Vol. 110, No.

4 STRUCTURE OF ANODIC OXIDE FILMS ON A1 267

Acknowledgments 5. K. Huber, Helv. Chim. Acta, 28, 1416 (1945); Bull.

Soc. Chim. France, D183 (1949).
T h e a u t h o r s w i s h to a c k n o w l e d g e t h e a s s i s t a n c e of 6. E. C. W. P e r r y m a n , "Polarised light in M e t a l l o g -
R. E. M a r t i n in p r e p a r i n g s o m e of t h e o x i d e films r a p h y , " B u t t e r w o r t h s , London (1952); J. Inst.
a n d a r e g r a t e f u l to t h e P l e s s e y C o m p a n y L i m i t e d Metals, 85, 567 (1956-7).
f o r p e r m i s s i o n to p u b l i s h t h i s w o r k . 7. J. D. E d w a r d s and F. Keller, Trans. AIME, 156, 288
(1944).
M a n u s c r i p t r e c e i v e d J u l y 11, 1962; r e v i s e d m a n u - 8. F. Keller, M. S. Hunter, and D. L. Robinson, This
script r e c e i v e d Oct. 1O, 1962. Journal, 100, 411 (1953).
9. C. J. L. Booker, J. L. Wood, and A. Walsh, Brit. J.
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 December 1963 Appl. Phys., 8, 347 (1957).
JOURNAL. 10. A. de S y and H. Haemers, Stahl u. Eisen, 61, 185
(1941).
REFERENCES 11. H. Mahl, Naturwiss., 30, 207 (1942).
1. A. Hone and E. C. Pearson, Metal Prog., 53, 363 12. R. E. Reason, M. R. Hopkins, and R. I. Garrod,
(1948). " M e a s u r e m e n t of Surface F i n i s h b y S t y l u s M e t h -
2. P. Lacombe, Trans. Inst. Metal Finishing, 31, 208 ods," p. 44, T a y l o r and Hobson Ltd., Leicester,
(1954). England.
3. P. L a c o m b e and L. B e a u j a r d , Journ~e des ~tats de 13. R. E. Reason, " P r o p e r t i e s of Metallic Surfaces,"
Surface (Paris), 44 (1945). Institute of Metals M o n o g r a p h (London) p. 327
4. J. H e r e n g u e l and P. Lelong, Congr6s de M6tallurgie (1953).
(Paris 1953); Compt. rend., 232, 248 (1951); Rev. 14. D. E. Bradley, Brit. J. Appl. Phys., 5, 65 (1954).
M~t., 49, 374 (1952); Rev. Mdt., 51, 411 (1954). 15. M. S. Hunter, P r i v a t e communication.

Control of AI Corrosion in Caustic Solutions

L. Bockstie, 1 D. Trevethan, 2 and S. Zaromb ~
Phi~co Scientific Laboratory, Blue Bell, Pennsylvania

ABSTRACT
I n aqueous solutions of 1-10M NaOH or K O H the corrosion of A1 can be
accelerated b y chemical p r o m o t e r s such as S = (or S H - ) ions a n d / o r b y a
t h e r m a l r u n a w a y mechanism, and inhibited b y surface a m a l g a m a t i o n , espe-
cially w i t h Z n O - s a t u r a t e d solutions, a n d / o r b y a l k y l d i m e t h y l b e n z y l a m m o n i u m
salts. Corrosion is also m a r k e d l y r e d u c e d at high anodic c u r r e n t densities.

T h e u s e of A1 a n o d e s in a l k a l i n e p r i m a r y b a t t e r i e s ,
as d i s c u s s e d in a n e a r l i e r p a p e r ( 1 ) , d e p e n d s in l a r g e ~ VOLUME0:" Hz FO~MEL,
p a r t on a d e q u a t e c o r r o s i o n control. T h e p r e s e n t
s t u d i e s d e a l first w i t h t h e a c c e l e r a t i o n a n d t h e n
m a i n l y w i t h t h e i n h i b i t i o n of A1 c o r r o s i o n in a q u e -
ous s o l u t i o n s c o n t a i n i n g 1-10M N a O H or K O H .

Experimental Procedure
T h e e x p e r i m e n t s w e r e p e r f o r m e d at r o o m t e m - 57~'/.0

p e r a t u r e w i t h s t a n d a r d s t r i p s of 10 c m 2 t o t a l s u r f a c e
a r e a A1 g r a d e 1145 c o n t a i n i n g a t l e a s t 99.45% A1,
--~0.55% ( S i + F e ) , ~ 0 . 2 0 % Mn, a n d ~ 0 . 0 9 % o t h e r
i m p u r i t i e s . F o r q u i c k c o m p a r a t i v e tests, s e v e r a l
C r a i g cells (2), m o d i f i e d as s h o w n in Fig. 1, w e r e
u s e d to r e a d d i r e c t l y t h e v o l u m e of H2 f o r m e d b y
the corrosion reaction
3
A1 W 3HeO -t- O H - --> A I ( O H ) 4 _ -t- --~-H2 [1] Fig. 1. Modified Craig cell for comparative corrosion tests

as a f u n c t i o n of t i m e of i m m e r s i o n in t h e t e s t e d T h e c o r r o s i o n r a t e as a f u n c t i o n of a n o d e c u r r e n t
solution. T h e s e r e a d i n g s w e r e c o n v e r t e d b o t h into density was measured with the apparatus shown
a v e r a g e r a t e of c o n s u m p t i o n of A1 a n d a v e r a g e l o c a l s c h e m a t i c a l l y in Fig. 2. T w o p o r o u s Ni a i r c a t h o d e s
a c t i o n c o r r o s i o n c u r r e n t b y m e a n s of t h e c o n v e r s i o n m o u n t e d on thin, flat, solid Ni f r a m e s w e r e c l a m p e d
f a c t o r s : 1 cc H2 at 3 0 0 ~ a n d 1 a t m / 1 0 cm2-sec is b e t w e e n r u b b e r g a s k e t s a n d glass flats on e a c h side
e q u i v a l e n t to 2.71 x 10 -5 c m (or 0.271~) A1 r e a c t e d / of a v e r t i c a l s u r f a c e - a m a l g a m a t e d A1 a n o d e s t r i p
sec or 785 m a / c m 2, i.e., 1~ A 1 / h r is e q u i v a l e n t to h e l d f i r m l y at t h e l o w e r ( s h o r t e r ) e d g e b e t w e e n a n
0.805 m a / c m ~. F e n a i l a n d a glass t u b e p a s s i n g t h r o u g h a r u b b e r
1 Present address: Corning Glass Works, Bradford, Pennsylvania. s t o p p e r . A s h a l l o w p o o l of H g j u s t a b o v e t h e s t o p p e r
e Present address: Radio Corporation of A m e r i c a , Moorestown, assured continued anode surface amalgamation and
N e w Jersey.
s a t i s f a c t o r y e l e c t r i c a l c o n t a c t b e t w e e n t h e A1 a n d
~9 P r e s e n t a d d r e s s : R e s e a r c h a n d C o n s u l t i n g C o r p o r a t i o n , 1125 E a s t
102 S t r e e t , B r o o k l y n 36, N e w Y o r k . t h e F e nail. W i t h t h e c a t h o d e s c o n n e c t e d in p a r a l l e l ,

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 268 JOURNAL OF THE ELECTROCHEMICAL SOCIETY A p r i l 1963

a n d / o r boiling H~O. In v i e w of the high free e n e r g y

of reaction [ 1 ], this t y p e of chain m e c h a n i s m w o u l d
VbL ' be e x p e c t e d at a n y A l - a q u e o u s solutiofi i n t e r f a c e
'~EdT~ZY~
Z~Vs
w e r e it not for the p r o t e c t i v e l a y e r of oxide s t r o n g l y
a d h e r i n g to the A1. E v e n in h i g h l y a l k a l i n e solutions
in which the oxide r e a d i l y dissolves, a thin, s l o w l y
dissolving oxide l a y e r m a y still account for o b s e r v e d
s t e a d y corrosion r a t e s at low t e m p e r a t u r e s . The ac-
tion of chemical a c c e l e r a t i o n of A1 corrosion p r o b -
a b l y consists then of w e a k e n i n g the coherence
a n d / o r a d h e r e n c e of the p r o t e c t i v e layer. It was thus
observed in the p r e s e n t studies t h a t a d d i t i o n of
0.1-t.0M Na~S to solutions of 1.0-3.0M N a O H r e n -
ders t h e m s e v e r a l times m o r e corrosive to A1,4 p r o b -
a b l y due to the w e a k e n i n g of the p r o t e c t i v e film on
s u b s t i t u t i o n of an O = (or O H - ) b y a S = (or S H - )
ion.
Corrosion Inhibition.--Inorganic inhibitors.--Lim-
ited inhibition of A1 corrosion in caustic solutions
b y ZnO is k n o w n to occur in t h e Zn i m m e r s i o n p r o c -
ess (4) based on the r e a c t i o n
Fig. 2. Apparatus for simultaneous current density and corrosion
rate determinations.
2A1 + 3Zn (OH) 4=-~ 2A1 ( O t t ) 4 - + 4 O H - + 3Zn [2]

In p r e l i m i n a r y e x p e r i m e n t s , the use of ZnO in 10M

a l k a l i solutions was p a r t l y effective in i n h i b i t i n g the
corrosion of A1. However, t h e l a y e r of Zn f o r m e d on
the A1 tends to flake off on c o n t i n u e d immersion,
w i t h a r e s u l t i n g corrosion of the A1 at a r a t e of t h e
z J o r d e r of 10 m a / c m 2. This is a b o u t 6 times l o w e r t h a n
o t I, I I lo~ w i t h o u t the ZnO, b u t still too high for b a t t e r y a p p l i -
oJ - - zo
cations. However, w h e n Hg2SO4 was a d d e d to the
solution, t h e r e was no sign of flaking and the b u b -
bling of H2 a p p e a r e d quite low.
To c l a r i f y t h e role of Hg~SO4 in the corrosion i n -
0 ~ h i b i t i n g mechanism, i d e n t i c a l A1 strips w e r e p l a c e d
in t h r e e b e a k e r s c o n t a i n i n g 10M NaOH s a t u r a t e d
0.4 - - 40 ~
w i t h ZnO and e i t h e r one of t h e following: (a) HgO,
(b) Hg2SO4, a n d (c) Hg. The r a t e of corrosion a p -
p e a r e d slowest in b e a k e r (c) a n d fastest in b e a k e r
(a). Hence it was the m e t a l l i c Hg f o r m e d on d e c o m -
~02 -- 0
position of Hg2SO4 t h a t was effective in b e a k e r ( b ) .
20
5 I0 15 20 25 F u r t h e r m o r e , d i r e c t contact of the Hg w i t h A1 was
ANODE CURRENT DENSITY , i O (mo/cm 2) found to be m o r e p r o t e c t i v e t h a n m e r e presence of
Fig. 3. Corrosion rate and current efficiency at room temperature
Hg in t h e container.
as functions of current density at surface-amalgamated AI grade W h e n p r o p e r l y a m a l g a m a t e d and in contact w i t h
1 1 4 5 anodes in 3 M K O H plus 0 . S M AI(OH)3 plus on excess of ZnO. Hg, c o m p l e t e l y s u b m e r g e d A1 ( g r a d e 1145) anodes
corroded at room t e m p e r a t u r e in Z n O - s a t u r a t e d 10M
the cell was d i s c h a r g e d t h r o u g h a resistance decade K O H or NaOH solutions at a r a t e of less t h a n 0.15~/
box. S i m u l t a n e o u s recordings of the v o l t a g e across a hr. If the corrosion r a t e could be m a i n t a i n e d i n -
given s t a n d a r d resistance and of the v o l u m e of H2 definitely at such a low value, t h e n an A1 sheet 0.3
as a function of time y i e l d e d the d a t a shown in cm thick would lose less t h a n 10% of its w e i g h t b y
Fig. 3. corrosion from both sides over a p e r i o d of 1000 hr.
Thermal and chemical corrosion acceleration.- However, v e r y r a p i d corrosion f r e q u e n t l y occurred
a't u n p r e d i c t a b l e times (cf. the p r e c e d i n g section and
It is w o r t h noting first of all t h a t the corrosion r e a c -
tion [1] dissipates about 1.5 ev or 36 k c a l / g - e q u i v a - discussion of Table I b e l o w ) .
The i n h i b i t i n g effect of Hg in a l k a l i n e solutions
lent of free e n e r g y (1, 3) c o r r e s p o n d i n g to 4 k c a l /
m a y seem s u r p r i s i n g at first sight in v i e w of its
(g A1 r e a c t e d ) . This t r e m e n d o u s e n e r g y dissipation
is localized at the A l - e l e c t r o l y t e i n t e r f a c e a n d m a y k n o w n corrosion a c c e l e r a t i n g effects (3, 5) in n e u -
t r a l and acidic solutions. The p r o b a b l e e x p l a n a t i o n
thus give rise to hot spots if the r a t e of corrosion is
sufficiently high a n d / o r the r a t e of h e a t r e m o v a l is that, w i t h most of the p r o t e c t i v e oxide l a y e r a l -
r e a d y r e m o v e d b y the s t r o n g alkali, a n y f u r t h e r
sufficiently low. Since reaction r a t e s increase r a p i d l y
w i t h t e m p e r a t u r e , t h e hot spots m a y give rise to a ~E.G., a d d f t i o n o f 0.1M NaeS t o 1M B a ( O P I ) s a n d llVI N a O H +
0.1M B a (OH)e s o l u t i o n s i n c r e a s e d t h e c o r r o s i o n r a t e s f r o m 5~e/hr t o
k i n d of chain reaction m e c h a n i s m which m a y come 3 0 ~ / h r a n d f r o m 1 0 / ~ h r t o 2 5 ~ / h r , r e s p e c t i v e l y . A d d i t i o n of 1M
NaeS t o a 10M N a O t t s o l u t i o n i n a L u c i t e c o n t a i n e r c a u s e d p a r t i a l
to end only after f o r m a t i o n of l a r g e b u b b l e s of H2 m e l t i n g of t h e L u c i t e f r o m t h e u n c o n t r o l l a b l y f a s t A1 c o r r o s i o n rate.

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 Vol. 110, No. 4 A1 C O R R O S I O N IN CAUSTIC SOLUTIONS 269

Table I. Typical average rates of corrosion of AI (Grade 1145) in alkaline solutions at room temperature

N o m e n c l a t u r e : H y a m i n e 3500 is a 50% a q u e o u s s o l u t i o n of m i x e d (C12tol4 a l k y l ) N M e 2 B z C 1 ; H y a m i n e 1622 is

( d i - i s o b u t y l p h e n o x y e t h o x y e t h y l ) N M ~ 2 B z C 1 ; H y a m i n e 10X is ( d i - i s o b u t y l c r e s o x y e t h o x y e t h y l ) N M e 2 B z C 1 ; Hy-
a m i n e 2389 is a m i x t u r e of 4 p a r t s
Me -F 1 p a r t Me
I H 1
~_--~ CH2NMe3C1 C1Me3N - - C __ ~ CH2NMeaC1
-- -- H vI
I
C~2 a l k y l C12 a l k y l
H y a m i n e 1450 is a m i x t u r e of C14 a l k y l NMe2BzC1 a n d c a r b a m i d e ; T r i t o n X-400 is (stearyl, i.e., n - C l s
a l k y l ) N M e 2 B z C 1 ; A l i q u a t 4 is (C12 a l k y l ) N M e 3 C l ; A l i q u a t 6 is ( p a l m i t y l , i.e., n-C16 alkyl)NMe3C1.

A. Plain vs. surface-amalgamated AI

A v g c o r r o s i o n r a t e ( / ~ h r ) i n 3M s o l u t i o n s o f
KOI-I NaOI'~
Set Plain Amalgamated Plain Amalgamated
No. Additive AI A1 A1 A1

1 None 25 13-15 75 13-15

2 0.5MZn(OH)4 = 25 -- 25 --
3 0.5M A l ( O H ) 4 - 60 13-25 75 25-60
4 0 . 5 M Z n ( O H ) 4 = -{- 0.5M A l ( O H ) 4 - 20 0.6-1.0 20 0.6-1.5
5 10% H y a m i n e 3500 35-38 0.05-0.25 25-38 0.03-0.13
6 10% H y a m i n e 3500 -{- 0.5M Z n ( O H ) 4 = 5 0.13-0.5 2.5 0.25-0.5
7 10% H y a m i n e 3500 + 0.5M A l ( O H ) 4 - 25 7.5-25 25 2.5-10
8 10% H y a m i n e 3500 -{- 0.5M Z n ( O H ) 4 = Jc 0.5M
Al(OH)4- 5 0.13 5 0.13
9 1% H y a m i n e 1622 -- -- 25 0.08-0.13
10 1% H y a m i n e 1622 -{- 0.5M Z n ( O H ) 4 = -- 0.06-0.18 5 0.06-0.2
11 1% H y a m i n e 1622 + 0.1M Z n ( O H ) 4 = -- -- 75 0.i
12 0.1% H y a m i n e 1622 -- 50 0.1-0.5
13 1% H y a m i n e 10X -- -- 33-38 0.13-0.25
14 1% H y a m i n e 10X -{- 0.5M Z n ( O H ) 4 = -- 0.05-0.18 5 0.08-0.18
15 1% H y a m i n e 10X ~ 0.1M Z n ( O H ) 4 = - - - - 10 0.08

16 0.1% H y a m i n e 10X -- 50 0.08

17 0.1% or 1% T r i t o n X-400 -- 30-50 3
18 10% H y a m i n e 2389 -- -- 50 0.025
19 10% H y a m i n e 2389 -t- 0.5M A l ( O H ) 4 - -- -- 38 0.13
20 10% H y a m i n e 2389 ~- 0.5M Z n ( O H ) 4 = -- -- 7.5 0.08
21 10% H y a m i n e 2389 -{- 0.5M Z n ( O H ) 4 = -~ 0.5M
Al(OH)4- -- 2.5 0.25
22 1M K I -{- 0.1M H g O 0.5 -- --
23 100% M e O H ( n o n a q u e o u s s o l u t i o n ) 1.3 0.25 --
24 100% E t O H ( n o n a q u e o u s ) 5 1.3 -- --
25 50% M e O H -{- 10% H y a m i n e 3500 40 0.1 43 0.08
26 50% E t O H -/- 10% t t y a m i n e 3500 38 0.05 100 0.13
B. Surface-amalgamated AI

A v g corrosion rate (/dhr) in solutions of

4.5M N a O H
Set 4M N a O t I 3.5M N a O H + [Link] ZnO
No. Organic corrosion inhibitor 3M N a O H + [Link] Z n O {- [Link] A1 (OH) + 0.5M A1 (OH) a

27 None 5 0.3-1.8 5-7.5 0.6-1.8

28 1% Me3(C16H33)NBr 0.1-0.25 0.18-0.6 0.4-1.3 0.5
29 1% E t (C16H33) M e 2 N B r 0.25 0.25 0.25 0.25
30 1% M e 2 ( B z ) N 4 0.25 6.3 0.5
31 1.2% MesNBzC1 1.5 0.25 2.5 0.8
32 5% P h N M e a O H 2.5 2.5 5 1.8
33 I % P h N M e s C 1 (or I) 2.5 0.8 2.5 0.8
34 1% Me4NI 5 0.13 8 0.25
35 1% H y a m i n e 1450 0.13 0.25 0.25 0.13
36 1% A l i q u a t 4 0.8 0.08 1.3 0.2
37 1% A l i q u a t 6 0.13 1 0.8 1.3
38 1% T r i t o n X-400 0.8-3 0.5 0.5 0.25

w e a k e n i n g of t h i s l a y e r b y a m a l g a m a t i o n is o u t - w h i c h t h e n b e c o m e s t h e r a t e - l i m i t i n g s t e p in t h e
weighed by the Hg-induced increase in overvoltage corrosion mechanism.
f o r t h e He e v o l u t i o n r e a c t i o n U n f o r t u n a t e l y , a m a l g a m a t i o n of A1 p r e s e n t s s e v -
e r a l p r a c t i c a l d i s a d v a n t a g e s . L a c k of r e p r o d u c i b i l i t y
1 would result from improper amalgamation (the best
H 2 0 + e - -* O H - + -~- H2 [3]
p r o c e d u r e c o n s i s t i n g of p r e - e t c h i n g t h e A1 i n 10M

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 270 JOURNAL OF THE ELECTROCHEMICAL SOCIETY A p r i l 1963

K O H , d i p p i n g i m m e d i a t e l y into Hg, l e a v i n g t h e A1 c h l o r i d e s h o w e d no s i g n i f i c a n t effects w h e n a d d e d in

in c o n t a c t w i t h at l e a s t a d r o p of H g , a n d i m m e r s i n g c o n j u n c t i o n w i t h t h e H y a m i n e s or w i t h T r i t o n
i m m e d i a t e l y in t h e e l e c t r o l y t e ) . E x p o s u r e to a i r r e - X-400.
sults in r a p i d a t t a c k of t h e a m a l g a m a t e d A1 b y a t - A n u m b e r of s i m i l a r l y t e s t e d a d d i t i v e s such as
m o s p h e r i c Oz. H e n c e , a n i n e r t gas a t m o s p h e r e w a s CrC13, CrO4 =, VO4 =, Na2B4OT, Na4SiO4, NafSiF6, d i -
used both during and after the amalgamation pro- butylsulfide, and several quinolinium, pyridinium,
c e d u r e p r i o r to i m m e r s i o n in e l e c t r o l y t e . A m a l g a - a n d i n d o l i u m c o m p o u n d s s h o w e d no c o r r o s i o n i n -
m a t i o n in t h e e l e c t r o l y t e b y a d i s p l a c e m e n t r e a c t i o n h i b i t i n g effects.
w i t h d i s s o l v e d HgI4 = a p p e a r e d s a t i s f a c t o r y at first In summary, the organic amine compounds which
(cf. set 22 of T a b l e I ) , b u t r a p i d c o r r o s i o n s u d d e n l y i n h i b i t t h e c o r r o s i o n of A1 in c a u s t i c s o l u t i o n s e i t h e r
o c c u r r e d a f t e r s e v e r a l h o u r s ( p r o b a b l y d u e to a c o n - b y t h e m s e l v e s or in c o m b i n a t i o n w i t h Z n O a n d H g
t a m i n a t i n g c o r r o s i o n a c c e l e r a t o r i n t r o d u c e d into t h e b e l o n g m a i n l y to t h e g r o u p of d e r i v a t i v e s of
s o l u t i o n f r o m t h e c o n t a c t i n g r u b b e r s t o p p e r or f r o m Me4NOH a n d Me~NBzOH w h e r e Me = m e t h y l a n d
i m p u r i t i e s in t h e d i s s o l v i n g A1 a n d r e s u l t i n g in t h e Bz = b e n z y l . F u r t h e r m a r k e d i m p r o v e m e n t s m a y
t y p e of t h e r m a l c h a i n r e a c t i o n d e s c r i b e d in t h e p r e - r e s u l t f r o m s u b s t i t u t i n g one of t h e m e t h y l s in
c e d i n g s e c t i o n ) . H o w e v e r , e v e n if a m a l g a m a t i o n Me4NOI-I o r Me~NBzOH b y a long c h a i n g r o u p i n -
w i t h HgI4 = or HgfSO4 w e r e e n t i r e l y successful, t h e c l u d i n g 12 to 18 C a t o m s such as d o d e c y l , t e t r a -
above-mentioned reactivity with atmospheric oxy- decyl, h e x a d e c y l , s t e r y l , d i - i s o b u t y l p h e n o x y - e t h -
gen m a d e it d e s i r a b l e to s e a r c h for a m o r e s u i t a b l e oxy-ethyl, di-isobutylcresoxy-ethoxy-ethyl, etc.
inhibitor. S u b s t i t u t i o n of a H a t o m in a Bz r a d i c a l of
Organic corrosion inhibitors.--The a v e r a g e c o r r o s i o n Me3NBzOH b y a l o n g c h a i n g r o u p such as l i s t e d
r a t e s g i v e n in T a b l e I c a n o n l y s e r v e for c o m p a r a t i v e a b o v e also a p p e a r s s a t i s f a c t o r y .
rather than predictive purposes. The most commonly Corrosion inhibitio~ by means of current drain.--A
observed irreproducibility would arise from sud- m a r k e d d e c r e a s e of c o r r o s i o n r a t e w i t h i n c r e a s i n g
d e n l y a c c e l e r a t i n g corrosion, p r o b a b l y i n i t i a t e d b y anode current density was reported by Hisamatsu
an a c c e l e r a t o r . I m p r o p e r s u r f a c e a m a l g a m a t i o n (cf. (5) f o r a m a l g a m a t e d A1 in sea w a t e r ( p H v a l u e s b e -
t h e p r e c e d i n g s e c t i o n ) also a c c o u n t s f o r s o m e of t h e t w e e n 4 a n d 10), w h o r e l a t e d this effect to a n o d e
i r r e p r o d u c i b i l i t y w i t h a m a l g a m a t e d A1 (sets 2, 4-7, p o l a r i z a t i o n . T h e s a m e d e c r e a s e w a s o b s e r v e d in t h e
10, 12-14, 27, a n d 28). p r e s e n t studies. I n 10M K O H c o n t a i n i n g no i n h i b i -
Nevertheless, significant conclusions may be tors, t h e c o r r o s i o n of a n u n a m a l g a m a t e d A1 a b a t e d
d r a w n f r o m T a b l e I. S e t s 2, 4, etc., s h o w r e d u c e d H2 to a m i n i m u m l o c a l a c t i o n c o r r o s i o n c u r r e n t of a p -
p r o x i m a t e l y 10 m a / c m 2 f o r a n o d e c u r r e n t d e n s i t i e s
evolution but serious Zn sponge formation with ZnO
as a d d i t i v e in a b s e n c e of Hg. C o m p a r i s o n of sets 5-8 of t h e o r d e r of 50 m a / c m 2.
w i t h 1-4 s h o w s a m a r k e d r e d u c t i o n of c o r r o s i o n r a t e A m o r e a c c u r a t e d e t e r m i n a t i o n of t h e c o r r o s i o n
u p o n a d d i t i o n of 10% H y a m i n e 3500. S e t s 9-16 s h o w r a t e d e p e n d e n c e on a n o d e c u r r e n t d e n s i t y w a s
s i m i l a r c o r r o s i o n i n h i b i t i o n w i t h 1% H y a m i n e 1622 a c h i e v e d b y m e a s u r i n g t h e r a t e of H2 e v o l u t i o n d u r -
or 1% H y a m i n e 10 X, b u t p o o r e r i n h i b i t i o n w i t h i n g c u r r e n t d r a i n . T h e r e s u l t s for s u r f a c e - a m a l g a -
o n l y 0.1% of t h e s e H y a m i n e s . S e t s 17-21 s h o w s i m i - m a t e d A1 g r a d e 1145 a n o d e s in a Z n O - s a t u r a t e d
l a r t h o u g h s o m e w h a t p o o r e r r e s u l t s w i t h 1% T r i t o n s o l u t i o n c o n t a i n i n g 3M K O H p l u s 0.5M A I ( O H ) ~ a r e
X - 4 0 0 or 10% H y a m i n e 2389. C o m p a r i s o n of a d j a - g i v e n in Fig. 3, w h i c h s h o w s c u r r e n t efficiencies of
c e n t c o l u m n s in sets 1-26 s h o w s t h e r e m a r k a b l e at l e a s t 80% f o r a n o d e c u r r e n t d e n s i t i e s of 3-25
effect of a m a l g a m a t i o n , e s p e c i a l l y in c o n j u n c t i o n ma/cm 2.
w i t h t h e s a m e H y a m i n e s . S e t s 36-38 s h o w d i s t i n c t Other examples of corrosion inhibition with in-
c o r r o s i o n i n h i b i t i o n b y 1% A l i q u a t 4 or 6 or 1% creasing current density are shown in Fig. 7 and 9
T r i t o n X - 4 0 0 w h e n c o m p a r e d w i t h t h e c o n t r o l sets of an earlier paper (1).
1-4. S i m i l a r l y , sets 28, 29, a n d 31 c o m p a r e d w i t h Conclusions
sets 1-4 s h o w i n h i b i t i o n b y 1% MesC16H3~NBr, 1%
Et(C16H3a)MefNBr, a n d 1.2% Me3NBzC1, sets 32-34 A l t h o u g h c o r r o s i o n i n h i b i t i o n is q u i t e effective
s h o w s o m e i n h i b i t i o n b y P h N M e a O H , PhNMe3C1 or w i t h b o t h t h e f a i r l y l a r g e n u m b e r of a d d i t i v e s l i s t e d
PhNMe3I, a n d Me4NI, set 30 s h o w s a q u e s t i o n a b l e in T a b l e I a n d w i t h a n u m b e r of a l c o h o l solutions,
a d v a n t a g e of MefBzN, a n d set 35 s h o w s d i s t i n c t i n - it is m o s t f r e q u e n t l y a c c o m p a n i e d b y i n c r e a s e d
h i b i t i o n b y H y a m i n e 1450. a n o d e p o l a r i z a t i o n . N e v e r t h e l e s s , s e v e r a l of t h e i n -
h i b i t o r s i n c l u d e d in T a b l e I, as w e l l as t h e o b s e r v a -
C o r r o s i o n a b a t e d m a r k e d l y in n o n a q u e o u s M e O H
tions on c h e m i c a l a n d t h e r m a l a c c e l e r a t i o n a n d on
or E t O H s o l v e n t s ( s e t s 23 a n d 24), b u t n o t in 1:1
i n h i b i t i o n b y c u r r e n t d r a i n m a y l e a d to t h e d e v e l o p -
w a t e r - a l c o h o l s o l u t i o n s (sets 2 5 - 2 6 ) . S i m i l a r l y r e -
m e n t of p r a c t i c a l A1 b a t t e r i e s (1).
p l a c e m e n t of w a t e r b y 100% M e O H r e d u c e d t h e a t -
t a c k o n p l a i n ( H g - f r e e ) A1 in 2M L i f S f r o m 18 t~/hr Manuscript received Feb. 12, 1962; r e v i s e d m a n u -
to <0.03 ~ / h r . script received Nov. 1, 1962.
No significant effect w a s c a u s e d b y 0.5M A I ( O H ) 3 A n y discussion of this p a p e r will a p p e a r in a Discus-
in sets 3, 8, 21, 27, 29, 32, a n d 33, b u t d i s t i n c t i n t e r - sion Section to be p u b l i s h e d in the D e c e m b e r 1963
JOURNAL.
f e r e n c e w i t h t h e i n h i b i t i n g effect of H y a m i n e 3500
REFERENCES
is s h o w n in set 7 a n d also w i t h o t h e r i n h i b i t o r s in
1. S. Zaromb, This Journal, 109, 1125 (1962).
sets 19, 28, 30, 31, a n d 3 4 - 3 7 . . O n t h e o t h e r h a n d , 2. G. Vinal, " P r i m a r y Batteries," p. 96, J o h n W i l e y
10-20% polyvinylbenzene trimethylammonium & Sons, Inc., New Y o r k (1951).

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 VoI. 110, No. 4 A1 C O R R O S I O N I N C A U S T I C S O L U T I O N S 271

3. W. M. Latimer and J. H. Hildebrand, "Reference A. G. Gray, Editor, John Wiley & Sons, Inc., New
Book of Inorganic Chemistry," Macmillan Co., York (1953).
New York (1950). 5. Yoshihiro Hisamatsu, J. E l e c t r o c h e m . Soc. ( J a p a n ) ,
4. F. Keller in "Modern Electroplating," pp. 514-517, 27, E73-75 (1959).

Correction
In the papers "Theory and Design Principles of the (2n + 1)~x
e-c2n + z)2v2D~'/4a 2 sin [42]
Reversible Electroplating Light Modulator" and 2a
"Geometric Requirements for Uniform Current Den-
sities at Surface-Conductive Insulators or Resistive The last line of footnote 4 should read:
Electrodes" by Solomon Zaromb, published in Vol. i n C a n d j,s Eq. w (2), a n d a d d i n g + c~.
109, pp. 903-918, October 1962 JournaL, the following The line preceding Eq. [50] should read:
changes should be made:
[42], results in a solution of the form 5
p. 908, Eq. (V') should read
( 3 ) and Eq. [50'] is
~-Is-+Ag +---~I- ~(3I-+Ag+)~AgI3 = (V')
L Fa aWL Fa "~
P a g e 909: B o u n d a r y condition [40'] is:
an amount q a / F injected at x = a and tp = ~-~ [40'] -b "' 1 -- ~ e-~2Dtp'/4a 2 sin 2a [50']
qr
Eq. [42] is:
cox(x, tp') = Page 910, column 2, Eq. [50'"'] is

zqa2 ~ (2n -t- 1)~rx Cox(X, 0) ~-- - 2qd

~ a [ 1 -t- ":-2
1 e--•2Dtp'/4a2 ] -Xa
- for t= ---- O
~-r ( - - i ) ~ e-(2n+l)2cr2Dtp'/4a 2 sin
F a n=0 2a [50'"']
+4ci ~. (2n -t- 1)~rx On p. 914, fourth line from bottom of column 1,
e - (2n + 1)2~r2Dtp'/4a 2 s i n
~r n=0 2a Eq. [19] should read Eq. [9].
On p. 916, column 2, in the line following Eq. [77']
insert ) following [7]; in the next line delete the ,
= Fa + ~ following [39].

Properties of Evaporated Thin Films of SiO

D. B. York
C o m p o n e n t s Division, I n t e r n a t i o n a l B u s i n e s s Machines Corporation, Kingston, N e w Y o r k

ABSTRACT
The absorption coefficient and transmission of vacuum deposited films of
SiO were used as a measure of the reproducibility of the relative composition
of the resulting films. The optical properties of the films can be reproduced
by controlling the evaporation rate and partial pressure of oxygen. Repro-
ducibility of optical properties does not insure reproducible electrical prop-
erties since the surface condition of the electrode material greatly affects the
electrical properties.

Recently, SiO has received considerable attention on condensation the compound probably dispropor-
in the fabrication of thin films by v a c u u m evapora- tionates according to the following reaction
tion technique due to its low vapor pressure, rela-
tive chemical inertness, sublimation of bulk m a t e - 2Si0-~ Si + Si02
rial, and flexibility of boat design. V a c u u m deposited
thin films of SiO have been widely used in the The condensed material obtained for the experi-
areas of optical coatings, encapsulation of electrical ments to be discussed varied in composition depend-
and optical devices, and as an insulator or dielectric ing on conditions of preparation. As would be ex-
in thin film electrical devices. pected, this variation in composition greatly affected
Although this material has found wide applica- the optical and electrical properties of the thin films.
tion in the thin film area, there is a question con- The purpose of this investigation was to study
cerning the existence of a true chemical compound the influence of the partial pressure of oxygen and
SiO in the solid state (1-13). It has been established the evaporation rate of the SiO and to relate these
that SiO does exist in the gas phase (7-8) whereas findings to their optical and electrical properties.

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