h e alloy
~ G 800% or i n t h e oxide scale.
0
0 20 40 60 80 100 120 140 160 A c o m p a r i s o n of the r a t e of o x i d a t i o n of t h e t h r e e
Time (min.)
alloys at l l 0 0 ~ shows o n l y m i n o r differences i n the
Fig. 1. Effect of temperature on oxidation Fe-Cr-AI alloy 1, a m o u n t of o x i d a t i o n or i n t h e final r a t e of o x i d a t i o n .
7.6 cm Hg of O~, abraded through 4 / 0 .
P r a c t i c a l p e r f o r m a n c e tests of alloys i n T a b l e I show
200, , [ alloy 1 to be s u p e r i o r to 2 a n d 3.

~ C IOiO~ -

A I IO0~
160

120
r
i j j AIIO0~
. ~ D 950~
~c so +
B I050~
I /D 950~ ---

~ F 850~ ~_~r " I , , , ~ F 850~

o 8oo.c + , G 800~
Oc~ 20 40 60 80 I00 120 140 160 O0 20 40 60 80 I00 120 140- 160
Time (rain.) Time (mini
Fig. 2. Effect of temperature on oxidation of Fe-Cr-AI alloy Fig. 3. Effect of temperature on o x i d a t i o n of Fe-Cr-AI
2, 7.6 cm Hg of 02, abraded through 4 / 0 . alloy 3, 7.6 cm Hg of 02, abraded through 4 / 0 .

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 V o l . 106, N o . 4 OXIDATION STUDIES ON Fe-Cr-A1 ALLOYS 297
20,000 ~
I100 1000 9 0 0 8 0 0 700

/ IQ-n
,~.t, r, t I
% r6,ooo r
/ /',ll I I I I - 2 hrs - -

//
3 - 4 hrs - -
5 - 6 hrs

E 12,00O
::k
I I
_c 8,000 / l ll~l
II~.~I I
!
c)
CO
% ~'~ I II I\l I

N]
4,000
II

o
E II
0 20 40 60 80
Time (min)
100 120 140 I 0-~4 II
II
< ]I

Fig. 4. Oxidation Fe-Cr-AI alloy 2, 1100~ 7.6 cm Hg of

0~, abraded through 4 / 0 , parabolic plot, A = 2.16 x 10 -~
(g/crn=) =sec -1. i d ~ __
II It
II I I ~1
I 0,0 0 0

N
E
~J
/"
8,000
fJ
/
j r"

16*J,60 .70
II
II
II
.80 .90
I I
II
I0
1_ x l0 s
T
I I0 120 LSO

6,000 r
Fig. 6. Oxidation Fe-Cr-AI alloy 1, log A vs. 1 / T A H
76,900 cal/rnole.
_ 4000

f'
o
~C
II00 IO00 9 0 0 8 0 0 700
LO-'~
2,000 I ,1. T !
iV I I o I - 2 hrs - -
~ ! I 5 - 4 hrs - -

o ~t,t t 5- 6 hrs
o 2o 120 ]WII~,I I
-F-
40 60 80 100 140
T~me (rain.) IG m
i 11 i
Fig. 5. Oxidation Fe-Cr-AI alloy 2, 1000~ 7.6 cm Hg of I l] I I
0_~, abraded through 4 / 0 , parabolic plot, A = 0.695 x 10 -12
(g/cm2) =sec -~.
I. II ~11
- I013j
'o
tl] I~1 I
Parabolic rate l a w . - - T h e p a r a b o l i c r a t e l a w is u s e -
f u l i n e v a l u a t i n g t h e n a t u r e of o x i d a t i o n r e a c t i o n s
I I]
I1
II
I\1
i-T-
e v e n t h o u g h d e v i a t i o n s m a y occur, since the l a w is !
II
[ I I I I T '~

b a s e d on f u n d a m e n t a l p h y s i c a l p r i n c i p l e s (1, 2). =
, [
Ii 7L
Physical and chemical changes occurring in the ox- I II I I II I
ide film a r e n o t e d as d e v i a t i o n s f r o m the r a t e law.
T h e e q u a t i o n states t h a t W ~ = A t -F C. H e r e W is
I1 3!
I|
Ii II
t h e w e i g h t gain, t is the time, a n d A a n d C a r e
c o n s t a n t s . F i g u r e 4 shows a p a r a b o l i c r a t e l a w plot
I1 IJ 111 I
a t 1100~ for a l l o y 2. A g r e e m e n t w i t h the t h e o r e t i c a l
,o-,, .'60 .70
!! 11 .80 90
111
I0 I I0
l
120 130
i x 103
~-
l a w w a s good except for t h e i n i t i a l p a r t of t h e r e -
action. Fig. 7. Oxidation Fe-Cr-AI alloy 2, log A vs. 1 / T • =
F r o m 750 ~ to 900~ t h e p a r a b o l i c r a t e l a w c o n - 76,900 cal/mole.
s t a n t i n c r e a s e s d u r i n g t h e first s e v e r a l h o u r s of r e -
a c t i o n over the i n i t i a l v a l u e , w h i l e a b o v e a n d b e l o w s t r a i g h t l i n e r e l a t i o n s h i p w a s observed. B e t w e e n
this t e m p e r a t u r e r a n g e the p a r a b o l i c r a t e l a w c o n - 900 ~ a n d 1050~ t h e plots show t h e t r a n s i t i o n p h e -
s t a n t decreases w i t h time. T h e s e effects also m a y b e n o m e n o n a l r e a d y noted. T h e slopes of t h e log A vs.
r e l a t e d to m i n o r c h a n g e s i n the c o m p o s i t i o n or p h y s - 1 / T plot a n d t h e a b s o l u t e v a l u e s of A for t h e t h r e e
ical s t r u c t u r e of the oxide film. I n t h e t e m p e r a t u r e alloys w e r e similar. A n a l y s i s of the slopes of Fig. 6-8
range 900~176 a major change occurred in the for alloys 1 a n d 2 shows h e a t s of a c t i v a t i o n of 76,900
alloy or oxide film, since the t e m p e r a t u r e coefficient c a l / m o l e a n d for a l l o y 3, 76,500 c a l / m o l e . T h e s e are
of t h e r e a c t i o n w a s n e a r zero. A c h a n g e also occurs v e r y h i g h for o x i d a t i o n processes.
i n the oxide film or a l l o y as a f u n c t i o n of t i m e for
this t e m p e r a t u r e r a n g e . This was seen i n t h e 1000~ Strain Oxidation
p a r a b o l i c r a t e l a w plot s h o w n i n Fig. 5. T h e p a r a - T h e s e v e r a l alloy s p e c i m e n s w e r e oxidized at
bolic r a t e l a w c o n s t a n t d e c r e a s e d r a p i d l y d u r i n g the 900~ to f o r m a n oxide film of a b o u t 44.7/~g/cm "~or
first 60 m i n of r e a c t i o n a f t e r w h i c h a n e a r l y c o n s t a n t a n e s t i m a t e d oxide t h i c k n e s s of 2410A. A f t e r s t r a i n -
value was found. i n g 2 - 4 % , t h e s p e c i m e n s w e r e r e - o x i d i z e d at 900~
T e m p e r a t u r e d e p e n d e n c e . - - F i g u r e s 6 to 8 show F i g u r e 9 shows t h e r e s u l t s for a 2 % s t r a i n for a l l o y
plots of the l o g a r i t h m of t h e p a r a b o l i c r a t e l a w c o n - 1. T h e o x i d a t i o n c u r v e a f t e r 2% s t r a i n w a s n e a r l y
s t a n t A vs. 1 / T for the t h r e e alloys. B e l o w 900~ a c o n t i n u o u s w i t h t h e c u r v e for the i n i t i a l o x i d a t i o n .

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 298 JOURNAL OF THE ELECTROCHEMICAL SOCIETY A p r i l 1959
~
I100 IO00 9 0 0 8 0 0 700 Time (min.)
6000 o 40 80 12o
I0 " ,~ 9 l

500(
b
%
4001
E
v
300C

200C

100( ~ 4 ~ 1 7 6 ~ d reh[ ~

4O 80
Time (min.)

Fig. 10. Strain oxidation of Fe-Cr-AI alloy 1, 4 % strain:

tO"16 a, 900~ 7.6 cm Hg of 02, A = 4.09 x 10 -'3 (g/crn~):/sec;
,60 70 80 90 10 110 120 130
I
b, 900~ 7.6 cm Hg of 0=, after cooling, stretching 4 % and
u x 103
reheating, A = 5.12 x 10 -= (g/cm~)2/sec.
Fig. 8. Oxidation Fe-Cr-AI alloy 3, log A vs. I / T --AH
76,500 cal/mole. Time (min.)
0 40 80 120
6000
Time (rain.)
5000 0 40 80 IY0
/
/
5000
N b
4000 %
, 4ooo
E l/b
3000

o
2000

,ooo
:sreche 2 % and reheoled _
.c_
. ~ 3000
& 2000
"~
1000
~
~c~
~Coole
I
d, slretched
2 % and reheated_
. 0
f 40 80
,
o I
Time (min.) 0 40 6o
Time ( m i n )
Fig. 9. Strain oxidation of Fe-Cr-AI alloy 1, 2 % strain:
a, 900~ 7.6 cm Hg of Os, A = 3.55 x 10 -~3 (g/cm2)=/sec; Fig. ]1. Strain oxidation of Fe-Cr-AI alloy 2, 2 % strain:
b, 900~ 7.6 cm Hg of 02, after cooling, stretching 2 % and a, 900~ 7.6 cm Hg of 0~, A = 3.40 x 10 -~ (g/crn:)S/sec,
reheating, A = 4.0 x 10 -~ (g/cm2)~/sec. b, 900~ 7.6 cm Hg of Os, after cooling, stretching 2 % and
reheating, A = 6.41 x 10 -~s (g/cms)~/sec.
F i g u r e 10 s h o w s t h e s t r a i n - o x i d a t i o n c u r v e f o r a l l o y
1 for a 4% s t r a i n . A m a r k e d c h a n g e in t h e c o u r s e l o n g - p e r i o d d a m a g e f o r b o t h 2 a n d 4% s t r a i n s for
of o x i d a t i o n w a s n o t e d as a r e s u l t of t h e 4% s t r a i n . a l l o y 1.
T h e u s u a l effect of s t r a i n b e t w e e n t h e s e v e r a l F i g u r e s 11 a n d 12 s h o w t h e r e s u l t s of s t r a i n o x i d a -
o x i d e l a y e r s a n d t h e m e t a l is f l a k i n g of t h e o x i d e t i o n s t u d i e s of a l l o y s 2 a n d 3. B o t h a l l o y s s h o w s h o r t -
w i t h loss of p r o t e c t i o n of t h e m e t a l ( 5 ) . F o r h e a t r e - a n d l o n g - p e r i o d d a m a g e r e s u l t i n g f r o m a 2% s t r a i n .
sistant alloys 1-4% strain may not visually destroy A c o m p a r i s o n of t h e s t r a i n o x i d a t i o n t e s t s f o r a l l o y s
the bonding between the oxide and metal but local- 1, 2, a n d 3 s h o w a l l o y 1 to b e s u p e r i o r . T h e s e r e s u l t s
i z e d d a m a g e on a m i c r o s c o p i c or s u b m i c r o s c o p i c l e v e l a r e in a g r e e m e n t w i t h t h e u s e f u l life t e s t s g i v e n in
m a y o c c u r w h i c h affects t h e r a t e of o x i d a t i o n . T a b l e I. T h e u s e f u l l i f e t e s t s a r e t e m p e r a t u r e c y c l i n g
S o m e d a m a g e in t h e o x i d e or a t t h e i n t e r f a c e b e - t e s t s a n d a r e u s e d to e v a l u a t e h e a t e r a l l o y s .
t w e e n m e t a l a n d o x i d e h a s o c c u r r e d as a r e s u l t of
4 % s t r a i n of a l l o y 1 as s h o w n in Fig. 10. T h i s d a m a g e Crystal Structure Studies
w a s s m a l l e r t h a n t h a t o b s e r v e d on o t h e r a l l o y s f o r T a b l e I I s h o w s t h e r e s u l t s of c r y s t a l s t r u c t u r e
t h e s a m e a m o u n t of s t r a i n ( 5 ) . T w o t y p e s of d a m a g e s t u d i e s on 2 - h r o x i d a t i o n e x p e r i m e n t s f o r t h e t h r e e
a r e p o s t u l a t e d to o c c u r as a r e s u l t of s t r a i n i n g of t h e a l l o y s a n d for t h e s e v e r a l t e m p e r a t u r e s . C r y s t a l
a l l o y . T h e first is a s h o r t - t e r m d a m a g e w h i c h is structure studies were made above and below the
r a p i d l y r e p a i r e d b y f u r t h e r o x i d a t i o n . T h e s e c o n d is t r a n s i t i o n t e m p e r a t u r e r e g i o n of 1000~ The x-ray
l o n g - t e r m d a m a g e . This d a m a g e i n v o l v e s a n i n c r e a s e d i f f r a c t i o n p a t t e r n s s h o w e d s h a r p l i n e s f o r a l l of t h e
in t h e r a t e of r e a c t i o n w h i c h c o n t i n u e s o v e r l o n g oxide scales studied.
p e r i o d s of t i m e . A c o m p a r i s o n of t h e p a r a b o l i c r a t e C o m p l e t e i d e n t i f i c a t i o n of a l l of t h e d i f f r a c t i o n
law constants before and after strain shows some l i n e s w a s n o t p o s s i b l e since t h e s t r i p p i n g p r o c e s s r e -

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 Vol. 106, No. 4 OXIDATION STUDIES ON Fe-Cr-A1 ALLOYS 299

Table II. Summary crystal structure studies Fe-Cr-AI alloys

Alloy 1 Alloy 2 Alloy 3

T e m p , *C Crystal structures Temp, ~ Crystal structures Temp, ~ C r y s t a l structures

850 ~-AI~O~ 800 ~-ALO~

s.a. Cr~O~ Cr20~
s.a. MnO MnO
950 ~-AI=O~ 950 a-AI=O~ 900 a-A120~
s.a.* Cr20~ tr. Cr203 Cr20~
tr.# MnO MnO
1050 ~-A1~O3 1050 ~-AI~O~ 10.50 a-A120~
s.a. a-Fe~O~ MnO
tr. Cr~O8
tr. spinel a, = 8.12A tr. spinel ao --- 8.12A tr. spinel a~ = 8.12A

* s.a. = s m a l l a m o u n t .
%tr. = trace.

m o v e s c a r b i d e s , n i t r i d e s , etc. f r o m t h e s u r f a c e l a y e r
of t h e a l l o y . A s a r e s u l t a n u m b e r of e x t r a r e f l e c t i o n s
occur. I d e n t i f i c a t i o n of t h e m a j o r o x i d e c o m p o n e n t s
w a s r e a d i l y m a d e . O x i d e s p r e s e n t in t r a c e a m o u n t s
w e r e i d e n t i f i e d w i t h less r e l i a b i l i t y b y t w o o r t h r e e
c h a r a c t e r i s t i c reflections.
Alpha-Al~O, was the principle oxide found in all
of t h e o x i d e scales s h o w n in T a b l e II. Cr~O~ a n d M n O
a p p e a r in t h e o x i d e scale a t t e m p e r a t u r e s of 900~
a n d l o w e r . T h e i d e n t i f i c a t i o n of M n O is o p e n to s o m e
q u e s t i o n since its d i f f r a c t i o n p a t t e r n is n e a r l y i d e n -
t i c a l to t h o s e for NbC, NbN, a n d T a C (17). T h e s e
c o m p o u n d s c o u l d c o n c e i v a b l y b e p r e s e n t in t r a c e
a m o u n t s in h i g h - t e m p e r a t u r e alloys. S p e c t r o s c o p i c
a n a l y s e s of t h e a l l o y s in T a b l e I s h o w e d no e v i d e n c e
for N b o r T a in t h e m e t a l .
I n t h e t r a n s i t i o n t e m p e r a t u r e zone t h e Cr~O~ c o n -
t e n t of t h e o x i d e scale d e c r e a s e s . I n a d d i t i o n , a s p i -
nel, p r o b a b l y F e O . AI~O~, a p p e a r s in t h e o x i d e h a v i n g
a p a r a m e t e r of 8.12A ( 1 7 ) . T h e s e c h a n g e s in o x i d e
c o m p o s i t i o n o c c u r f o r a l l of t h e a l l o y s .
A l l o y 3 c o n t a i n i n g t h e l o w e s t a m o u n t s of A1, Cr,
a n d M n s h o w s t h e l a r g e s t a m o u n t of M n O s t r u c t u r e
in t h e o x i d e scale. A l l o y 3 also s h o w s t h e l a r g e s t
a m o u n t of d a m a g e in t h e o x i d e in s t r a i n o x i d a t i o n
tests.
We conclude that crystal structure differences
e x i s t in t h e o x i d e scales of t h e t h r e e a l l o y s as a r e -
s u l t of m i n o r d i f f e r e n c e s in a l l o y c o m p o s i t i o n . T h e s e
Time (min)
5000 o 40 80 120
c~ 4000
c r y s t a l s t r u c t u r a l d i f f e r e n c e s affect t h e a d h e s i o n
p r o p e r t i e s of t h e o x i d e as s h o w n b y t h e s t r a i n o x i -
d a t i o n s t u d i e s o r b y p r a c t i c a l p e r f o r m a n c e tests.
T h e s e d i f f e r e n c e s do n o t a p p r e c i a b l y affect t h e r a t e
of o x i d a t i o n a t c o n s t a n t t e m p e r a t u r e s a b o v e a n d b e -
l o w t h e t r a n s i t i o n t e m p e r a t u r e zone.
Thermodynamic Interpretation
T a b l e I I I s h o w s t h e p r i n c i p a l t y p e s of r e a c t i o n s
w h i c h m a y o c c u r in t h e o x i d a t i o n of F e - C r - A 1 alloys.
T h e s e d e t e r m i n e in p a r t t h e c o n s t i t u t i o n of t h e o x i d e
scale f o r m e d at h i g h t e m p e r a t u r e s . P r e c i s e c a l c u -
l a t i o n s of t h e t h e r m o d y n a m i c p r o p e r t i e s of t h e o x i -
d a t i o n p r o d u c t s n e c e s s i t a t e c o n s i d e r a t i o n of t h e r e l a -
t i v e r a t e s of a t t a c k of t h e s e v e r a l m e t a l s a n d i n t e r -
d i f f u s i o n p r o c e s s e s in t h e a l l o y , as p o i n t e d o u t b y
W a g n e r (18) f o r a n u m b e r of b i n a r y s y s t e m s .
T h e t h e r m o d y n a m i c e v i d e n c e g i v e n b e l o w for m o s t
of t h e s e r e a c t i o n s a s s u m e s a s t a n d a r d s t a t e of u n i t
a c t i v i t y f o r t h e c o m p o n e n t m e t a l s . F o r m a n y of t h e
c a l c u l a t i o n s , t h e a c t i v i t y c o r r e c t i o n is s m a l l c o m -
p a r e d to t h e f r e e e n e r g y c h a n g e in t h e r e a c t i o n i t -
self.
T a b l e IV s h o w s l o g a r i t h m s of t h e d i s s o c i a t i o n
Table III. Types of surface reactions occurring on Fe-Cr-AI alloys
A. Direct o x i d a t i o n
2Cr (s) + 3/20~ (g) ~ - Cr=O~ (s), etc.
B. Solid phase reactions
2A1 (s) + Cr~O3 (s) ~AI~O~ (s) + 2Cr (s), etc.
C. F o r m a t i o n of spinels
F e O (s) + Al~O8(s) ~-FeO-AI~O8 (s), etc.
D. F o r m a t i o n of silicates
AI~O~(s) + SiO2 (s) <-~-~A1~O8.SiO2(s), etc.
E. D e c a r b u r i z a t i o n reactions

fA,s,relche
E Cr203 (s) + 3C (solid solution) ~ 2Cr (s) + 3CO (g), etc.
< F. Vaporization reactions
~3000 Cr ( s ) ~ C r ( g ) , etc.
::L
2000 Table IV. Dissociation pressures of the oxides

- - l o g po2 atmospheres
looo 2 % and reheated- Temp,
~ Fe203 A120~ Cr~Os SiO2 MnO CoO

0 40 80 25 85.5 184.6 121.8 144.6 127.2 75.4

Time (rain) 200 50.8 112.4 73.4 87.6 77.4 44.5
400 33.0 75.7 48.9 58.8 52.1 28.9
Fig. 12. Strain oxidation of Fe-Cr-AI alloy 3, 2 % strain: 600 23.4 55.8 35.6 43.2 38.4 20.4
a, 900~ 7.6 cm Hg of 02, A = 3.29 x 10 -18 (g/crn~)S/sec; 800 17.4 43.3 27.3 33.5 29.8 15.1
b, 900~ 7.6 cm Hg of 02, after cooling, stretching 2 % and 1000 13.3 34.7 21.6 26.8 24.0 11.4
reheating, A = 4.34 x 10 -1~ (g/cm~)2/sec. 1200 10.3 28.4 17.4 21.9 19.6 8.8

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 300 JOURNAL OF THE ELECTROCHEMICAL SOCIETY April 1959
Table V. Solid phase reactions of ferric and chromic oxides with Table VII. Vapor pressure of metals
Cr, AI, Si, and Mn
loglcK~
1. 2 C r (s) + FeeOs (s) ~ C r 2 O s (s) + 2 F e (s) Temp,
~ Fe Cr A1 Si Mn Co
2. 2A1 (s, 1) + Fe2Oa (s) ~ A 1 2 0 ~ (s) + 2 F e (s)
3. 2A1 ( s , l ) + Cr203 (s) ~ A l ~ O 8 (s) + 2 C r (s)
4. 31Y[n (s) + Fe.oOs (s) ~ _ 3 M n O (s) + 2 F e (s) 400 --23.1 --18.2 --26.3 --14.5 --25.3
5. 3Si (s) + 2Fe203 (s) ~ 3SiO= (s) + 4 F e (s) 600 --16.1 --12.5 --18.55 --9.6 --17.8
6. 3 S i ( s ) + 2Cr,~O~ (s) ~ 3SlOe (s) + 4 C r (s) 800 --11.65 --8.95 --13.7 --6.5 --13.05
900 --9.95 --7.6 --11.8 --5.3 --11.25
logloK
1000 --9.83 --8.55 --6.5 --10.3 --4.35 --9.75
1100 --8.63 --7.4 --5.5 --8.9 --3.5 --8.5
Temp, Reac- Reac- Reac- Reac- Reae- Reac- 1200 --6.4 --4.7 --7.85 --2.8 --7.35
~ tion 1 tion 2 tion 3 tion 4 tion 5 tion 6

25 +54.1 +148.2 -{-94.1 +62.1 +176.4 +68.3 oxide. E v e n t h o u g h M n a n d Co are p r e s e n t i n m i n o r

200 33.9 92.4 58.5 39.9 110.5 42.6 a m o u n t s i n t h e alloy, t h e y c a n s u b s t i t u t e i n t h e
400 23.8 63.9 40.1 28.6 77.3 29.8 s p i n e l s t r u c t u r e a n d t h u s a p p e a r i n the oxide film.
600 18.4 48.6 30.2 22.5 59.5 22.8 T h e f o r m a t i o n of silicates m a y be e x p e c t e d f r o m
800 14.9 38.9 24.0 18.6 48.2 18.5
1000 12.5 32.2 19.7 16.1 40.5 15.5 p h a s e d i a g r a m s t u d i e s of t h e oxides (20). These
1200 10.8 27.2 16.4 14.0 34.9 13.4 c o m p o u n d s c a n e x e r t a m a j o r i n f l u e n c e on t h e oxi-
d a t i o n process since t h e y m a y c o n c e n t r a t e at t h e
p r e s s u r e s of t h e oxides f r o m 25 ~ to 1200~ as c a l - oxide-alloy interface.
culated from equations given by Kubaschewski and T h e role of t h e d e c a r b u r i z a t i o n r e a c t i o n is n o t
E v a n s (19). A l l of the oxides are s t a b l e i n the a t m o s - understood. Calculations using data from K u b a -
pheres and temperatures used in the oxidation ex- s c h e w s k i a n d E v a n s (19) show that, if a c a r b o n c o n -
periments. t e n t of 0.05% is a s s u m e d for t h e r e a c t i o n of c a r b o n
T h e e q u i l i b r i u m c o n s t a n t s for the s e v e r a l solid w i t h ferric oxide, t h e e q u i l i b r i u m c a r b o n m o n o x i d e
p h a s e r e a c t i o n s are g i v e n i n T a b l e V. A l l are t h e r - p r e s s u r e is 1 a t m at 1000~ S i m i l a r c a l c u l a t i o n s for
m o d y n a m i c a l l y possible over the t e m p e r a t u r e r a n g e . c h r o m i c oxide, a l u m i n u m oxide, a n d s i l i c o n d i o x i d e
A l t h o u g h f e r r i c oxide m a y f o r m i n i t i a l l y , b o t h Cr show t h e r e a c t i o n to occur u n d e r v a c u u m c o n d i t i o n s
a n d A1 c a n r e a c t to f o r m c h r o m i u m a n d a l u m i n u m at 1000~ As the c a r b o n c o n t e n t is depleted, the i m -
oxide as s h o w n b y t h e positive v a l u e s of logloK. p o r t a n c e of this r e a c t i o n d i m i n i s h e s .
E v e n t u a l l y a l u m i n u m oxide s h o u l d c o n s t i t u t e t h e T a b l e VII shows t h e v a p o r p r e s s u r e s of t h e m e t a l s
b u l k of the oxide film. of i n t e r e s t i n this s t u d y f r o m 25 ~ to 1200~ E x c e p t
X - r a y c r y s t a l s t r u c t u r e s t u d i e s ( T a b l e II) c o n - for i r o n the d a t a are c a l c u l a t e d f r o m a r e c e n t s u r v e y
firm t h e t h e r m o d y n a m i c p r e d i c t i o n s t h a t AI~O~ b y S t u l l a n d S i n k e (21). T h e d a t a for i r o n are t a k e n
s h o u l d be t h e chief oxide i n t h e scale. Solid p h a s e f r o m a r e c e n t s t u d y b y t h e a u t h o r s (22) u s i n g t h e
r e a c t i o n s m a y a c c o u n t for t h e decreases i n c h r o m i u m vacuum microbalance method. The measured values
oxide c o n t e n t of the scale at t e m p e r a t u r e s a b o v e for t h e v a p o r p r e s s u r e of i r o n w e r e l o w e r t h a n t h e
900~ T h e p r e s e n c e of M n O m a y be d u e to the h i g h e x t r a p o l a t e d v a l u e s g i v e n b y S t u l l a n d S i n k e (21).
m o b i l i t y of m a n g a n e s e a n d to its h i g h t h e r m o d y - W e i g h t loss c a l c u l a t i o n s b a s e d on T a b l e V I I for
namic stability. oxide free F e - C r - A 1 alloys show r a p i d e v a p o r a t i o n
T h e f o r m a t i o n of s p i n e l s or o t h e r m i x e d oxide sys- of A1, Cr, a n d M n a b o v e 1000~ i n h i g h v a c u u m .
t e m s m a y be e x p e c t e d b u t t h e r m o d y n a m i c d a t a for H o w e v e r , r a p i d e v a p o r a t i o n of these m e t a l s has n o t
s p i n e l s o t h e r t h a n Fe~O4 a r e n o t a v a i l a b l e . H o w e v e r , b e e n o b s e r v e d i n o u r s t u d i e s or i n o t h e r s t u d i e s (6)
t h e s t a b i l i t y of the s e v e r a l spinels of i n t e r e s t c a n b e on these alloys.
d e d u c e d f r o m s t r u c t u r a l i n f o r m a t i o n . T a b l e VI shows I n a n o t h e r s t u d y (22) t h e w e i g h t loss c u r v e s for
the l a t t i c e p a r a m e t e r s of s o m e of the k n o w n a l u m i - oxide free surfaces of p u r e iron, a 5 A 1 - F e a l l o y a n d
n a t e s (17) h a v i n g the s p i n e l s t r u c t u r e as a f u n c t i o n a 5 A1-23 C r - F e alloy, w e r e d e t e r m i n e d . T h e alloys
of t h e ionic r a d i i of t h e b i v a l e n t ions. T a b l e V I shows w e r e p r e p a r e d f r o m p u r e m e t a l s . The 5 A 1 - F e a l l o y
t h a t Co, Fe, a n d M n c a n f o r m s p i n e l s w i t h a l u m i n u m gave a w e i g h t loss c u r v e s o m e w h a t l o w e r t h a n t h a t
for p u r e i r o n w h i l e the 5 A1-23 C r - F e a l l o y gave a
Table VI. Parameters of aluminate spinels of a number of metals w e i g h t loss c u r v e a little h i g h e r t h a n t h a t for iron.
C h e m i c a l a n a l y s e s of t h e v a p o r i z e d deposits s h o w e d
Parameter of t h e v a p o r f r o m t h e 5 A1-Fe alloy consisted e s s e n -
Divalent Atomic Radius of Parameter of aluminate
metal number ion, A oxide MO,* A (17). A t i a l l y of iron, w h i l e the v a p o r f r o m the 5 A1-23
C r - F e a l l o y consisted l a r g e l y of Cr a n d Fe. W e c o n -
Ni 28 0.74 4.168 8.06 c l u d e t h a t A1 does n o t v a p o r i z e effectively f r o m a 5
Mg 12 0.75 4.203 8.10 A 1 - F e alloy. H o w e v e r , Cr a n d F e do v a p o r i z e f r o m
Co 27 0.78 4.24 8.085 a n o x i d e free s u r f a c e of a 5 A1-23 C r - F e alloy. O t h e r
Fe 26 0.80 4.332t 8.119 s t u d i e s (6, 22) show t h a t o x i d a t i o n of a n F e - C r - A 1
Zn 30 0.83 8.087
Cu 29 8.09 a l l o y r e d u c e s t h e e v a p o r a t i o n losses at 1050~ S i n c e
Mn 25 0.83 4.4345 8.28 Cr~O~ is n o t a n i m p o r t a n t c o m p o n e n t i n t h e oxide
Cd 48 0.99 4.689 scale at 1050~ one m u s t c o n c l u d e t h a t a-AI~O~ acts
Ca 20 1.05 4.797 as a b a r r i e r to t h e diffusion of c h r o m i u m .
T a b l e V I I shows m a n g a n e s e to h a v e a h i g h v a p o r
* Coordination number of six.
Stoichi, o m e t r i c c o m p o s i t i o n , pressure. I n these alloys m a n g a n e s e is p r o b a b l y c o m -

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 Vol. 106, No. 4 OXIDATION STUDIES
b i n e d w i t h s u l f u r or w i t h o x y g e n t h u s l o w e r i n g its
activity, a n d little m a n g a n e s e w o u l d vaporize.
Effect of Vapor Pressure in Oxidation
W i t h t h e e x c e p t i o n of o x i d a t i o n r e s i s t a n t m e t a l s
a n d a l l o y at high t e m p e r a t u r e s , the v a p o r p r e s s u r e of
the m e t a l has no d i r e c t effect on t h e m e c h a n i s m of
o x i d a t i o n . This is b e c a u s e b r e a k d o w n of n o r m a l o x i -
d a t i o n processes occurs b y o t h e r m e c h a n i s m s , such as
loss of a d h e s i o n at the o x i d e - m e t a l i n t e r f a c e . T h e
first e v i d e n c e for a v a p o r p r e s s u r e effect was f o u n d
i n the o x i d a t i o n of c h r o m i u m (23). T h e r a p i d i n -
crease i n t h e r a t e of o x i d a t i o n of c h r o m i u m w a s e x -
p l a i n e d as s h o r t c i r c u i t i n g b y v a p o r i z a t i o n of n o r m a l
ion t r a n s f e r a n d diffusion processes. This occurs
w h e n the t r a n s f e r of m e t a l ions into t h e oxide b y
e v a p o r a t i o n a p p r o a c h e s the r a t e of r e a c t i o n . V a p o r
t r a n s f e r of m e t a l c a n occur at surfaces o t h e r t h a n t h e
m e t a l - o x i d e i n t e r f a c e . I n this sense the n o r m a l d i f -
f u s i o n processes are s h o r t circuited. T h e p r e s e n t
s t u d y shows a r a p i d i n c r e a s e i n t h e r a t e of o x i d a -
tion at 1050~ for the F e - C r - A 1 alloys. T h e v a p o r
p r e s s u r e of t h e m e t a l l i c c o m p o n e n t s m a y be i m p o r -
t a n t in t h e h i g h - t e m p e r a t u r e o x i d a t i o n of t h e s e
alIoys, as i n t h e case of c h r o m i u m .
The v a p o r p r e s s u r e effect c a n be s t u d i e d i n t w o
ways. C o m p a r e t h e r a t e of e v a p o r a t i o n of m e t a l
a t o m s f r o m a free s u r f a c e w i t h t h e r e a c t i o n r a t e e x -
p r e s s e d i n t e r m s of m e t a l a t o m s l e a v i n g t h e o x i d e -
m e t a l i n t e r f a c e . Since t h e r a t e of e v a p o r a t i o n has a
h i g h e r t e m p e r a t u r e coefficient t h a n t h e r a t e of o x i -
d a t i o n , a s h a r p b r e a k i n t h e r a t e of o x i d a t i o n s h o u l d
occur at the t e m p e r a t u r e w h e r e t h e t w o r a t e s i n t e r -
sect. C r y s t a l s t r u c t u r e s t u d i e s also c a n be u s e d to
show the v a p o r p r e s s u r e effect. If the v o l a t i l i t y of a
c e r t a i n m e t a l b e c o m e s i m p o r t a n t , t h e oxide of this
m e t a t c o u l d a p p e a r i n t h e o x i d e film e v e n t h o u g h
o t h e r m e t a l s f o r m m o r e s t a b l e oxides.
A l l o y 1 h a v i n g the l o w e s t r a t e of o x i d a t i o n i n t h e
1-2 h r p e r i o d is t h e best alloy for c h e c k i n g t h e v a p o r
p r e s s u r e effect. F i g u r e 13 shows a p l o t of t h e r a t e of
o x i d a t i o n i n t e r m s of b o t h i r o n a n d a l u m i n u m r e -
a c t i n g a n d t h e e x p e r i m e n t a l w e i g h t loss d a t a for t h e
Temp ~
I100 1050 I000 950 900 850 800 750
10-7
'i I
~
c 8
- 2
b K i n e t i c s t u d i e s show a u n i q u e c h a n g e i n r a t e of
io-e
E c
UA
10-9
I 76-77 k c a l / m o l e for t h e t h r e e alloys.
1 C r y s t a l s t r u c t u r e studies s h o w e d a-Al~O3 to b e t h e
10 4(
I m a i n oxide over t h e t e m p e r a t u r e r a n g e . B e l o w 950~
7.0 7.5 8.0 8.5 9.0 9.5
~ITx 104
Fig. 13. Comparison weight loss 5AI-23Cr-Fe alloy (curve
A) with rate of oxidation in terms of Fe (curve B) or AI
(curve C), log rate vs. l / T , alloy 1.
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ON Fe-Cr-A1 ALLOYS 301
5 A1-23 C r - F e alloy. T h e r a t e of o x i d a t i o n shows
a s h a r p b r e a k at the t e m p e r a t u r e w h e r e the m e t a l
t r a n s f e r b y e v a p o r a t i o n e q u a l s the r a t e of reaction.
T a b l e II shows t h e oxide scale at 1050~ to be
~-Fe~O~, a-ALOe, a n d a low p a r a m e t e r s p i n e l ( p r o b -
a b l y FeO.AI,.,O~). B e l o w 1050~ i r o n oxides w e r e n o t
observed. Both the r a t e s t u d i e s a n d c r y s t a l s t r u c t u r e
s t u d i e s show t h a t t h e h i g h - t e m p e r a t u r e r a t e of o x i -
d a t i o n a n d c r y s t a l s t r u c t u r e of t h e scale a r e r e l a t e d
closely to the v a p o r p r e s s u r e of the m e t a l s in t h e
alloy. T h e a-A120~ scale l i m i t s i n some m a n n e r t h e
v a p o r p r e s s u r e effect of c h r o m i u m .
T a b l e II shows for alloy 3, w h i c h h a s t h e l o w e s t
u s e f u l life v a l u e , t h e f o r m a t i o n of M n O a n d a t r a c e
of Cr,.,O~. This suggests t h a t t h e l o w e r a l u m i n u m c o n -
t e n t of the alloy 3 is n o t l i m i t i n g the f o r m a t i o n of
M n O a n d Cr~O~ i n t h e oxide scale.
General Principles
T h e selection of m e t a l s for h i g h h e a t r e s i s t a n t
alloys b a s e d on i r o n s h o u l d b e m a d e on t h e f o l l o w i n g
p r i n c i p l e s : (a) a l l o y i n g e l e m e n t s s h o u l d l o w e r t h e
r a t e of o x i d a t i o n ; (b) solid p h a s e r e a c t i o n s h o u l d b e
c o n s i d e r e d so as to give a n oxide h a v i n g a good c r y s -
t a l s t r u c t u r e m a t c h w i t h t h e m e t a l ; this p r o p e r t y
s h o u l d m a x i m i z e a d h e r e n c e of t h e oxide to t h e m e t a l
a n d m i n i m i z e t h e effects of stress or s t r a i n ; a n d (c)
a l l o y i n g e l e m e n t s s h o u l d b e chosen to l o w e r t h e alloy
v a p o r p r e s s u r e a n d to l i m i t t h e v a p o r p r e s s u r e of t h e
m o r e v o l a t i l e b u t still d e s i r a b l e e l e m e n t s .
Those studies show t h a t i n c r e a s i n g t h e c h r o m i u m
a n d a l u m i n u m c o n t e n t s i n alloys 1 to 3 i m p r o v e s t h e
p h y s i c a l p r o p e r t i e s of t h e o x i d e - m e t a l i n t e r f a c e as
determined by the strain oxidation experiments. A
s m a l l e r i m p r o v e m e n t is n o t e d on t h e c o n s t a n t t e m -
p e r a t u r e o x i d a t i o n rate.
Summary
T h r e e F e - C r - A 1 alloys w e r e s t u d i e d s y s t e m a t i c a l l y
i n r e g a r d to t h e i r o x i d a t i o n b e h a v i o r f r o m 700 ~ to
1100 ~ K i n e t i c studies w e r e m a d e u s i n g t h e v a c u u m
microbalance method. Crystal structure studies were
m a d e on t h e oxide film e l e c t r o c h e m i c a l l y r e m o v e d
f r o m the o x i d i z e d alloy. S t r a i n - o x i d a t i o n s t u d i e s
w e r e m a d e to d e t e r m i n e t h e a d h e r e n c e c h a r a c t e r -
istics of the o x i d e film. T h e e x p e r i m e n t a l r e s u l t s w e r e
i n t e r p r e t e d b y t h e r m o d y n a m i c a n d r a t e a n a l y s e s of
t h e o x i d e - m e t a l systems.
o x i d a t i o n at 900~ O v e r t h e r a n g e of 9 0 0 ~ 1 7 6
t h e r a t e of o x i d a t i o n w a s n e a r l y c o n s t a n t . A b o v e
1050~ the r a t e of o x i d a t i o n a g a i n i n c r e a s e d . T h e
p a r a b o l i c r a t e l a w could be a p p l i e d w i t h i n i t i a l
d e v i a t i o n s over t h e c o m p l e t e t e m p e r a t u r e r a n g e . F o r
the temperature range 700~176 a l o g a r i t h m i c plot
of the p a r a b o l i c r a t e l a w c o n s t a n t s vs. 1/T gave a
s t r a i g h t l i n e a n d c a l c u l a t e d h e a t s of a c t i v a t i o n of
1.0
some Cr~O~ a n d M n O w e r e o b s e r v e d . These oxides
d e c r e a s e d i n t h e oxide scale on p a s s i n g t h r o u g h t h e
t r a n s i t i o n t e m p e r a t u r e region. A t 1050~ the o x i d e
was l a r g e l y a-A120~.
 302 JOURNAL OF THE ELECTROCHEMICAL SOCIETY A p r i l 1959

The crystal studies confirmed thermodynamic pre- 5. E. A. G u l b r a n s e n and K. F. A n d r e w , A S T M Tech-

d i c t i o n s as to t h e c o m p o s i t i o n of t h e scale. S o l i d
p h a s e r e a c t i o n s of a l u m i n u m w i t h c h r o m i u m o x i d e
w e r e p r o p o s e d to e x p l a i n t h e s h i f t in o x i d e c o m -
p o s i t i o n a t 950~
S t r a i n o x i d a t i o n s t u d i e s s h o w e d t h e o x i d e scale on
a l l o y 1 to b e less s u s c e p t i b l e to d a m a g e t h a n t h e
scale on a l l o y s 2 a n d 3. T h e s e s t u d i e s can be c o r -
r e l a t e d w i t h p r a c t i c a l p e r f o r m a n c e tests.
C o m p a r i s o n of t h e r a t e of o x i d a t i o n w i t h a v a i l -
able vapor pressure data showed that metal transfer
b y v a p o r i z a t i o n w a s t h e r a t e - c o n t r o l l i n g f a c t o r in
t h e o x i d a t i o n of F e - C r - A 1 a l l o y s a t 1050~ and
a b o v e . D e s i g n p r i n c i p l e s w e r e p r o p o s e d for h i g h h e a t
r e s i s t a n t alloys.
T h e F e - C r - A 1 a l l o y s a r e g o o d e x a m p l e s of w e l l
d e s i g n e d h i g h h e a t r e s i s t a n t alloys.
M a n u s c r i p t r e c e i v e d A p r i l 23, 1958. This p a p e r was
p r e s e n t e d before the O t t a w a Meeting, Sept. 28-Oct. 2,
1958.
A n y discussion of this p a p e r will a p p e a r in a Discus-
sion Section to be p u b l i s h e d in the D e c e m b e r 1959
JOURNAL.
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Deposition of New Chromium-Iron

Alloy Plate of Banded Structure
L. D. McGraw, J. A. Gurklis, and C. L. Faust
Electrochemical Engineering Division, Battelle Memorial Institute, Columbus, Ohio

and J. E. Bride
Diamond Alkali Company, Cleveland, Ohio

ABSTRACT
A n e w b a t h composition and its o p e r a t i n g conditions are described for
electrodeposition of hard, bright, c h r o m i u m - i r o n alloy p l a t e h a v i n g b a n d e d
microstructure. A p r e c i p i t a t i o n m e c h a n i s m is proposed to account for the m i -
c r o s t r u c t u r e of the plate. The process p r o d u c e s plate h a v i n g almost the same
physical p r o p e r t i e s as conventional h a r d c h r o m i u m from a b a t h composition
not based on chromic acid. The p l a t i n g r a t e and cathode c u r r e n t efficiency for
the alloy are h i g h e r than for p l a t i n g c h r o m i u m f r o m a conventional bath.

A high-speed chromium-iron-alloy plating proc- h a d as its o b j e c t i v e t h e d e v e l o p m e n t of h a r d , w e a r -

ess w a s d e v e l o p e d in t h e s e l a b o r a t o r i e s ( 1 ) . T h e b a t h
is e s s e n t i a l l y a c h r o m i c - a n d f e r r i c - a l u m s o l u t i o n
w i t h a d d i t i o n s of a m m o n i u m s u l f a t e a n d o t h e r salts.
I n t h e c o u r s e of t h e d e v e l o p m e n t p r o g r a m , it w a s
observed that bright chromium-iron-alloy plate hav-
ing banded microstructure was obtained when hy-
p o p h o s p h i t e w a s u s e d as a b a t h a d d i t i v e .
T h e o p p o r t u n i t y to s t u d y t h i s p a r t i c u l a r a l l o y p l a t e
a r o s e w h e n a p r o g r a m for t h e N a v y D e p a r t m e n t (2)
resistant plate from a high-efficiency bath. Since
p l a t e s of l a m i n a r ( b a n d e d ) s t r u c t u r e r e s e m b l e c o n -
ventional hard chromium, they were developed with
t h e u l t i m a t e o b j e c t i v e of i m p r o v e d a b r a s i o n r e s i s t -
ance.
Preliminary e x p e r i m e n t s . - - F r e l i m i n a r y efforts
w e r e s u c c e s s f u l in d e p o s i t i n g b r i g h t c h r o m i u m - i r o n
alloy having banded microstructure onto 2.5-cm
( 1 - i n . ) - d i a m e t e r c i r c u l a r a r e a s of s t e e l c a t h o d e s

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