JOURNAL OF THE ELECTROCHEMICAL SOCIETY

SOLID-STATE SCIENCE
JULY
--AND TECHNOLOGY
1972

On the Mechanism of Low-Temperature Oxidation

(23~176 of Polycrystalline Nickel
M. J. Graham and M. Cohen*
Division of Chemistry, National Research Council of Canada, Ottawa, Ontario, Canada KIA OR9

ABSTRACT
The oxidation of "clean" nickel has been investigated from 24 ~ to 450~ at
oxygen pressures of 5 X i0 -s to 6 X 10-* Tort. Ultra-high vacuum techniques
made it possible to start oxidation on specimens free of oxide and surface
impurities such as C, Si, and S. Oxygen uptake was measured manometrically
with a capacitance gauge of submonolayer sensitivity. Initial rapid oxygen ad -
sorption (and place exchange) on nickel was followed by slower oxidation
obeying a logarithmic rate law over the thickness range 8-30A. Growth of
thicker films was in accord with a parabolic rate law, transport through the
oxide occurring predominantly via easy diffusion paths. The value of 41 kcal.
mole -I calculated from an Arrhenius plot of the parabolic rate constants from
300 ~ to 450~ is an approximate measure of the activation energy for growth via
leakage paths. A pt/6 dependence of the parabolic growth rate on oxygen
pressure was found at 450~

Nickel oxidation is considered to be one of the sim - pler systems Specimen ~naterial.--Zone-refined nickel sheet (0.02 cm
of study since o n l y one oxide, NiO, is produced, and p a r t l y for thick) supplied b y Materials Research Corporation was used. It was
this reason has been the subject of n u m e r o u s investigations (1). analyzed to be 99.998% nickel, con - t a i n i n g as impurities (in
NiO, a p - t y p e semiconductor, grows by the o u t w a r d m o v e ppm atomic): C, 2; O, 3; F, <0.1; Na, 0.2; Mg, 0.5; Si, 0.7; C1, 0.2;
m e n t of nickel cations and electrons via vacancies and holes. K, 0.2; Cr, 0.6; Fe, 6; S, not detected.
At high temperatures, say >1000~ parabolic growth is g e n e r a l l Gases.--Spectroscopically standardized oxygen (<70 v p m
y observed. However, at m o d e r a t e t e m p e r a - impurities) and h y d r o g e n (<14 v p m impurities) were used
tures ( a r o u n d 500~ a v a r i e t y of e x p e r i m e n t a l kinetics (Baker Chemical C o m p a n y ) .
have been reported . These include parabolic
(2) , two stage logarithmic (3, 4), and logarithmic followed by Specimen preparation.--Coupons, 0.02 by 1 cm and from 2 to
quartic (5) rates of oxidation . It m a y be that differences in m a t e r 4 cm long, were degreased, chemically polished for 30 sec at 85~ in
i a l purity, surface preparation, and p r e t r e a t r n e n t could a m i x t u r e of 30% v o l u m e nitric acid, 10% sulfuric acid, 10%
account for the v a r i a t i o n in e x p e r i m e n t a l data, and the phosphoric acid, and 50% acetic acid, and t h e n electropolished for
present w o r k on we]l - characterized surfaces was u n d e r t a k e 2 rain at 23~ in a 4 - v o l u m e sulfuric a c i d : 3 - v o l u m e w a t
n in an attempt to resolve some of the discrepancies and, if possible, e r m i x t u r e at a c u r r e n t density ,.-0.5 A 9cm -~. Chemical
to present a simplified model for the l o w - t e m p e r a t u r e polishing removed about 5 ~,m a n d electropolishing 8
oxidation of nickel.
ION pUMP
Experimental
Apparatus.--The oxidation a p p a r a t u s is shown sche-
matically in Fig. 1. It is a n i m p r o v e d design of an earlier m a n
M.K.S TO GAS
o m e t r i c system (6), h a v i n g u l t r a - h i g h v a c u u m CAPACITANCE ~/HANOLING
capabilities (pressures <3 X 10 -*~ Torr after GAUGE --
bakeout at 250~ and e m p l o y i n g a sensitive capaci - tance gauge LEAK
to follow the p r e s s u r e decrease with time d u r i n g oxidation . VALVE
The gauge was an M.K.S. I n s t r u - m e n t s 90H - l, held at 30~
by a t e m p e r a t u r e controller (Type 1090-1). W i t h the
exception of the quartz speci-m e n c h a m b e r the apparatus was
all m e t a l a n d con - t a i n e d a w o r k i n g v o l u m e of about 1 TO OIL
DIFFUSION
liter. At oxida - tion pressures ~ 5 X 10 - s Torr, s u b - m o n o l a y PUMP
e r ad - sorption was readily measured . D u r i n g pressure m e a -
surements, the reference side of the capacitance gauge w a s p u m p e
d w i t h a n 8 liter 9 sec -1 ion pump . Speci - m e n heating was b y PARTIAL
L PRESSURE
a t u b e f u r n a c e (hot zone variation of • 1 7 6 a r o u n d the SPECJMEN GAUGE
quartz tube . CHAMBER TEE
VALVE
9Electrochemical Society Active Member.
K e yw o r d s : kinetics , p r e s s u r e d e p e n d e n c e , m a n o m e t Fig. I. Manometricoxidationsystem
r i c apparatus.

879

Downloaded on 2014-05-12 to IP 152.14.125.198 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 880 J. Electrochem . Soc.: SOLID-STATE SCIENCE AND TECHNOLOG
Y J u l y 19 72
#m of material . T h e s p e c i m e n was t h e n placed on a p l a t i
n u m support in t h e quartz t u b e of t h e o x i d a t i o n system.
0.6
40
Oxidation . ~Afte r bakeout, t h e following p r o c e d u r e s w e
r e c a r r i e d out. o<
(i) W h e n the system had cooled, 1 T o r r o x y g e n was a d so
m i t t e d for 1 hr to s a t u r a t e the walls of t h e system; this m i n 0,4 500~ C
i m i z e d surface adsorption during a subsequent o x i d a t i o n e x E
periment. 20 ~
N

(ii) To decrease the carbon i m p u r i t y concentration t h e 200~ C

specimen was h e a t e d to 700~ and enough o x y g e n a d m i t t e x
o
0.2

d to produce ~ 1 0 0 A of NiO. D u r i n g continued a n n e a l i n g 25 ~ C

Io
of the film in v a c u u m , CO evolved . [Gas analyzed by an A.E.1
Minimass p a r t i a l pressure gauge (Fig. 1)]. In some e x p e r i m e
n t s t h e capacitance gauge was used to follow t h e pressure I 1 I i I
0 2 4 6 8 I0
increase in the system due to CO formation, p r e s u m a b l y by the TIME, rain
reaction: C 4- NiO -~ CO 4- Ni, and corresponded a f t e r 2~/z h r
Fig. 3. Early stages of oxidation of polycrystalline nickel up
at 700~ to the r e m o v a l of > 1 p p m of C f r o m the speci - men .
to 340~ in 5 X 10 - ~ Torr oxygen; expansion of data in Fig. 2.

(iii) The r e m a i n i n g oxide was reduced w i t h 1 Torr

h y d r o g e n at 600~ Gas was a d m i t t e d for 5 min, p u m p e d
out, and t h e system refilled w i t h fresh h y d r o - gen.
(iv) H y d r o g e n was p u m p e d out and the t e m p e r a t u r
e set to the oxidation t e m p e r a t u r e . W h e n t h e r m a l e q u i
- l i b r i u m was established and the pressure was ~ 5 • 10 - 9 Torr,
the oxidation was performed . T h e "tee" v a l v e (Fig. 1) was first
closed and the initial o x y g e n dose size m e a s u r e d before
oxidation of t h e specimen began. In this way, w h e n the tee v a l v
e was opened
the e x t r e m e l y rapid initial uptake by t h e specimen could be
determined . Calibration runs w i t h o u t speci - mens at each e x p
e r i m e n t a l t e m p e r a t u r e m e a s u r e d the small uptake on
the walls of t h e system. O x i d a - tion pressures r a n g e d from 5
• 10-~ to 6 • 10 -1 Torr; pressures quoted are a v e r a g e values and
d u r i n g the course of oxidation w e r e adjusted to ~25% above
(by a d m i t t i n g m o r e o x y g e n ) , and allowed to fall ~25%
below these values .
Surface and oxide examination.--To ensure that no c o n t a m
i n a t i o n had occurred, surfaces p r e t r e a t e d as above and oxidized
at l o w t e m p e r a t u r e s w e r e a n a l y z e d for i m p u r i t i e s by
x - r a y emission techniques (7). Replicas of oxide surfaces and stripped
oxide films w e r e e x a m i n e d by electron microscopy .
Results
The kinetic curves for the oxidation of p o l y c r y s - talline
nickel (-~120 #m a v e r a g e grain d i a m e t e r ) from room t e m
p e r a t u r e to 450~ in 5 • 10 - s T o r r oxygen are shown in Fig. 2.
Uptake is expressed as #g o x y g e n
cm -2. Mean oxide thicknesses are also g i v e n and h a v e been
calculated assuming a roughness factor of 1 and an NiO density of
6.75 (1 #g o x y g e n cm - ~ e q u i v a l e n t to 69.2A of NiO) . U p
t a k e s are low up to 340~ and the e a r l y stages of oxidation are b
e t t e r o b s e r v e d in the e x p a n d e d plot of Fig. 3. Duplicate e
x p e r i m e n t s w e r e carried out at most t e m p e r a t u r e s ;
the r e p r o d u c i b i l i t y of oxidation is indicated by the two runs
at 200~
As seen in Fig. 3, an initial e x t r e m e l y rapid oxida - tion is f o
l l o w e d by a transition to a period of l o w e r oxidation rate. At
room t e m p e r a t u r e an uptake of 0.15 ~g o x y g e n cm - 2 is
approached, e q u i v a l e n t to a limiting oxide thickness of about
10A. A t 200~ a continuing uptake is m e a s u r e d and t h e data
are found to follow a direct l o g a r i t h m i c l a w of the form, x =
A in t + B, w h e r e x is t h e o x y g e n u p t a k e (thickness) and t
the oxidation time (see Fig. 4). Thin film data (up to ~ 3 0 A ) at h i
g h e r t e m p e r a t u r e s also follow a logarithmic law; the d u r a
t i o n of the log dependence diminishes w i t h t e m p e r a t u r e
and at 340~ (as seen in Fig. 4) applies for only the first 2 rain of
oxidation . Thicker films ( > 3 0 - 4 0 A ) , as illustrated by data at
340 ~ and 400~ in Fig. 5, g r o w in accordance with a p a r a - bolic
rate law.
L
c~ 9 eJ
E o-e~ 0-60' E
o 0.2~ /9 | o
Z ---~ Z
200~C 9 --
a_ 0.45 a_

I i ] - i - - I I
I0, ~ ~ 7 0 0
0.15 9 , , , I , , ~ ~1 , , , r , ,, =dO.30
OJ 0.5 1.0 5.0 I0
TIME, min
Ec~8J ,600
Fig. 4. Logarithmic plot of data from oxidation of a
polycrystalline nickel at 200 ~ and 340~

61 r
i ~'B,.o ~ ~
45o'c _~
c~c~
I0 ::L
,- g

~_00
~0.5 340 ~ C -O

~ / 365- ~100 400 ~ C

-- 340
_ ~oop 9~ , 9
I P I I I 0
,; 2'0 s'0 4o 5o 6o 0 I0 20 50 40 50 60
TIME, rnin TIME, rain
Fig. 2. Oxidation of polycrystalline nickel from 23 ~ to 450~ in Fig. 5. Parabolic plot of data from oxidation of polycrystalline
5 X 10 - 3 Torr oxygen. nickel at 340 ~ and 400~

Downloaded on 2014-05-12 to IP 152.14.125.198 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
Vol. 119, No. 7 LOW-TEMPERATURE
ICKEL 881
'E
500 6 I0 t
O0
20 40 60 80
TIME, rain
Fig. 6. Parabolic plots of data from the oxidation of
polycrystalline nickel at 450~ in 5 X 10 - 3 , 5 X 10 - 2 , and 6
X 10 - t Tort oxygen.
To e x a m i n e the effect of pressure on the kinetics, oxygen
uptakes at 450~ were m e a s u r e d at three dif - ferent pressures: 5
X 10 - 3 , 5 X 10 - 2 , and 6 X 10 -1 Torr. I n Fig. 6 the data are
plotted parabolically and a good relationship is observed.
Expressing the rate constant, Kp, proportional to (oxygen pressure,
p)l/n, the value of n can be obtained by plotting lOgl0Kp against
logl0P. F r o m Fig. 7 the data fit a reciprocal slope of n = 6 m u c h
better t h a n one of n = 4. Although only three orders of m a g n i t u
d e of pressure could be covered with the present gauge, a pl/6
relationship would seem to be applicable, at least over the present r
a n g e of study.
Discussio n
The oxidation m a y be considered to proceed in three stages.
Initial adsorption (and place exchange) is fol-lowed by slower
oxidation obeying a logarithmic law (from oxide thicknesses 8-
30A), and if the t e m p e r a - t u r e is sufficiently high for f u r t h
e r t h i c k e n i n g to occur, this continued growth obeys a
parabolic rate law.
Initial stage.--Evaporated metal films have been used
extensively for m e a s u r e m e n t s of sticking coeffi-cients (8),
heats of adsorption (9, 10), and surface potentials (11, 12) of
oxygen on nickel from --196 ~ to
150~ On nickel single crystals, electron diffraction techniques have
identified s u b - m o n o l a y e r structures (13-16). If nickel and
other metals such as Fe, Co, and Ti are exposed to oxygen at room
temperature, more t h a n a m o n o l a y e r of oxygen is r a p i d l y
adsorbed with an u n c h a n g i n g heat of adsorption. The heats of
ad - sorption m e a s u r e d are similar to heats of formation of the
oxide (9), and coverage values on nickel at saturation correspond to
about two to three oxygen atoms per surface metal atom (9, 10).
The present data at room t e m p e r a t u r e give a n i n s t a n t a n
e o u s uptake
3.4
/ anisotropy of oxidation i n the t h i n - film range reflecting a v a r y
-3.6 /
n=4//
(2_ //
d -3,8 //
//
-3,0 -2.0 -I.0
Loglo P
Fig. 7. Logarithm of parabolic rate constants for oxidation of
polycrystalline nickel at 450~ plotted against logarithm of oxida-
tion pressure. The bars on the data indicate the considered
errors. Lines drawn have reciprocal slopes n = 6 and n = 4.
OXIDATION OF N
approaching a coverage value of three. It is considered that r e a r r
a n g e m e n t of the initial adsorbed layer occurs b y a process of
rapid place exchange (17, 18), r e s u l t - ing in the formation of
nickel oxide.
Logarithmic growth.--Continued growth on the initial
oxide occurs m u c h more slowly and the present data follow a
logarithmic rate law from ,~8-30A, a s illustrated b y results at 200 ~
and 340 ~ i n Fig. 4.
Previous w o r k on nickel oxidation in this thickness range has
also indicated logarithmic growth (19, 20), and m a n y theories
have b e e n developed to account for logarithmic kinetics (21-27).
Besides t h e difficulty in deciding w h e t h e r t h i n film data
follow a direct or i n - direct logarithmic law (the present results fit
the former b e t t e r ) , the absence of other i n f o r m a t i o n such
I00 120 as the pressure dependence and the effect of electric fields on t h i n
film growth, makes it difficult to favor a particular process (either
electron or ionic transport, or chemisorption at the outer oxide
surface) as the r a t e - d e t e r m i n i n g step.
Parabolic growth.--For oxide thicknesses above 30-40A the
data follow parabolic kinetics (see Fig. 5 and
6) . 1 As m e n t i o n e d earlier various rate laws h a v e been
previously reported for nickel oxidation at 400~176 including
parabolic (2), two stage logarithmic (3, 4), and logarithmic followed
b y f o u r t h power (5). We would consider that the v a r i e t y of
results arise from the development of s t r u c t u r a l l y different
oxides whose formation has b e e n influenced b y the n a t u r e of
the starting surface. I n this i n t e r m e d i a t e t e m p e r a t u r e
range where g r a i n b o u n d a r y diffusion is a n i m p o r t a n t
factor, a change in oxide grain size with oxidation time could cause
a c o n t i n u e d decrease i n the a p p a r e n t parabolic rate
constant (28), accounting for deviation from parabolic kinetics. The
initial oxide g r a i n size and epitaxy will depend on the n a t u r e
(both chemical and physical) of the surface prior to oxidation. I m -
purities such as c a r b o n and sulfur t e n d to segregate at the
nickel surface (29, 30) and the influence of carbon and silicon on the
oxide epitaxy has b e e n reported
(31) . Also, the presence of a prior oxide film affects s u b s e q u e
n t oxide morphology and growth, a point which is demonstrated i n
the following paper (32). The oxide - free starting surfaces in this w
o r k are considered to be clean; the e x p e r i m e n t a l procedure
resulted in surface i m p u r i t y concentrations of sulfur, silicon,
and iron below the limit of detection of the x - r a y emission
technique (7), which is about 5% of a monolayer . Carbon i m p u r i
t y levels w e r e also u s u a l l y as low, although w i t h decreasing
oxidation t e m p e r a , l u r e there was an increased p r o b a b i l i
t y of carbon c o n t a m i n a t i o n due to cracking of the <10 - 9
Torr back - ground carbon monoxide .
Oxides produced on these "clean" and fiat nickel surfaces were
not well oriented; t h i n n e r oxides (a few h u n d r e d angstroms
thick) exhibited preferred orienta - tion, b u t with increasing
thickness tended to become more polycrystalline . I n addition,
oxide grain size increased with temperature, from --100A at
/ 300~176 to ,~1000A at 450~ The m a n y grain boundaries, and
/
/ perhaps s u b g r a i n b o u n d a r i e s present i n these oxide films
/
/
/ are considered to be paths for easy nickel diffu-sion (33, 34), the
/ i n g density of these high - diffusivity paths (35). Because of s t r u
c t u r a l changes of the oxide with t e m p e r a t u r e , the
activation e n e r g y of 41 kcal 9mole - t calculated from the
parabolic rate
constants over the t e m p e r a t u r e r a n g e 300~176 (see Fig. 8)
is considered to be o n l y an approximate m e a - sure of the
activation e n e r g y for growth via leakage paths. 2
1 Good parabolic behavior was maintained in the longest oxidation
e x p e r i m e n t performed ---- 64 h r a t 450~( o x i d e t h i c k n e s s ~ 1 ~ m ) .
2 As w i l l b e s e e n i n t h e f o l l o w i n g publication, a lin
e of slope 37
kcal.mole-~ may be drawn through the present
data and rates of
oxidation from 500 ~ t o 700~ T h i s value,, w h i l e again pr
obably not
an a c c u r a t e m e a s u r e of t h e a c t i v a t i o n e n e r g y f o r g r o w t h v i a l e a k a g e
p a t h s b e c a u s e t h e s t r u c t u r e of t h e o x i d e is c h a n g i n g w i t h t e m p e r - a t u
r e , is s i g n i f i c a n t l y l e s s t h a n v a l u e s --~52 k c a l ' m o l e -1 r e p r e s e n t a t i v e
of l a t t i c e d i f f u s i o n t h r o u g h n i c k e l o x i d e (32).
Downloaded on 2014-05-12 to IP 152.14.125.198 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 882 J. Electrochem . Soc.: SOLID-STATE SCIENCE A N DT E C H N O
LOGY July 1972

9. D. B r e n n a n , D. O. Hayward, and B. M. W. Trapnell,

4"01@~
Proc. Roy. Soc. (London), A256, 81 (1960).
10. D. B r e n n a n and M. J. Graham, Discussions Faraday Soc.,
41, 95 (1966).
-

11. C. M. Q u i n n a n d M. W. Roberts, Trans. Faraday Soc.,

60, 899 (1964).
12. T. A. Delchar and F. C. Tompkins, Proc. Roy. Soc. (London),
A3~), 141 (1967).

t
13. L. H. G e r m e r and A. U. MacRae, J. Appl. Phys., 33, 2923
(1962).
14. R. L. P a r k and H. E. Farnsworth, J. Chem. Phys., 40, 2345
(1964).
15. A. U. MacRae, Surface Sci., 1, 319 (1964).
-a.0 -o ~ ~ o b
16. P. B. Sewell and M. Cohen, Appl. Phys. Letters, 7, 32 (1965).
1.4 1.5 1.6 1.7 17. M.A.H. L a n y o n and B. M. W. Trapnell, Proc. Roy Soc.
I / T a K xlO 5
(London), A227, 387 (1955).
18. D. D. Eley and P. R. Wilkinson, ibid., A254, 327 (1960).
Fig. 8. Logarithm of parabolic rate constants for oxidation of
polycrystalline nickel from 300 ~ to 450~ in 5 X 10- 3 Torr oxy-gen 19. W. E. Campbell and U. B. Thomas, Trans. & J. Elec-
plotted against (absolute temperature)-1. trochem. Soc., 91, 623 (1947).
20. K. Hauffe and B. Ilschner, Z. Electrochem., 58, 382 (1954).
Pressure dependence of parabolic growth . -- The 21. N. F. Mott, Trans. Faraday Soc., 36, 472 (1940).
degree of ionization of nickel vacancies in NiO has been a m a t t e r 22. N. Cabrera and N. F. Mott, Rept. Progr. Phys., 12, 163 (1948-
for discussion (36). F r o m electrical con - ductivity m e a s u r e m 49).
23. T. B. G r i m l e y and B. M. W. Trapnell, Proc. Roy. Soc.
e n t s at high t e m p e r a t u r e s (around (London), A234, 405 (1956).
1000~ both singly ionized (37-39) and d o u b l y ion - ized 24. A. T. Fromhold, Jr. and E. L. Cook, Phys. Rev., 158, 600
vacancies (40-42) have been proposed as the pre - d o m i n a n t (1967).
defect. The present results of the effect of oxygen pressure (5 X 10 - 25. I. M. Richie and G. L. Hunt, SurJace Sci., 15, 524 (1969).
3 to 6 X 10 -1 Torr) on the oxidation rate at 450~ as seen in Fig. 7,
26. F. P. F e h l n e r and N. F. Mott, Oxid. o] Metals, 2, 59
fit a pl/~ dependence, consistent with the formation and move - m e (1970).
n t of doubly charged cation vacancies. 27. D. E. Davies, U. R. Evans, and J. N. Agar, Proc. Roy. Soc.
(London), A225, 443 (1954).
28. E. A. G u l b r a n s e n and K. F. Andrew, This Journal,
Acknowledgment 1Ol, 128 (1954).
The authors t h a n k Dr. D. Caplan for helpful dis-cussion. This 29. E. N. Sickafus, Surface Sci.,19, 181 (1970).
was paper N.R.C.C. No. 12444. 30. J. M. Blakely, J. S. Kim, and H. S. Potter, J. Appl. Phys., 41,
2693 (1970).
M a n u s c r i p t s u b m i t t e d Nov. 29, 1971; revised m a n u - 31. L. B. G a r m o n , Ph.D. Thesis, Univ . of Virginia (1966).
script received Feb. 15, 1972.
32. M. J. Graham, G. I. Sproule, D. Caplan, and M. Cohen, This
A n y discussion of this paper will appear in a Discus-sion Journal, 119, 883 (1972).
Section to be published in the J u n e 1973 JOURNAL. 33. J. M. Perrow, W. W. Smeltzer, a n d R. K. Ham, Acta. Met.,
15, 577 (1967).
REFERENCES 34. J. M. Perrow, W. W. Smeltzer, and J. D. E m b u r y , ibid., 16,
1. G. C. Wood, I. G. Wright, and J. M. Ferguson, Cor-rosion 1209 (1968).
Sci., 5, 645 (1965). 35. J. V. Cathcart, G. F. Petersen, a n d C. J. Sparks, Jr., This
2. W. J. Moore and J. K. Lee, Trans. Faraday Soc., 48, 916 Journal, 116, 664 (1969).
(1952). 36. Z. M. Jarzebski a n d S. Mrowec, Oxid. of Metals, 1, 267
3. It. H. Uhlig, J. Pickett, and J. MacNairn, Acta Met., 7, 111 (1969).
(1959). 37. H. H. B a u m b a c h and C. Wagner, Z. Physik. Chem., B24,
59 (1934).
4. J. C. Rocaries and M. Rigaud, Scripta Met., 5, 59 (1971). 38. I. Bransky and N. M. Tallan, J. Chem. Phys., 49, 1243
5. K. Hauffe, L. Pethe, R. Schmidt, and S. R. Morrison, This (1968).
Journal, 115, 456 (1968). 39. J. T. Cox and C. M. Quinn, J. Mater. Sci., 4, 33 (1969).
6. M. J. Graham, S. I. All, and M. Cohen, ibid., 117, 513 (1970). 40. S. P. Mitoff, J. Chem. Phys., 35, 882 (1961).
7. P. B. Sewell, D. F. Mitchell, and M. Cohen, Develop. Appl. 41. S. Pizzini and R. Morlotti, This Journal, 114, 1179 (1967).
Spectr., 7A, 61 (1969).
42. Y. D. T r e t y a k o v and R. A. Rapp, Trans. AIME, 245,
8. A. M. Horgan a n d D. A. King, SurSace Sci., 23, 259 (i970) . 1235 (1969).

Downloaded on 2014-05-12 to IP 152.14.125.198 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).