The Oxidation of Niobium in the Temperature Range

450~176
J. S. Sheasby
Faculty of Engineering Science, The University of Western Ontario, London, Ontario, Canada

ABSTRACT
The oxidation properties of n i o b i u m were studied i n the t e m p e r a t u r e r a n g e
450~176
at oxygen pressures 1-760 Torr. P a r t i c u l a r emphasis was placed
on correlating the morphology of the reaction products with the oxidation
kinetics. During the initial, approximately parabolic oxidation period the
scale appears compact, and at the transition from parabolic to l i n e a r kinetics
the scale blisters and cracks. Scale formed d u r i n g l i n e a r oxidation grows i n a
series of crude layers. F r o m the relationships d e t e r m i n e d b e t w e e n the rate
of oxidation and the thickness of the oxide layers, it is deduced that the rate
of oxidation is controlled at all times by the diffusional properties of the
oxide layer in contact ,with the metal phase. The sensitivity of the rate of oxidation to oxygen pressure is ascribed to the pressure sensitivity of the u n d e r lying parabolic rate constant of formation of the n i o b i u m pentoxide, and to a
lesser extent to changes in the width of the oxide layers with the rate of
their formation. The inversion in the t e m p e r a t u r e coefficient of the oxidation
reaction as the t e m p e r a t u r e is lowered from 625~176
is associated with the
disappearance of layers of NbO and NbO2 from the reaction zone and the
appearance of a metastable platelet phase.

The oxidation behavior of n i o b i u m has been studied

b y m a n y workers, a n d the l i t e r a t u r e was reviewed
most recently by Seybolt (1). Niobium exhibits u n usual oxidation features, for at each t e m p e r a t u r e and
oxidation pressure the oxidation rate is found to follow a complex series of time laws. This paper describes
an investigation into the oxidation behavior of niob i u m in the t e m p e r a t u r e r a n g e 450~176
at oxygen
pressures n e a r atmospheric, for times from 2 m i n to
several hours. At times shorter than this, or for the
e q u i v a l e n t oxygen uptake at lower pressures, H u r l e n
(2) reports that the oxygen rate is time independent.
At reaction times longer than several hours a second
b r e a k a w a y reaction has been reported by Kolski (3)
and b y McLintock a n d Stringer (4).
The field u n d e r study is characterized b y a time
i n d e p e n d e n t rate (linear reaction rate law), which is
u s u a l l y preceeded by a short period of a p p r o x i m a t e l y
parabolic behavior. The linear reaction rate is pressure-sensitive and also decreases i n m a g n i t u d e as the
t e m p e r a t u r e is increased from 600 ~ to 625~ The m a jor part of the weight gain is associated with the form a t i o n of n i o b i u m - p e n t o x i d e although oxygen is also
consumed by the formation of lower or suboxides and
b y solution i n the m e t a l phase. Whereas there is good
a g r e e m e n t b e t w e e n previous studies on the rates of
oxidation and types of time laws observed at various
oxidation conditions, there is no agreement as to the
physical events and the n a t u r e of the rate controlling
steps associated with each stage. P a r t i c u l a r areas of
disagreement are: (i) the reaction products formed
d u r i n g parabolic oxidation, and the rate controlling
step; (ii) the m e c h a n i s m of the t r a n s i t i o n from p a r a bolic to linear oxidation kinetics; (iii) the r a t e - c o n trolling step d u r i n g l i n e a r oxidation; (iv) the mechanism of the rate inversion at 600~
Previous workers (2, 4, 5) have considered the high
pressure sensitivity of the oxidation rate and the
linear oxidation kinetics indicative of e q u i l i b r i u m
oxygen adsorption at an interface, followed by a phase
b o u n d a r y controlled reaction. However, Sheasby, W a l l work, and Smeltzer (6) have recently shown that in
the t e m p e r a t u r e r a n g e 720~176
the n i o b i u m p e n t oxide scale grows protectively, a n d that the parabolic
rate constant of its formation is pressure sensitive,
thus p e r m i t t i n g the pressure sensitive linear oxidation
kinetics to be rate controlled b y a b a r r i e r film mech-

anism. This paper describes the results of an investigation into this possibility.

Experimental
Specimens were cut in the form of squares approxi m a t e l y 1.1 cm 2 f r o m sheet 1 m m thick produced by
Fansteel. The specimens were prepared for oxidation
b y abrasion up to 600 grade silicon carbide paper, followed by electropolishing for 30 sec in a nitric acid
--30% hydrofluoric acid electrolyte at 24v using a
carbon cathode.
The kinetics of oxidation were e x a m i n e d using a
volumetric apparatus. E x p e r i m e n t a l r u n s were i n i t i ated by a d m i t t i n g oxygen to a specimen brought to
t e m p e r a t u r e u n d e r vacuum. Previous estimates of
specimen self-heating for this procedure gave a n
initial rise above the furnace t e m p e r a t u r e of about
30~ The specimens t h e n cooled to a steady value in
about 4 m i n to about 2~176 above the furnace t e m perature. For most of the experiments an oxygen
pressure of 380 Torr was used, and at this pressure a
1 cm m o v e m e n t of the m e r c u r y bead corresponds to
an oxygen u p t a k e of a p p r o x i m a t e l y 1.4 x 10 -5 g / c m 2.
At least two runs were made at each temperature, a n d
the rate constants so d e t e r m i n e d u s u a l l y agreed to
better t h a n 10%. After oxidation all the specimens
were e x a m i n e d metallographically. To obtain m i n i m u m loss of oxide the specimens were plunged while
still hot into c o l d - m o u n t i n g compound.

Experimental Results
Kinetic res~lts.---A series of specimens was oxidized at 380 Torr at a p p r o x i m a t e l y 25~ intervals over
the t e m p e r a t u r e r a n g e 450~176
to a weight gain of
about 0.01 g / c m 2. F u r t h e r specimens were oxidized
as r e q u i r e d for specific times, temperatures, and oxygen pressures.
A typical weight gain curve in which initial protective behavior breaks away to a t i m e - i n d e p e n d e n t
reaction rate is shown in Fig. 1. A plot of (weight
gain) 2 vs. time for the protective period gives a good
fit to a straight line intersecting the time axis close
to the origin. The weight gain curves for the series of
specimens oxidized at 380 T o r t w e r e analyzed for
values of the reaction rate constants Kpv and Klv.
Where Kpv, the parabolic reaction rate constant, and
Klv, the l i n e a r reaction rate constant, are defined by
695

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696

J. Electroche~n. Soc.:

ELECTROCHEMICAL SCIENCE

July 1968

20
720~

IO

7 5 0 m m Hg.

16

x
"

Kp v Volumetric
Kp 9 KI. X Wc

=~

z
<[

jU

(~ 8
v:c

~4

/;

. . . . .
IO

20

30

40

TIME

rains

50

,o

G'0

e
1"O

Fig. 1. Oxidation of niobium at 720~

I'1

~o ~
1'2

1"3

.~
1"4

I O 3 / TOK

750 Torr

Fig. 4. Dependence of the derived and measured parabolic rate

constants of oxidation of niobium at 380 Torr on temperature.

the equations
w ~ = Kpvt + a

rate constant Kp~ are shown in Fig. 4. No other values

have been reported for these reaction conditions.

w = Klvt + b

respectively; w is the weight of oxygen absorbed at

time t, and a and b are reaction constants.
It was found that below a p p r o x i m a t e l y 610~ the
protective period is too short to obtain a parabolic
rate constant, and below 550~
after the initial deviations of a p p r o x i m a t e l y 10-rain duration, the reaction rate tends to decrease slowly as oxidation proceeds, Fig. 2. This latter behavior has been reported
previously b y A y l m o r e et al. (7) a n d b y Cox and
J o h n s t o n (8) a n d will be discussed later. Values of
the linear rate constant K/v agree well with previous
investigations (Fig. 3), and in particular a decrease in
reaction rate is noted as the oxidation t e m p e r a t u r e is
increased from 600 ~ to 622~ Values of the parabolic

8
x

'j/jj

/ //

Metallographic
results.--The
principal reaction
product i n the r a n g e 10-760 T o r t 450~176
is ~ - n i obium pentoxide as designated b y Terao (9). Layers
of NbO and NbO2 are present at the metal surface on
specimens reacted above 620~
Below 600~ these
oxides are absent and are replaced by a platelet phase
t e n t a t i v e l y identified as the suboxide NbOz as design a t e d b y N o r m a n (10). The appearance or n o n a p p e a r ance of the e q u i l i b r i u m d i a g r a m oxides NbO a n d
NbO2 depends on the time, t e m p e r a t u r e , a n d pressure
of oxidation, and also on the local radius of c u r v a ture of the m e t a l - o x i d e interface. For instance, as
shown i n Fig. 5, for a specimen reacted at 626~ in
380 Torr oxygen, NbO and NbOs are stable on the
m a i n faces of the specimen, b u t not at the specimen
corners. The reaction conditions necessary for the formation of NbO and NbO2 are the subject of a c u r r e n t
study and will be reported later.
I n cross section the n i o b i u m pentoxide layer tends to
be thicker at specimen corners a n d edges t h a n on the

.~/

, ~

/ .~'is
7./
x/

2'o

~o

;o

TIME

(rain.)

~o

Fig. 2. Oxidation of niobium at 520~

curve B, 380 Torr; curve C, 150 Torr.

,;0

120

Curve A, 760 Torr;

X SHEASBY
9 KOFSTAD
& COX

iO"~=

r
o
&

~ld 8
7oo'c
I
1"O

6oo%
I
I'.1

112

11~3

1"4

IO3/T(~

Fig. 3. Dependence of the linear rate of oxidation of niobium

at 380 Torr on temperature. X This investigation, interpolated
values of 9 Kofstad et al. (1.3), a,d a Cox et al. (7),

Fig. 5. Cross section of specimen oxidized at 380 Torr, 626~

for 65 rain., showing abnormal edge effect. Magnification A
(top) ca. i00X, B (bottom) ca. 525X.

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Vol. 115, No. 7

OXIDATION

OF NIOBIUM

F R O M 450~176

697

Fig. 6. Cross section of specimen oxidized at 380 Torr, 575~

for 32.5 min, showing normal edge effect. Magnification 125X.

m a i n faces (Fig. 6), thus p r e v e n t i n g too literal an

i n t e r p r e t a t i o n of the reaction rate constants measured
b y the v o l u m e t r i c apparatus. The n i o b i u m - p e n t o x i d e
layer on all the specimens contains lenticular fissures
parallel to the metal surface giving the scale a l a m i n a r appearance. W h e n the scale is formed from niob i u m containing platelets these fissures or pores tend
to be aligned, r u n n i n g at an angle of about 60 ~ to
the metal surface and occurring i n pairs to give a
chevron p a t t e r n superimposed on the l a m i n a t i o n s
(Fig. 7). This chevron p a t t e r n of pores p r o b a b l y has
the same origin as the similar structure in t a n t a l u m
iaentoxide scales described and discussed b y S t r i n g e r
(11).
L a m i n a t i o n s in n i o b i u m pentoxide scale layers
formed from NbO a n d NbO2 are thicker t h a n those
formed from n i o b i u m c o n t a i n i n g platelets. L o w e r i n g
the oxidation pressure or raising the t e m p e r a t u r e
tends to increase the thickness of these laminations
so that above 725~ the oxide is not layered (6). W h e n
viewed in polarized light the oxide scales formed
at the higher t e m p e r a t u r e s are seen to be composed of c o l u m n a r crystals with the long axis n o r m a l
to t h e plane of the laminations, Fig. 8d. Similar structures have been observed in scales formed at lower
temperatures, b u t in general the layer widths and
oxide grain size are too small to m a k e observation
possible. The c o l u m n a r grains are continuous over
m a n y laminations, indicating that w h e n the oxide
layered r e n u c l e a t i o n of oxide crystals was not necessary. I n fact, in only r a r e instances in the several
h u n d r e d specimens examined, has a structure been
observed i n which n e w oxide grains appear to have
nucleated b e n e a t h a pore.
Several series of specimens were oxidized for v a r i ous lengths of time at specific t e m p e r a t u r e s and oxygen pressures. Photomicrographs of one such series
oxidized at 720~ in oxygen at 750 Torr for times of
13, 28, 68, and 100 rain are shown in Fig. 8 ( a - d ) , a n d
the associated weight gain curve in Fig. 1. The scale
is black d u r i n g the period of the first parabola and i n
cross section appears compact, Fig. 8a. Deviation from
the parabola is accompanied b y the appearance of

Fig. 7. Cross section of specimen oxidized at 750 Torr, 600~

for 120 min, showing chevron markings superimposed on the laminations. Magnification 100X.

Fig. 8. Cross sections of specimens oxidized at 720~ 760 Torr:

a, 13 min; b, 28 rain; c, 68 min; d, 100 min. Polarized light.
Magnifications 75X.

yellow blisters on the scale, which i n cross section are

seen to be regions w h e r e the scale has become detached from the metal a n d reacted with oxygen to
become stoichiometric, Fig. 8b. It is to be noted that
the pores act as barriers to f u r t h e r oxidation, a n d t h a t
u n t i l the oxide cracks b e t w e e n the blisters a second
layer does not form. G r o w t h of the n e w coherent layer
continues u n t i l it in t u r n blisters, a n d the cycle r e peats. The first two of three layers often form sufficiently in phase to be evident i n the kinetic curves.
Later, all traces of u n e v e n n e s s are lost and the reaction rate is linear.
Other series reacted at lower t e m p e r a t u r e s showed
similar relationships b e t w e e n the morphology of the
reaction product and the associated weight gain curve.
However, below 600~ the shortness of the period of
initial n o n l i n e a r behavior, combined with the u n c e r tainties introduced b y the t e c h n i q u e of starting the
reaction and overheating of the specimen w h e n first
introduced to oxygen, p r e v e n t s q u a n t i t a t i v e analysis

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J. Electrochem. Soc.: E L E C T R O C H E M I C A L

698

of either the volumetric or the metallographic m e a surements.

Analysis.--Because of the correlation b e t w e e n

the morphology of the oxide scale with the variations
i n the w e i g h t - g a i n curve it is proposed that this oxidation reaction is an excellent example of the class
of oxidation reactions k n o w n as "paralinear." The
layered oxide scale emanates from the growth of the
oxide to a critical thickness, cracking, and regrowth.
Throughout this cycle the rate of reaction is controlled
by diffusion across the l a y e r of oxide that is in the
process of growing.
The c o l u m n a r g r a i n structure of the layered oxide
indicates that there is no pause in the oxidation reaction associated with the nucleation of n e w oxide layers, On the other hand, the layer of oxide in contact
with the m e t a l phase was not observed to be significantly thicker than the other layers, though cooling
cracks make this observation less certain. It follows
t h a t the l i n e a r oxidation rate Klo should be related b y
the m e a n layer w i d t h Wc to the u n d e r l y i n g parabolic
rate constant Kp for the reaction (12), according to
the equation
Kp = K~o x Wc
This parabolic rate constant should have the same
value as that of the parabolic oxidation at the start
of the reaction as m e a s u r e d either by the volumetric
apparatus (Kp,) or metallographically. F u r t h e r m o r e ,
e v e n though the local l i n e a r rate constants KIo and
l a m i n a t i o n thicknesses as d e t e r m i n e d m e t a l l o g r a p h i cally can v a r y from point to point on a specimen, the
parabolic rate constant derived using the equation
above should h a v e the same value.
Measurements of the w i d t h of l a m i n a t i o n s i n the
n i o b i u m pentoxide scale were made at several points
on all specimens. It must be emphasized that p a r t i c u l a r l y at the lower t e m p e r a t u r e s the scale layers are
not clearly defined m a k i n g it e x t r e m e l y difficult to
measure We with a n y accuracy. D e t e r m i n a t i o n s from
the specimen shown i n Fig. 6 are given in Table I
where it can be seen that the derived parabolic rate
constants t e n d to increase as the local linear rate
constant increases. The higher values are associated
with the curved regions of the specimen and could
have been caused by two effects. First, the scale could
have cracked closer to the m e t a l at these points, and
second, m e a s u r e m e n t s m a d e at 750~ showed that the
parabolic rate constant of oxidation on a convex
metal surface could be enhanced 30% above that on
a flat surface. A p a r t from sites of more e x t r e m e edge
oxidation, values of K p derived from metallographic
m e a s u r e m e n t s t a k e n from a r o u n d a specimen g e n e r ally agreed to within 30% of a m e a n value. The derived parabolic rate constants of all the specimens reacted at 360 Torr as a function of (1/T~
are shown
in Fig. 4. Two lines c a n be d r a w n on this plot, the
h i g h - t e m p e r a t u r e line corresponding to specimens
with layers of NbO, a n d the l o w - t e m p e r a t u r e line to
specimens w i t h platelets. The data points at about
610~
b e t w e e n the two lines, were obtained from
specimens in which platelets formed initially, and only
later i n the reaction did a l a y e r of NbO stabilize. I n
Table I. Scale measurements on a specimen oxidized at 575~
at an oxygen pressure of 380 Tarr for 32.5 rnin. Linear reaction
rate as determined volumetrically, KIv, 5.16 x 10 - 6 g.cm2/sec

No. of layers

19
25
30
34
43
50
63
111

Layer thickhess Wc,/~

2.4
2.2
2.2
2.1
1.9
1.9
1.7

1.8

Local linear rate

of oxidation, KI
g/crn'~/sec

3.6
4.4
5.2
5.8
6.7
7.4
8.3

x 1 0 -~
x 10-~
x 10 -~
x 10 -6
x 10 -~
x 10-~
x lO-e
1 X 10 -6

Parabolic rate constant

Kp = Kl Wc X 1.56
ge/cm4/sec

1.4
1.5
1.7
1.9
2.0
2.2
2.2
4.4

x
x
x
x
x
x

10-s
10-s
10 -s
l0 s
1 0 -s
1 0 -8
l O -s
1 0 -s

SCIENCE

J u l y 1968

certain specimens this dual oxidation behavior persisted to the end of the run, Fig. 5, a n d values of Kp
could be t a k e n corresponding to the two extremes.
Discussion

F r o m the morphological and kinetic evidence presented the oxidation behavior of n i o b i u m i n the temp e r a t u r e r a n g e 450~176
and pressure range 1-760
Torr agrees both q u a l i t a t i v e l y a n d q u a n t i t a t i v e l y with
a "repeated-parabolic" or " p a r a l i n e a r " scaling model.
Differences in scaling behavior as the t e m p e r a t u r e is
lowered are to a large extent caused by a decreased
plasticity of the oxide. Above about 750~ the oxide
does not layer, and consequently the o v e r - a l l reaction rate is essentially parabolic (6). At an oxygen
pressure of 380 Torr at 720~ the oxide grows protectively to a thickness of about 40~, and as the t e m p e r ature is lowered to 625~ the protective thickness is
reduced to about 13~. Below 600~ the ini,tial oxide
grows to a thickness of only a few microns before
failing, possibly because the platelets promote cracking. D u r i n g this period of oxidation the n i o b i u m pe.ntoxide scale layer is growing by a m e c h a n i s m in which
oxygen is the p r e d o m i n a t e diffusing species. This is
evidenced by the sustained appearance of polishing defects from the initial p r e p a r a t i o n on the free oxide
surface. Calculations show that in this phase of the
reaction less t h a n 5% of the weight gain of a specim e n is associated with oxygen solution in the m e t a l
phase and the formation of sub or lower oxides. This
value decreases as the reaction proceeds.
After the onset of scale l a y e r i n g the reaction rate is
observed to be essentially linear. The excellent agreem e n t b e t w e e n the measured and calculated parabolic
rate constants above 625~ Fig. 4. confirms that the
rate of oxidation u n d e r these conditions is controlled
by the transport properties of the layer of oxide in
contact with the m e t a l phase. That is, the linear rate
of oxidation is not due to phase b o u n d a r y control, but
is the result of a repeated parabolic process. Below
625~ such direct confirmation of the oxidation m e c h anism is not available. However, the correlation of the
metallographic observations with inflections in the rate
curve, and the analysis of the enhanced oxidation at
specimen corners strongly supports the continued operation of a p a r a l i n e a r mechanism. There are no values
in the l i t e r a t u r e with which these calculated parabolic
rate constants can be directly compared, although they
appear to be a p p r o x i m a t e l y one order of m a g n i t u d e
faster t h a n those of G u l b r a n s e n and A n d r e w (13). It
is noted that below 625~ the oxides NbO a n d NbO2
are not present at the metal oxide interface as r e quired in their description of the oxidation reaction
by Cox and J o h n s t o n (8), b y Inouye (14), and b y
B l a c k b u r n (15).
The initial parabolic rate constants are k n o w n to
be sensitive to the oxidizing pressure (6). Further, it
has been observed both in this s t u d y and that of Kofstad and Kjollesdal (16), that the thickness of scale
laminations tends to increase as the oxidation pressure
is reduced. Hence the variation of both the l i n e a r rate
of reaction and the calculated parabolic rate is considered to e m a n a t e from these causes a n d not as a
result of phase b o u n d a r y control.
At t e m p e r a t u r e s below 550~
at some time well
after breakway, the rates of reaction tend to change
slowly to lower values. For example, in Fig. 2B, the
rate of reaction of a specimen reacted at 520~ at 380
Torr after 120 m i n has fallen to 0.6 that of the rate at
20 rain. This behavior has been reported previously
(7), and was considered to be due to a t h i c k e n i n g of
the b a r r i e r film. This could occur in two ways; the
average l a m i n a t i o n thickness Wc could increase, or the
l a m i n a t i o n thickness could r e m a i n constant b u t the
point at which a n e w l a m i n a t i o n forms could move
f u r t h e r from the metal-oxide interface. E x a m i n a t i o n
of oxidized specimens showed no evidence of a change
in l a m i n a t i o n w i d t h greater t h a n 0.85, whereas a
change of 0.6 is r e q u i r e d for the first mechanism. The

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Vol. 115, No. ?

OXIDATION

OF

NIOBIUM

second m e c h a n i s m requires the l a m i n a t i o n of oxide

adjacent to the specimen to be up to 1.3 times thicker
t h a n the average. However, the l a m i n a t e d structure
is not sufficiently well defined, p a r t i c u l a r l y n e a r the
m e t a l - o x i d e interface where cooling effects are most
disruptive, for such a j u d g m e n t to be made. A n alternative m e c h a n i s m is proposed by Cox and J o h n s t o n
(8) to explain this reduction i n rate, in which the
reaction is p a r t i a l l y stifled b y restriction of the gas
flow due to the growth of the porous outer scale. In
growing the porous structure is altered so that the
restriction the scale presents to the gas attains a l i m i t ing value. S u b s e q u e n t oxidation would t h e n obey a
linear rate law and show a n almost linear dependence
of the rate on gas pressure. A central feature of t h e i r
a r g u m e n t s is that the pressure sensitivity of the reaction is a consequence of the porous plug character of
the scale, and not due to s u b s e q u e n t phase b o u n d a r y
or t r a n s p o r t steps. However, it can be seen in Fig. 2,
that oxidation is pressure sensitive from the start of
reaction, that is before a porous plug has been
formed. Hence it is considered that resistance to oxidation caused by the detached scale l a m i n a t i o n s is
only of secondary importance.
One of the most p r o m i n e n t characteristics of the
oxidation behavior of n i o b i u m is the decrease in reaction rate of specimens as the t e m p e r a t u r e is i n creased from 600~176
This behavior is most evident i n the values of the derived parabolic rate constant, where association with the lower t e m p e r a t u r e
line correlates with platelets in the specimen, and
association with the h i g h - t e m p e r a t u r e line correlates
with NbO (and p r o b a b l y NbO2) at the m e t a l - o x i d e
interface. The platelet phase has been considered in
some detail by Cox and Sheasby (17), concluding that
the platelets are a metastable phase, and that they
form d u r i n g reaction and not while the specimen is
being cooled to room temperature. These conclusions
are based on the following arguments.
1. Norman, Kofstad, a n d K r u d t a a (18) noted that
platelets only form from supersaturated solutions of
oxygen in niobium, and they could not prepare an
oxide with the same structure as the platelets by
m e l t i n g together the appropriate quantities of metal
and pentoxide.
2. On certain specimens reacted just above 600~
it is possible for platelets to form at one point on a
specimen and for layers of NbO and NbO2 to form at
another. The n i o b i u m pentoxide scale formed above
the platelet phase is always much thicker t h a n that
formed above the layers of lower oxides. Typical m i crohardness traces b e n e a t h two such regions are
shown in Fig. 9. Theoretical diffusion gradients were
i

]
i
i
i
630"C 750mm Hg.
-- - ??:'n:nder

NbO

37p
400 \ \
HARDNESS \ \
D.P.N.
T
300

--G

450~176

699

Fig. 10. Taper section of niobium oxidized at 600~ at an oxygen pressure of 750 Torr for 60 min, showing a band of platelets
in the metal phase; taper ratio approx. 10:1. Magnification 250X.

calculated assuming a linear rate of interface motion,

v a r y i n g only the hardness value corresponding to the
oxygen concentration at the metal-oxide interface to
optimize the fit to the e x p e r i m e n t a l points. As NbO is
the stable phase, the hardness of the metal in contact
with it, i.e., at zero depth on the b r o k e n curve, corresponds to the e q u i l i b r i u m level of saturation of oxygen in niobium. The hardness value u n d e r the platelet
phase extrapolates to a higher hardness v a l u e at the
surface, i n d i c a t i n g that the m e t a l is supersaturated
with oxygen in this region. As platelets are only found
w i t h i n the supersaturated zone they are a metastable
phase.
3. Platelets have n e v e r been observed b e n e a t h a
continuous l a y e r of NbO.
4. If platelets are present at the end of oxidation,
traces of their previous existence in the metal, as described by S t r i n g e r (11) for oxidized t a n t a l u m , are
observable in the layered n i o b i u m - p e n t o x i d e . Further,
p a r t i c u l a r l y in taper sections, it often appears that
the center of single platelets has been consumed by
the advancing m e t a l - o x i d e interface, Fig. 10. It is i m probable that platelets n u c l e a t i n g i n d e p e n d e n t l y d u r ing cooling would so often l i n e u p with each other on
either side of a region of pentoxide.
The presence of platelets in the reaction zone can
therefore be t a k e n as evidence that the metal is
supersaturated with oxygen with respect to NbO, the
n e x t stable phase on the e q u i l i b r i u m diagram. It follows that in these circumstances the n i o b i u m - p e n t o x i d e
adjacent to the metal phase will be supersaturated
with niobium. The oxidation rate has been shown to
be controlled by the diffusional properties of the
n i o b i u m - p e n t o x i d e layer in contact w i t h the m e t a l
phase. Hence it is proposed that the increase in oxidation rate observed above the platelet phase is due to
the enhanced oxygen concentration gradient present in
the n i o b i u m - p e n t o x i d e u n d e r these conditions.

Nb205

Under platelets

175,u Nb205

\ ~ \
~ \ \

FROM

Acknowledgments

The author is grateful to Mr. E. K o h n for his assistance with the e x p e r i m e n t a l work. The research was
supported by the National Research Council of Canada
a n d The U n i v e r s i t y of W e s t e r n Ontario.
Manuscript received Feb. 16, 1968..

\\

A n y discussion of this paper will appear in a Discussion Section to be published in the J u n e 1969 JOURNAL.

200

| (~- ~

20

DEPTH JJ

REFERENCES
A. U. Seybolt, Advances in Physics, 12, 1 (1963).
T. Hurlen, J. Inst. Metals, 89, 273 (1960-61).
T. L. Kolski, Trans. ASM, 55, 119 (1962).
C. H. McLintock and J. Stringer, J. Less Com~non
Metals, 2, 233 (1960).
5. D. W. Bridges a n d W. M. Fassell, This Journal, 103,
326 (1956).
6. J. S. Sheasby, G. R. W a l l w o r k and W. W. Smeltzer,
ibid., 113, 1225 (1966).

1.
2.
3.
4.
60

Fig. 9. Microbordness gradients under two different regions of

the same specimen.

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700

J. Electrochem. Soc.: E L E C T R O C H E M I C A L

7. D. W. Aylmore, S. J. Gregg, a n d W. B. Jepson,

ibid., 107, 495 (1960).
8. B. Cox and T. Johnston, Trans. Met. Soc. AIME,
227, 36 (1963).
9. N. Terao, Japan, J. Appl. Physics, 2, 156 (1963).
1O. N. Norman, J. Less Common Metals, 4, 52 (1962).
11. J. Stringer, ibid., 11, 111 (1966).
12. J. Stringer, Met. Rev., 11, 113 (1966).
13. E. A. G u l b r a n s e n a n d K. F. A n d r e w , This JournaL,
105, 4 (1955).

SCIENCE

J u l y 1968

14. H. Inouye, " C o l u m b i u m Metallurgy," p. 649, Metals

Society, AIME, Conf. 1960.
15. P. E. Blackburn, This Journal, 109, 1142 (1962).
16. P. Kofstad a n d H. Kjollesdal, Trans. Met. Soc.
AIME, 221, 285 (1961).
17. G. W. Cox, Ph.D. Thesis, U n i v e r s i t y of N.S.W.
(1963).
18. N. Norman, P. Kofstad, a n d O. J. K r u d t a a , J. Less
Common Metals, 4, 124 (1962).

Insulator-Induced Conduction
Jerry M. Cantril and H. A. Pohl*
Department o$ Physics, Oklahoma State University, Stillwater, Oklahoma
ABSTRACT
The presence of i n s u l a t i n g particles, even those of higher resistivity t h a n
the liquid, was found to increase electrical conduction in several dielectrical
liquids. We believe this to be a general effect which will occur if the particles have a higher dielectric constant t h a n the liquid. I n particular, we observed i n several highly purified liquids (C C14 and toluene) that the c u r r e n t
conducted across a cylindrical electrode system was considerably e n h a n c e d
w h e n highly purified solids (e.g., p o l y v i n y l chloride, quartz, or sulfur) were
held against the smaller i n n e r electrode by dielectrophoretic force. A theory
for the effect is given. It emphasizes the effect of local field concentration
(field-focussing) by the particles. This "focussing" of the field in the liquid
acts to enhance carrier concentration and conduction since the conduction is i n
the n o n o h m i c space-charge-limited regime.
Solid particles with a dielectric polarization higher
t h a n that of the s u r r o u n d i n g liquid m e d i u m are pulled
dielectrophoretically into regions of highest field
strength. This effect has been used to accomplish
separations of solid particles in n o n u n i f o r m electric
fields (1-4). The present study has sought to i n q u i r e
e x p e r i m e n t a l l y as to what effect the deposition of solid
m a t e r i a l might have on electrical conduction t h r o u g h
the liquid.
The effects of particles on electrical conduction processes in liquids are as yet incompletely known. Conductive particles such as iron or wet particles such as
moist clay are k n o w n to play a n i m p o r t a n t role in dielectric b r e a k d o w n of liquids (6, 7). The role of i n sulating material particles in conduction in dielectric
liquids is less well known, especially at voltages well
below b r e a k d o w n values. Electrophoretic p h e n o m e n a
i n v o l v i n g the charging of particles and their subseq u e n t discharge after migration to an electrode are
well recognized (6,7). K o k (6) has expressed the
opinion that particles, themselves of a n insulating n a ture, have a negligible effect on c u r r e n t flow in liqquid dielectrics a n d t h a t their effect would be indistinguishable from the b a c k g r o u n d ionic current. Pohl
and Schwar (3) have suggested that rotational
B r o w n i a n motion of suspended particles m a y enhance
c u r r e n t flow by rotationally t r a n s p o r t i n g deposited
ions from the m e d i u m on the surface of the particles.
The effect on conduction due to i n s u l a t i n g particles
resting at an electrode has not been studied. I n the
case of p u r e l y ohmic conduction one would expect
the presence of particles of lower conductivity t h a n
the liquid to block c u r r e n t flow. Yet the earlier experiments of Pohl and Schwar had indicated that the
opposite might occur, and that the presence of i n s u l a t ing particles could enhance c u r r e n t flow in dielectric
liquids. The present work was u n d e r t a k e n to e x a m i n e
more q u a n t i t a t i v e l y the e x p e r i m e n t a l facts and to derive a theoretical u n d e r s t a n d i n g of them.
A somewhat distantly related p h e n o m e n o n is k n o w n
to occur in glow discharge tubes. W h e n the cathode is
entirely covered with a t h i n film of i n s u l a t i n g m a t e r i a l
* Electrochemical Society Active Member.

(5) a c u r r e n t increase is observed. The explanation

proposed was that a positive space charge was formed
either inside or at the surface of the i n s u l a t i n g m a t e riM, the positive charge being supplied by positive
ions from the gas plasma i n the tube. The r e s u l t a n t
high field in the i n s u l a t i n g layer pulled electrons
t h r o u g h it, some of which are emitted with high velocity into the conducting gas. This effect, as we shall
see, is different in an essential w a y from that which
we shall discuss for particles. The particles produce a
t h r e e - d i m e n s i o n a l p e r t u r b a t i o n in the electric field,
the film produces only a o n e - d i m e n s i o n a l one, a n d
different mechanisms are calIed into play.
The present experiments were conducted with p a r ticles held to an electrode in a n o n u n i f o r m field b y the
action of dielectrophoretic force. Great care was
t a k e n with regard to p u r i t y of the liquids and the
suspended particles. A c o m b i n a t i o n of exhaustive recycled sorption and electrical de-ionization was used
in a sealed test cell to achieve v e r y high p u r i t y and a
high degree of reproducibility. The experiments,
broadly speaking, were done using a slightly modified
form of dielectrophoretic technique with cylindrical
geometry (1-4). P o l y v i n y l chloride (PVC), sulfur, and
silicon dioxide were used as solids, carbon tetrachloride and carbon t e t r a c h l o r i d e - t o l u e n e m i x t u r e s were
used as liquids.

Experimental
Test system.--A schematic diagram of the test syst e m is shown in Fig. 1. The cell was designed so that
the purification system was i n t e g r a l w i t h it. The p u r i fication system comprised two parts; a sorption bed
of 6-12 mesh silica gel in the lefthand c h a m b e r of the
P y r e x glass cell, and a set of three concentric cylindrical stainless steel electrodes in the r i g h t h a n d c h a m ber. The latter electrodes were connected as shown to
a 45v battery. The central c h a m b e r served as the test
chamber. The sintered glass filter b e n e a t h the central
test c h a m b e r had a m a x i m u m pore size of 40-60~,
while that u n d e r the sorption bed had a m a x i m u m
pore size of 170-200~. The whole ceil was 21.6 cm high
and 14.0 cm wide. The chambers were constructed of

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