Vol. 105, No.

OXIDATION

OF AN A1-3% Mg ALLOY

General
I n t h e p r e c e d i n g discussion, t h e o x i d a t i o n k i n e t i c s
at t e m p e r a t u r e s g r e a t e r t h a n 350~ h a v e b e e n a p p r o x i m a t e d to p a r a b o l i c a n d l i n e a r r a t e e q u a t i o n s .
A c o m p a r i s o n of o x i d a t i o n a n d Mg e v a p o r a t i o n r a t e s
d e m o n s t r a t e d t h a t t h e o x i d e film o f f e r e d r e s i s t a n c e
to o x i d a t i o n at a l l s t a g e s of e x p o s u r e . M e t a l l o g r a p h i c
and x-ray examinations have shown that depletion
of Mg b y s e l e c t i v e o x i d a t i o n r e s u l t e d in f o r m a t i o n
of A1 i n c l u s i o n in t h e oxide. T h e s e inclusions, in
t u r n , c a u s e d a g r a y to b l a c k d i s c o l o r a t i o n of t h e
surface. M a n y of t h e v i e w s w h i c h h a v e b e e n e x pressed must remain speculative because chemical
c o m p o s i t i o n s a n d s t r u c t u r e s of t h e o x i d e s in t h e
c o m p o s i t e film, a n d d e t e r m i n a t i o n s of M g a c t i v i t i e s
a n d d i f f u s i v i t i e s for t h e a l l o y a n d o x i d e s a r e r e q u i r e d to e l u c i d a t e t h e o x i d a t i o n a n d Mg e v a p o r a tion behavior.

Acknowledgments
T h e a u t h o r w i s h e s to e x p r e s s his t h a n k s to f o r m e r
c o l l e a g u e s , e s p e c i a l l y J. S. K i r k a l d y a n d H. P.
G o d a r d , at A l u m i n i u m L a b o r a t o r i e s , for h e l p f u l d i s cussions.
M a n u s c r i p t r e c e i v e d Nov. 26, 1956.
A n y discussion of this p a p e r will a p p e a r in a Discussion Section to b e p u b l i s h e d in the D e c e m b e r 1958
JOURNAL.

71

REFERENCES
1. S. Dobinski a n d M. Niesluchowski, Nature, 144, 510
(1939).
2. L. De Brouck~re, J. Inst. Metals, 71, 131 (1945).
3. R. E b o r a l l and C. E. Ransley, ibid., 71, 525 (1945).
4. O. K u b a s c h e w s k i and H. Ebert, Metall]orschung, 2,
232 (1947).
5. M. W h i t a k e r and A. R. Heath, J. Inst. Metals, 82,
107 (1953).
6. A. J. Swain, ibid., 80, 125 (1951).
7. P. T. Stroup, "Controlled A t m o s p h e r e s , " A.S.M.
(1941).
8. E. A. Smith, Jr., Light Metal Age, 12, 24 (October,
1954).
9. W. W. Smeltzer, This Journal, 193, 209 (1956).
10. M. S. H u n t e r a n d P. Fowle, ibid., 103, 483 (1956).
11. T. E. Leontis and F. N. Rhines, Trans. Am. Inst.
Mining Met. Engrs., 166, 265 (1946).
12. I. A. Makolkin, Zhur. Priklad. Khim., 24, 460 (1951).
13. E. A. Gulbransen, Rev. Sci. Instr., 15, 201 (1944).
14. U. R. Evans, Trans. Am. Inst. Mining Met. Engrs.,
166, 292 (1946).
15. J. Loriers, Compt. rend., 231, 522 (1950).
16. W. W. Webb, J. T. Norton and C. Wagner, This
Journal, 103, 107 (1956).
17. E. A. Gulbransen, Trans. Electrochem. Soc., 87, 589
(1945).
18. C. Wagner, This Journal, 1{}3, 571 (1956).
I9. R. M. B a r r e r , "Diffusion in a n d T h r o u g h Solids,"
C a m b r i d g e U n i v e r s i t y Press, p. 19 (1951).
20. R. D. G u m i n s k i and R. A. Hines, P r i v a t e communication.

Metallographic Manifestations of the Air Oxidation

of Tantalum at 7S0~
Robert Bakish1
Sprague Electric Company, North Adams, Massachusetts
ABSTRACT
The c r y s t a l l o g r a p h i c and s t r u c t u r a l factors i n v o l v e d in the air oxidation of
t a n t a l u m at 750~ are presented. The role of t h e {100} planes in the oxidation
process is discussed, a n d a t e n t a t i v e m e c h a n i s m for the conversion of m e t a l to
oxide u n d e r these conditions is proposed.
T h e o x i d a t i o n of T a h a s b e e n s t u d i e d b y a n u m b e r
of i n v e s t i g a t o r s w i t h e m p h a s i s on t h e t y p e a n d
s t r u c t u r e of t h e o x i d e f o r m e d ( 1 - 4 ) o r on t h e k i n e t ics of o x i d a t i o n ( 5 - 9 ) . W o r k on t h e s o l u b i l i t y of
o x y g e n in T a h a s also b e e n r e p o r t e d (10). I n a l l
t h e s e i n v e s t i g a t i o n s , t h e n a t u r e of t h e o x i d e - m e t a l
i n t e r f a c e h a s b e e n c o m p l e t e l y d i s r e g a r d e d , a n d no
m e n t i o n of t h e c r y s t a l l o g r a p h i c d e p e n d e n c e of t h e
tantalum oxygen reaction has been made.
P u r e T a ( T a 99.9 + F e 0.03 m a x a n d C 0.03 m a x )
supplied by Fansteel Metallurgical Corporation was
u s e d for t h i s i n v e s t i g a t i o n .

Experimental Procedure
I t h a s b e e n s h o w n t h a t t a n t a l u m o x i d e e x i s t s in
a s t a b l e m o d i f i c a t i o n i n t h e t e m p e r a t u r e r a n g e 650 ~
1300~ ( 3 ) . T h e t a n t a l u m o x i d e u s e d in t h e m o s t
recent structure determination was prepared by
1 P r e s e n t address:
Switzerland.

Ciba Limited, R a r e

Metals

Division, Basle,

o x i d a t i o n of t h e m e t a l a t 700~
( 4 ) . I n o r d e r to
avoid possible complications introduced by working
with an unknown oxide, an oxidation temperature
w a s s e l e c t e d on t h e b a s i s of t h e a b o v e r e f e r e n c e s .
A l l s p e c i m e n s in t h i s i n v e s t i g a t i o n w e r e s u b j e c t e d
to 4 5 - m i n o x i d a t i o n in a i r a t 750~
followed by
q u e n c h i n g in a i r a t r o o m t e m p e r a t u r e .
X - r a y p o w d e r t e c h n i q u e w a s u s e d to i d e n t i f y t h e
o x i d e f o r m e d . T h e s i n g l e c r y s t a l s u s e d in this s t u d y
were grown by standard strain anneal technique
and their orientations determined using Greninger's
m e t h o d (11). T h e i d e n t i f i c a t i o n of t h e p l a n e of
o x i d a t i o n w a s c a r r i e d o u t as f o l l o w s : t w o s u r f a c e s
w i t h k n o w n a n g u l a r r e l a t i o n s w e r e g r o u n d on c r y s t a l s of k n o w n o r i e n t a t i o n , a n d t h e a n g l e s m a d e b y
t h e p l a n e s of p r e f e r r e d o x i d a t i o n w i t h t h e c o m m o n
e d g e w e r e m e a s u r e d . This i n f o r m a t i o n w a s t h e n
plotted stereographically and analyzed using a
s t a n d a r d c u b i c p r o j e c t i o n , in a c c o r d a n c e w i t h
s t a n d a r d p r o c e d u r e s (12).

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72

JOURNAL

OF THE ELECTROCHEMICAL

SOCIETY

February 1958

S t a n d a r d m e t a l l o g r a p h i c techniques w e r e applied
in this study, and a solution consisting of H~SO4
( 9 6 % ) , HNO~ ( 7 0 % ) , a n d HF (48%) in ratio
(2: 1: 1) was used as the etching reagent.
In o x y g e n e m b r i t t l e d Ta, both i n t e r - and t r a n s c r y s t a l l i n e f r a c t u r e can be observed. I n t e r g r a n u l a r
failure is predominant in relatively small grain size
material (about 0.I ram). The oxide distribution on
grain surfaces obtained by fracturing small grained
metal were examined in order to gain additional
information regarding the sites of preferred oxidation. These observations were m a d e on freshly fractured wires without any subsequent surface preparation.

Experimental Results
A i r o x i d a t i o n of Ta leads to surface o x i d a t i o n and
c r y s t a l l o g r a p h i c a l l y d e p e n d e n t i n t e r n a l oxidation.
The l a t t e r proceeds at h i g h e r rates along c e r t a i n
p l a n e s and directions in t h e Ta lattice. The o x i d e m e t a l i n t e r f a c e in p o l y c r y s t a l l i n e Ta oxidized in air
at 750~ is shown in Fig. 1. Observe here the s u r face oxide a n d the s p e a r - l i k e o r i e n t a t i o n - d e p e n d e n t
p l a t e l e t s of the oxide. Note t h a t no p r e f e r e n t i a l
o x i d a t i o n exists at the g r a i n b o u n d a r y . This t y p e of
i n t e r f a c e is t y p i c a l of the l a r g e n u m b e r of o x i d e m e t a l interfaces e x a m i n e d a n d is unaffected by
l o n g e r o x i d a t i o n t r e a t m e n t s which o n l y moves this
i n t e r f a c e into the m e t a l .
X - r a y s t u d y by a p p l i c a t i o n of p o w d e r t e c h n i q u e
indicates t h a t the oxide f o r m e d u n d e r these conditions is Ta20~, of the same v a r i e t y as c o m m e r c i a l l y
p r o d u c e d m a t e r i a l of this formula. The s t r u c t u r e of
this o x i d e has r e c e n t l y been r e e v a l u a t e d (4). X - r a y
lines c h a r a c t e r i s t i c of t h e oxide p a t t e r n w e r e also
d e t e c t e d after r e m o v a l of the surface oxide in specimens which, by m e t a l l o g r a p h i c e x a m i n a t i o n , w e r e
shown to h a v e i n t e r n a l p r e f e r e n t i a l oxidation.
The oxide f o r m e d on p o l y c r y s t a l l i n e Ta is of v e r y
fine p a r t i c l e size, as i n d i c a t e d b y diffuse x - r a y p a t terns. This oxide has a high d e g r e e of p o r o s i t y
which can be d e t e c t e d on c a r e f u l microscopic e x a m i n a t i o n of the polished oxide. The same t y p e of
p o l y c r y s t a l l i n e oxide seems to be f o r m e d on single
c r y s t a l surfaces.
X - r a y analysis of the i n t e r n a l o x i d a t i o n occurring
in single crystals shows that, w i t h i n the a c c u r a c y

Fig. 1. Oxide metal interface, cross section normal to

oxidized surface. 2000X before reduction for publication,

Fig. 2. Details of early stage internal oxidation. 2000X

before reduction for publication.

of the m e a s u r e m e n t s of about 2 ~, the p l a n e s of i n t e r n a l o x i d a t i o n are p a r a l l e l to the (100) planes of

the bcc lattice. On successive l a p p i n g and polishing
of single c r y s t a l surfaces n o r m a l to the oxidized s u r face, and in s e v e r a l cases n o r m a l to the ~ 1 0 0 ~ d i rections, it was found t h a t q u i t e often the solid
p l a t e l e t profile of (100) p l a n e s was s u b s t i t u t e d at a
g r e a t e r d e p t h b y a b e a d profile a n d e v e n t u a l l y w i t h
discrete sites of oxidation. S e e Fig. 2 for t h e a p p e a r a n c e of (100} traces at some d e p t h f r o m t h e
oxide m e t a l interface. (Observe both " b e a d " p r o file and discrete o x i d a t i o n sites.) These oxide p l a t e lets do not grow a p p r e c i a b l y in thickness n o r m a l
to the {100) p l a n e s a f t e r t h e y reach a thickness of
about 0.002 m m (see Fig. 3). H e a v i e r o x i d a t i o n is
c h a r a c t e r i z e d b y the presence of a g r e a t e r n u m b e r
of m o r e n a r r o w l y spaced platelets. The porous
oxide is but a t h o r o u g h o x i d a t i o n of the v o l u m e of
the m e t a l b y o x i d a t i o n along {100} planes. F i g u r e 4,
which is a t a p e r section of an oxidized surface of a
single crystal, supports this contention. Observe t h e
islands of porous oxide, t h e high d e n s i t y of p l a t e lets in their i m m e d i a t e vicinity, and the r e l a t i v e l y
s m a l l e r d e n s i t y of p l a t e l e t s as the d i s t a n c e f r o m the
oxidized surface is increased. That this a p p e a r s to
be the n a t u r e of o x i d a t i o n seems to be also supp o r t e d by e x a m i n a t i o n of polished oxide surfaces

Fig. 3. Traces of the {100} planes. 2000X before reduction

for publication.

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Vol. 105, No. 2

AIR OXIDATION

OF TANTALUM

F,g. 4. Taper seclion of oxidized single crystal surface.

500X before reduction for publication.

A T 750~

73

Fig. 7. Fractograph showing sites of nucleation of oxygen

metal reaction on a grain surface. 500X before reduction for
publication.

in t h e {100} p l a n e s a r e t h e d i r e c t i o n s of p r e f e r r e d
oxidation.
I n a d d i t i o n to o x i d a t i o n w i t h i n t h e g r a i n s , e v i d e n c e of i n t e r n a l o x i d a t i o n w a s f o u n d on g r a i n s u r faces. This i n f o r m a t i o n w a s o b t a i n e d b y m i c r o scopic e x a m i n a t i o n of f r a c t u r e d , fine g r a i n e d , o x i dized Ta wire. Figure 7 shows a distribution typical
of t h o s e o b s e r v e d .
Discussion of Results

Fig. 5. Polished oxide surface (polarized light). 500X before

reduction for publication.

u n d e r p o l a r i z e d l i g h t (see Fig. 5). T h i s r e v e a l s a

fine s t r u c t u r e w i t h e l e m e n t s p a r a l l e l to t h e t r a c e s
of t h e {100} p l a n e s of t h e s u b s t r a t e .
A n o t h e r a s p e c t in w h i c h t h e c r y s t a l l o g r a p h i c d e p e n d e n c e of o x i d a t i o n m a n i f e s t s i t s e l f is t h e f o r m a t i o n of s t e p s b o u n d b y {100} s u b s t r a t e p l a n e s o n
t h e o x i d e - m e t a l i n t e r f a c e of s i n g l e c r y s t a l s . F i g u r e 6
s h o w s t h e a p p e a r a n c e of such a n i n t e r f a c e as v i e w e d
on a (112) p l a n e . W h e n such s i n g l e c r y s t a l s w e r e
s u b j e c t e d to o x i d a t i o n , it w a s p o s s i b l e to o b s e r v e
t h a t t h e < 1 0 0 > d i r e c t i o n s in t h e {100} p l a n e s w e r e
t h e d i r e c t i o n s of a h i g h e r r a t e of o x i d a t i o n . This
o b s e r v a t i o n a n d t h e o c c u r r e n c e of t h e {100} s t e p
f o r m a t i o n , t e n d to s h o w t h a t t h e ~ 1 0 0 ~ d i r e c t i o n s

T h e f i n d i n g s of t h i s i n v e s t i g a t i o n s h o w t h e p r e s e n c e of a set of h i g h a c t i v i t y p l a n e s in t h e (100}
p l a n e s of t h e T a l a t t i c e .
T w o a l t e r n a t i v e s a r e o f f e r e d as p o s s i b l e e x p l a n a tions of t h e h i g h a c t i v i t y of t h e {100} p l a n e s : it c a n
b e d u e e i t h e r to t h e i n h e r e n t h i g h a c t i v i t y of this
p l a n e ; o r it c a n b e t h e r e s u l t of t h e p r e s e n c e of
f a v o r a b l y o r i e n t e d i m p e r f e c t i o n s w h i c h c o u l d act as
short circuiting paths for diffusion and oxidation.
I t is on t h e s e i m p e r f e c t i o n s t h a t t h e m e t a l - o x i d e r e a c t i o n a p p e a r s to n u c l e a t e . No p r e f e r e n t i a l g r a i n
b o u n d a r y o x i d a t i o n w a s o b s e r v e d in this s t u d y . T h e
o x i d a t i o n p r o c e s s s e e m s to p r o c e e d b y n u c l e a t i o n of
o x i d a t i o n a t h i g h l y l o c a l i z e d sites a l o n g t h e t r a c e s
of t h e {100} p l a n e s , l e a d i n g to t h e g r o w t h of o x i d e
p l a t e l e t s p a r a l l e l to t h e {100} p l a n e s . T h e s e p l a t e l e t s
g r o w in t h i c k n e s s u n t i l t h e y r e a c h a b o u t 0.002 m m .
Further oxidation proceeds by nucleation and the
g r o w t h of a d d i t i o n a l p l a t e l e t s u n t i l a l l t h e m e t a l is
c o n s u m e d in t h e r e a c t i o n . T h e h i g h a c t i v i t y u s u a l l y
a s s o c i a t e d w i t h g r a i n b o u n d a r i e s in o x i d a t i o n r e a c t i o n s is n o t a p p a r e n t f r o m e x a m i n a t i o n of m e t a l o x i d e i n t e r f a c e s i n t h i s s t u d y . No s a t i s f a c t o r y e x p l a n a t i o n for t h i s b e h a v i o r c a n b e a d v a n c e d a t p r e s ent. O x i d e - m e t a l r e a c t i o n , h o w e v e r , w a s f o u n d to
n u c l e a t e at d i s c r e t e sites on g r a i n s u r f a c e s , a n d d i s c r e t e o x i d e p a r t i c l e s c a n b e seen on o b s e r v a t i o n of
t h e s e s u r f a c e s . T h e e x a c t n a t u r e of t h e sites w h i c h
act as n u c l e a t i n g c e n t e r s for t h e o x i d e - m e t a l r e a c t i o n is n o t k n o w n . T h e i r a p p e a r a n c e a n d d i s t r i butions suggest the possibility that they are dislocations. This, h o w e v e r , c a n n o t b e a s s e r t e d a t p r e s e n t .
Conclusions

Fig. 6. Crystallographic (100} steps on oxide metal interface plane of photomicrograph parallel to (112). 2000X before reduct,on for publication.

O n t h e b a s i s of this s t u d y , it is p r o p o s e d t h a t
o x i d a t i o n of T a p r o c e e d s b y p r e f e r e n t i a l o x i d a t i o n

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74

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OF THE ELECTROCHEMICAL

a l o n g t h e {100} p l a n e s i n t h e ~ 1 0 0 D d i r e c t i o n . T h e
c o m p l e t e c o n v e r s i o n of the m e t a l to o x i d e is effected
b y the n u c l e a t i o n a n d g r o w t h of {100} plates, w h i c h
e v e n t u a l l y fill t h e v o l u m e of the m e t a l . T h e i n d i v i d u a l plates do n o t exceed 0.002 m m i n t h i c k n e s s .
O n e x a m i n a t i o n of t a p e r e d sections, t h e Ta~O~
shows c l e a r l y the c r y s t a l l o g r a p h i c d e p e n d e n c e of its
g r o w t h process a n d the o r i e n t a t i o n of t h e traces of
t h e {i00} p l a n e s of t h e s u b s t r a t e . L a t t i c e i m p e r f e c tions, b e l i e v e d to b e dislocations, s e e m to act as sites
for t h e n u c l e a t i o n of t h e m e t a l - o x i d e reaction.

Acknowledgment
T h e a u t h o r w i s h e s 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 D. Rogers a n d N. H a r v i n i n the course of this
work. T h a n k s are also d u e to W. B e r n a r d for r e a d i n g the m a n u s c r i p t .
Manuscript received A p r i l 22, 1957. This paper was
p r e p a r e d for delivery before the Buffalo Meeting, Oct.
6-10, 1957.

SOCIETY

F e b r u a r y 1958

A n y discussion of this paper will appear in a Discussion Section to be published in the December 1958
JOURNAL.
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1. G. Brauer, Z. anorg, u. allgem. Chem., 248, 1 (1941).
2. S. Lagergren and A. Magneli, Acta. Chem. Scand.,
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4. L. K. F r e v e l and H. W. Rinn, Anal. Chem., 27, 1329
(1955).
5. E. G u l b r a n s e n a n d K. F. Andrews, This Journal, 99,
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6. E. G u l b r a n s e n and K. F. Andrews, Trans. Am. Inst.
Mining Met. Engrs., 186, 586 (1950).
7. R. C. Petersen, et al., ibid., 200, 1038 (1954).
8. J. T. Waber, J. Chem. Phys., 20, 734 (1952).
9. J. T. Waber, et al., This Journal, 99, 121 (1952).
10. E. G e b h a r d t and H. Preisendanz, Plansee Proceedings, 254 (I956).
11. A. B. Greninger, Trans. Am. Inst. Mining Met.
Engrs., 17, 61 (1935).
12. C. S. Barrett, S t r u c t u r e of Metals, 40 (1952).

Cathodic Reduction of Oxide Films on Iron

II.

Determinationof a-FeO and FeO

K. H. Buob, A. F. Beck, and M. Cohen

National Research Council, Ottawa, Ontario, Canada

ABSTRACT
A study of the cathodic reduction of a-Fe~O~ on iron has been made with
the object of using the technique for the accurate d e t e r m i n a t i o n of both the
a-Fe~O~ and Fe~O4 formed d u r i n g the oxidation of iron. The films were exa m i n e d after oxidation a n d after various stages of cathodic reduction. Exa m i n a t i o n was made b y weight change, electron diffraction, x-ray diffraction,
and chemical analysis of the films. Some evidence for the existence of a t h i n
layer of ~-Fe~O~ b e t w e e n the layers of Fe~O~ and a-Fe~O~ was found. A standard
p a t t e r n for Fe:~O4 was obtained.

W h e n F e is oxidized i n o x y g e n at t e m p e r a t u r e s u p
to a b o u t 450~ a d u p l e x film of Fe~O4 n e x t to t h e
m e t a l a n d a-Fe~O~ is f o r m e d . T h e o v e r - a l l g r o w t h
of the oxide film s h o u l d be r e l a t e d to the r a t e s of
g r o w t h of these two layers. I n a p r e v i o u s p a p e r (1)
t h e r e w a s d e s c r i b e d a t e c h n i q u e for the cathodic r e d u c t i o n of a-FelOn. I n this p a p e r the a p p l i c a t i o n of
this t e c h n i q u e to t h e d e t e r m i n a t i o n of a-Fe~O~ a n d
Fe~O4 is described.

To check on the v a l i d i t y of this m e t h o d , reflection

e l e c t r o n d i f f r a c t i o n i d e n t i f i c a t i o n of the oxide w a s
m a d e d u r i n g v a r i o u s stages of the cathodic r e d u c t i o n process. F i l m s w e r e s t r i p p e d for i d e n t i f i c a t i o n
by both diffraction and chemical analysis, and the
effect of cathodic r e d u c t i o n on m a g n e t i t e films w a s
determined.

T h e m e t h o d p r o p o s e d was to w e i g h t h e oxidized
s p e c i m e n a n d to r e d u c e it c a t h o d i c a l l y u n t i l t h e p o t e n t i a l of t h e F e i n d i c a t e d a c h a n g e i n the cathodic
process. T h e s p e c i m e n was r e w e i g h e d a n d the Fe~O~
d e t e r m i n e d b y difference. T h e Fe~O, w a s c a l c u l a t e d
f r o m the t o t a l w e i g h t g a i n e d a n d the w e i g h t of
FelOn.

m e n s m e a s u r i n g 5 x 1 cm w i t h a h a n d l e 2.5 x 0.2 cm
w e r e cut f r o m r o l l e d A r m c o I r o n sheet 0.150 m m
thick. T h e F e c o n t a i n e d 0.113% t o t a l i m p u r i t i e s .
The specimens were degreased in benzene, wiped
d r y w i t h K l e e n e x , stored i n a desiccator for 1 hr,
a n d w e i g h e d o n a m i c r o b a l a n c e to x 10 4 g. T h e y
w e r e t h e n s u p p o r t e d i n a q u a r t z t u b e over w h i c h a

Experimental
Preparation of oxidized s p e c i m e n s . - - T h e speci-

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