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Oxidation of Metals, Vol. 3, No.

3, 1971

Oxidation of Copper at High Temperatures


S. Mrowec* and A. StokIosa*

Received October 21, 1970--Revised January 13, 1971

The kinetics and mechanism of copper oxidation have been measured over the
temperature range 900-1050~ and the pressure range 5 x 10 -3 to 8 • 10-1
arm. It has been shown that, at the pressures lower than the dissociation pressure
of CuO, the oxide scale formed on fiat fragments of the copper specimens is
compact and composed of a single layer, adhering closely to the metallic base.
Growth of the scale proceeds under these conditions by outward diffusion of
metal. The rate of the process under the conditions for which single-phase
scales are formed increases with increasing oxygen pressure according to the
equation :
kp = const p1~3.9
tt

the activation energy for oxidation is 24 +_ 2 kcal/mole. On the basis of the


Fueki-Wagner method and the method proposed in the present work, the self-
diffusion coefficients of copper in cuprous oxide were calculated as a function
of oxygen pressure and temperature. It has been shown that distribution of the
defect concentration in the growing layer of the scale is linear.

INTRODUCTION
The mechanism of high-temperature oxidation of copper has been a subject
of extensive theoretical and experimental studies. 1-3 Classical works of
Wagner *-v published in the 1930's were concerned with the kinetics and
mechanism of copper oxidation and with physicochemical properties of
cuprous oxide, which was the main product of the oxidation. In the following
* Institute of Solid State Chemistry, School of Mining and Metallurgy, Cracow, Poland.
291
292 Mrowec and Stok]7osa

years studies on the copper-oxygen system were concerned with the elucida-
tion of the kinetics and mechanism of scale formation and the physico-
chemical properties of the two oxides of copper. 1-1~
It has been shown that the scale formed on fiat fragments of the copper
specimens is compact and its growth takes place by outward diffusion of the
metal. ~~ Hence it may be assumed that the defect structure in cuprous
oxide is limited only to the cation sublattice. This conclusion is in full agree-
ment with the results of studies on deviations from stoichiometry in this oxide,
conducted at various temperatures and at various oxygen pressures, and is
confirmed by the results of Hall effect measurements 13,14and by the observed
dependence of the electrical conductivity on the oxygen pressure, s;15'~6
Specifically, it has been proved that cuprous oxide shows deviations from
stoichiometry involving cation defects (Cu2_yO) and that the electrical
conductivity of this oxide increases with increasing oxygen pressure, electron
holes being the current carriers. Cuprous oxide is thus a p-type, metal-deficit
semiconductor, having cationic vacancies and electron holes. These con-
clusions are also confirmed by the results of studies on. diffusion of copper
and oxygen in Cu20, which show that the mobility of the metal in the
cuprous oxide is considerably higher than the mobility of oxygen. 11 17
Although much information has been collected, many problems related to
the mechanism of copper oxidation and physicochemical properties of
Cu20 await solution. In particulaar there exist marked discrepancies between
the results obtained by-~arious authors concerning the dependence of the
oxidation rate on the oxygen pressure 7'~8'~9 and the dependence of defect
concentration on the equilibrium pressure of oxygen. ~6'2~ Accurate data
on the mobility of point defects in Cu20 are also lacking. The only data
available reported by Moore and Seliks~Sn,1~ are limited to one pressure of
oxygen and were subjected to considerable experimental error because of the
very short half-life of 64Cu ('~1/2 ~--- 12 hr).
Because of the discrepancies mentioned above, one cannot formulate
unambiguous conclusions about the defect structure of cuprous oxide and in
particular about the degree of ionization of cation vacancies and their
mobility. Therefore, the mechanism of copper oxidation cannot be described.
The present work is an attempt to explain these problems on the basis of
precise measurements of parabolic rate constants of copper oxidation as a
function of oxygen pressure and temperature.

EXPERIMENTAL
Kinetics Measurement
The kinetics of copper oxidation were studied with the continuous
gravimetric method in an apparatus containing a spiral microbalance, a
Oxidation of Copper at High Temperatures 293

constant

~er
gas o1.1,

8
F

10

Fig. 1. Vacuum microbalance. 1, Hooks


for hanging the spiral; 2, tungsten spiral;
3, thermostatic cooler; 4, damping device ;
5, window to measure the spiral elongation
with a microscope; 6, water cooler; 7,
quartz plates ; 8, asbestos shield ; 9, ceramic
casing ; 10, heating elements ; 11, thermo-
couple controlling the furnace temperature.

schematic diagram of which is shown in Fig. 1. A detailed description of this


apparatus is given elsewhere. 21 The sensitivity of the microbalance was
26 mg/cm, which was equivalent to measuring the mass gains with the
accuracy of _+2 x 10- 6 g at a load not exceeding 700 mg. The oxidation was
294 Mrowec and StokJcosa

conducted in a constant stream of gas, the flow rate of which was varied
between 5 and 15 ml/min. The oxygen pressure ranged from 6.6 x 10 -3 to
0.8 atm and the temperature from 900 to 1050~ The lower limit of the pres-
sure range was set by evaporation of cuprous oxide which under these
conditions began to affect the results of the kinetics. The upper value of the
pressure was determined by the dissociation pressure of cupric oxide (CuO).
The experiments were carried out on spectrally pure copper (Matthey and
Johnson). The flat specimens, 12.5 x 8.00 x 0.45 ram, were cut from sheet
obtained by cold rolling of 5 mm diameter rods of copper. The surface of the
specimens was polished with emery paper through 4/0, and then washed
successively with water, acetone, and methanol. After fixing, the specimen in
the reaction chamber, purified argon was passed through the apparatus. The
reaction chamber was then evacuated down to the pressure of the order of
10-6 mm Hg, which, taking into account the preliminary purification of the
system with argon, enabled the partial pressure of oxygen to be reduced to
about 10- lo atm. Under these conditions the specimen was not oxidized in
the temperature range applied. After the pressure was reduced to 10-6 mm
Hg, the reaction chamber was heated to the desired temperature. After the
desired temperature was attained, the specimen was further heated for 20 min,
and then oxygen was admitted, its pressure and flow rate being controlled by
Alpert-type valves. The oxidation kinetics were followed by registering the
mass gains of the oxidized samples as a function of reaction time. The
required pressure of oxygen was established within 2 min, and this time was
regarded as the zero on the time scale.

Calculation of Parabolic Rate Constants


To determine accurately the values of parabolic rate constants of metal
oxidation by the gravimetric method, the reaction conditions must ensure
that a single-layer scale forms which adheres to the metallic substrate
throughout the entire test. If scale growth proceeds by outward diffusion of
metal, full contact between the reaction product and the metal is preserved
by plastic deformation of the scale. 22-24 However, plastic deformation is
possible only on the fiat regions of the oxidized specimen. However, plasticity
occurs only for reaction times for which the ratio of the scale thickness to
the size of the flat surface is considerably less than one. 25'26 The specimen
edges make the scale rigid, acting subsequently as an obstacle to plastic
deformation.22 26 Due to this behavior one must estimate the duration for
which the scale remains adherent to the metallic core. It was shown by
preliminary measurements that the scale adhered well when its thickness did
not exceed 0.17 ram. This was equivalent to a reaction time of about 3 hr at
900~ and of 1 hr at 1050~
Oxidation of Copper at High Temperatures 295

Another essential factor affecting the value of a parabolic rate constant is


the surface area by which the mass gains are divided when calculating kp
from the Pilling and Bedworth equation 27 :
(Am/q) 2 = k~t + C (1)
where Am is a mass gain after a time t, q is the surface area of metal, k~ is the
parabolic rate constant, and C is a constant.
Most studies do not take into account the decrease of surface area during
the reaction and, thus, the division of successive mass gains by the initial
surface area leads to larger and larger errors. In precise experiments this fact
is reflected in distinct departures from the parabolic rate law (Fig. 2). These
departures were usually considered as inherent in the oxidation process and
not as a result of systematic experimental errors. This problem has been

I
!

20 30 5O 7O

tmm

Fig. 2. K i n e t i c s of c o p p e r o x i d a t i o n at 1000~ at Po2 = 2.6 x 10 2 a t m


( p a r a b o l i c plot). C u r v e 1, using the initial surface a r e a ; 2, using a n
a v e r a g e surface area.
296 Mrowec and StoMosa

discussed by the present authors in a separate paper. 28 Correct results are


obtained if one uses the mean surface area qi, which is the average of the initial
surface area and the instantaneous area. This is obtained by measuring the
initial and final surface area and assuming that the change is a linear function
oflthe change in the mass gain:

que = qo -- P Am (2)
9~here qM~ is the instantaneous surface area, q0 is the initial surface area, p is
a constant. This equation was used to calculate gh. An example of kinetic
curves for copper oxidation at a pressure of 2.6 x 10 -3 a t m is shown in
Fig. 3. Values of the parabolic rate constants obtained are given in Table I.
9 The temperature dependence of the oxidation rate is plotted in Fig. 4 for
various pressures of oxygen. Curves 1-5 correspond to the oxygen pressures
below the dissociation pressure of CuO. These conditions are those for which
single-phase scales of cuprous oxide are formed. Curve 6 corresponds to the
oxygen pressure in air. This latter pressure exceeds the dissociation pressure
of C u O except at 1050~ This curve represents the temperature dependence

2 2

25 50 '75

t m/n

Fig. 3. Kinetics of copper oxidation at Po2 = 2.6 x 10 -2 atm for


several temperatures (parabolic plot). Curves 1-5 correspond, respect-
ively, to 900, 950, 980, 1000, and 1050~
Oxidation of Copper at High Temperatures 297

Table I. Parabolic Rate Constants of Copper Oxidation in the Temperature Range 900 1050~
(k~ x 108 g2 cm-4sec-1)

Temperature
(~
900 950 980 1000 1050
Pressure \ .
(Po2 X 103 atm)

6.6 1.83 2.87 3.8 3.9 5.7


13.2 2.22 3.47 4.6 4.9 7.0
19.7 2.47 -- 4.8 -- --
26.3 2.67 4.08 5.2 5.9 7.8
39.5 2.82 4.57 5.7 6.5 9.3
52.6 -- 4.58 6.3 7.0 9.8
79.5 2.80 -- 6.7 7.7 11,1
100.0 2.80 4.58 6.8 8.1 --
134 -- -- -- 12.5
144 -- -- 6.7 -- --
180 -- -- -- 8.2 13.8
265 -- -- 6.7 -- 14.5
400 -- -- 8.1 17.1
500 -- -- 17.0
600 -- -- -- 16.8
Error Ak~ +0.03 -+0.08 -+0.1 -+0.1 -+0.3

of the o x i d a t i o n rate for a duplex scale. T h e a c t i v a t i o n energy of o x i d a t i o n is


24 _+ 2 k c a l / m o l e for the m o n o p h a s e scale (curves 1-5) a n d 33.5 kcal/mole
for the duplex scale (curve 6).
D a t a for the t e m p e r a t u r e d e p e n d e n c e of the rate of f o r m a t i o n of the
m o n o p h a s e scale o n c o p p e r are l a c k i n g in the literature ; therefore, the value
of the a c t i v a t i o n energy o b t a i n e d in the present work c a n n o t be c o m p a r e d
with o t h e r data. The c o m p a r i s o n m a y be made, however, for the duplex
scale formed at a m b i e n t oxygen pressure 0.21 atm. I n T a b l e II the values of
the a c t i v a t i o n energy of copper o x i d a t i o n in air available in the litera-
ture 19'z9-32 are c o m p a r e d with those o b t a i n e d in the present w o r k (curve 6).
The values o b t a i n e d by different a u t h o r s vary considerably. This m a y be due
to the different degrees of p u r i t y of the copper sample a n d also to the errors
m a d e in the d e t e r m i n a t i o n of the p a r a b o l i c rate constants. 26'zs
T h e d e p e n d e n c e of the rate of o x i d a t i o n o n the oxygen pressure is
plotted in Fig. 5. T h e r e a c t i o n rate increases with increasing oxygen pressure
u p to a point, a b o v e which it r e m a i n s constant, a n d at 1050~ it decreases
slightly. I n the r a n g e of pressures below the dissociation pressure of c u p r o u s
oxide, the v a c a n c y c o n c e n t r a t i o n g r a d i e n t in the g r o w i n g scale, C u 2 0 , is
d e p e n d e n t o n the oxygen pressure, i n c r e a s i n g with increasing oxygen
298 Mrowec and Stokr

Table II. Activation Energy of Copper Oxidation in Air

Activation energy Temperature range


Literature (kcal/mole) (~

Tylecote 29 29.4 600- 900


Valensi 3~ 37.7 700-1000
Kofstad 31 35 750-1000
Bridges e t al. 19 31.5 700-1000
Czerski e t a l ) 2 38 900-1050
Present work 33.5 901~1050
Present work (at the oxygen pressure 2.6 x 10 . 2 atm) 24 +_ 2 900-1050

r ~
f050 ~ 1000 o 950 ~ 900 *

~za

07~ QSO O.e4

r "K
Fig, 4, Temperature dependence of the rate of copper oxidation for
several oxygen pressures. Curves i - 5 correspond, respectively, to
6.6 x 1 0 - 3 a t m , 1.3 x 1 0 - 2 a t m , 2.6 x 1 0 - 2 a t m , 3.9 x 1 0 - 2 a t m ,
and 7.9 x 10 -2 atm. Curve 6 corresponds to the oxygen pressure of air.
Oxidation of Copper at High Temperatures 299

//

-7,o ///z////
"t,
Ii ii
g / o o

-~'8

-2.0 ~2,5 -ZO -0~5

(og Po~ otto

Fig. 5. Dependence of the copper oxidation rate on oxygen pressure.


Curves 1-5 correspond, respectively, to 900, 950, 980, 1000, and 1050"C.
The broken line shows the boundary between the single-phase scale
(region I) and the two-phase scale (region II).

pressure. Since the reaction rate is determined by the diffusion of cation


vacancies in the scale, the parabolic rate constant for oxidation increases with
an increase in the defect concentration gradient in the scale. In region II, at
pressures exceeding the dissociation pressure of CuO, there always exists a
thin layer of CuO on the exterior scale surface which separates the Cu~O from
the oxidizing atmosphere. The partial pressure of oxygen at the Cu~O-CuO
boundary, which determines the value of the concentration gradient in the
Cu20 phase, is thus independent of the external oxygen pressure and is
equal to the dissociation pressure of CuO. Because nearly the whole scale
consists of Cu20 (CuO represents about 1% of the scale), the oxidation rate
at a given temperature should be independent of the external oxygen pressure
300 Mrowec and Stok4osa

whenever CuO exists. This conclusion is verified by the results presented in


Fig. 5. In order to confirm the above conclusions, the dissociation pressures
of CuO at various temperatures were calculated from the thermodynamic
data reported by various authors 33-36 and compared with the values of the
oxygen pressures at which the break of the curves in Fig. 5 was observed. The
results of these calculations are presented in Fig. 6. As expected, the values
of the oxygen pressures at which the break in the straight lines of Fig. 5 is
observed correspond to the values of the dissociation pressures of cupric
oxide derived from thermodynamic data.

Metallographie Studies
The measurements of oxidation kinetics were supplemented by studies on
material transport through the scale using the marker method. A platinum
r ~
f050 9 fO00 9 950 9 900 9

E]
-0.5

.~ -/.0

-/.5

0.78 0.80 0.'8/~

-/-/0 3 ,/(
T
Fig. 6. Dependence of the dissociation pressure of cupric oxide (CuO)
on temperature. (D, Kubashevski31; A, Landolt32; [], Charotta3;
Z~, Bidwell 3s ; 0 , present work.
Oxidation of Copper at High Temperatures 301

wire, 30 g in diameter, was used as a marker. Sections of this wire, 2 mm long,


were placed on the sample surface which was then oxidized in a horizontal
position. The sample was subsequently mounted in polyester resin and then
cut perpendicularly to the surface covered with the markers. The location of
the marker in the scale was determined microscopically. Marker studies
were performed for some extreme temperatures and oxygen pressures. The
studies proved that the scale was compact and single-layered in its entire
cross section and that the platinum markers were located at the metal-scale
phase boundary. It follows from these facts that scale growth in this case takes
place exclusively by outward diffusion of metal.

DISCUSSION
The kinetic data obtained allow us to formulate a number of important
conclusions concerning the mechanism of high-temperature oxidation of
copper, the mobility of point defects in cuprous oxide, and the degree of
ionization of cation vacancies in this oxide. It has been found, that under
suitably selected conditions the oxidation of copper produces a single-
layered compact scale adherent to the metal. Scale growth proceeds under
these conditions by outward diffusion of metal. These facts corroborated by
strictly following the parabolic rate law imply that the slowest process
determining the rate of scale growth is diffusion of cation vacancies according
to the theoretical model of Wagner. 37 Good contact of the scale with the
metallic core during the determination of the kinetics and strict parabolic
behavior suggest that, under the conditions described above, there are no
perturbations of local thermodynamic equilibria at either phase boundary.
The results of the kinetics may be thus employed in calculations of self-
diffusion coefficients of copper in cuprous oxide from the general equation of
Wagner 37 :
--.--(a'~/zx ) (3)
kr=ceqj~kl-~D~e + Dx d l n a x
where kr is a rational oxidation constant expressed in gram equivalents per
centimeter per second; Ceq is the concentration of metal ions in gram
equivalents per cm 2 of the scale; z 1 and z2 are the valences of metal and an
oxidant in the reaction product, respectively; a~ and a~ are the thermo-
dynamic activities of the oxidant at the metal scale and scale-oxidant phase
boundaries; and DM, and Dx are the self-diffusion coefficients of metal and
anions in the scale. Since in the case under consideration Dcu >> Do2,17 the
general equation of Wagner can be simplified to the following form :
~ Z1
kr = C~q
~f -- D~e d In a x
k Z2
(4)
302 Mrowec and Stok4"osa

The rational rate constant in Eqs. (3) and (4) may be replaced by the parabolic
rate constant kp expressed in g2 • cm-4 x sec i.

kr = ~Mox(z2/Ax) 2 k~ (5)
Substituting the oxidant activity by its partial pressure, one obtains the
following relation between the parabolic rate constant of oxidation and the
cation self-diffusion coefficient in the scale :
,, A~zl fpk
k p - -2 3 Duedlnpx (6)
V~MeXZ2 p,.
where Pr denotes the oxidant pressure at the metal-scale phase boundary
and Px is the oxidant pressure at the outer phase boundary. To integrate
Eq. (6) we should know a priori the dependence of self-diffusion coefficient of
metal in the scale on the oxidant pressure. Fueki and Wagner 39 have proposed
the solution of this problem which does not require the knowledge of the
dependence of DMe on the oxidant pressure. They drew attention to the fact
that Pr is, at a given temperature, independent of the oxidant pressure.
According to the assumptions of the Wagner theory,37 a local thermo-
dynamic equilibrium is attained at the metal-scale phase boundary, and
hence the partial pressure at this phase boundary is very close to the dissocia-
tion pressure of the scale. The above-mentioned assumption of the Wagner
theory was proved in a number of experiments.4~ Taking this fact into
account we may integrate Eq. (6) to give:

zt~ Ax ] ~dtnpx]p.
In the case of copper oxidation to Cu20, Eq. (7) assumes the form :
I dk"
Dc~ = 1.818| ---'~p | (8)
ld log Po2]v,
To calculate the self-diffusion coefficient of metal in the scale, it is
necessary to determine the dependence of the oxidation rate on oxygen
pressure. Having determined this function, one can calculate the value of
DM~by finding the differential of the function for a given pressure. Fueki and
Wagner 39 performed these calculations for the Ni-NiO-Oz system and
Mrowec, Walec, and Werber 42 for the Co-CoO-O 2 system. The results
reported were in agreement with the data obtained with the use of radio-
isotopes of nickel and cobalt. Analogous agreement was also found by
Mrowec 43'4~ for the Fe-FeS-S2 system. Equation (8) has been employed in
the present work for calculations of the self-diffusion coefficients of copper
in Cu20 at selected oxygen pressures and at a temperature of 1000~
Oxidation of Copper at High Temperatures 303

However, owing to the comparatively narrow range of oxygen pressures,


over which the oxidation of copper was studied, the accurate determination
of k~ = f(log Po2) and its differentiation were difficult, and the values of
Dcu were associated with considerable error.
Considering this problem, we have observed that the self-diffusion
coefficient of a metal in a p-type semiconductor scale may be calculated in a
much simpler way if log k~ is a linear function of log Po2. In this case the
reaction rate increases with an increase in the oxidant pressure according to
the equation :
kp = const plx/"
tt
(9)
It follows from the above relationship that the self-diffusion coefficient of a
metal should be an analogous function of the oxidant pressure, because
diffusion of cation vacancies in the scale is in this case the slowest partial
process determining the oxidation rate:
DMe = DoP~/n (10)
Substituting Eq. (10) into Eq. (6) and integrating, one gets:

A2xzl D n ~-I/n
kp- iv~__3 o ~ex - p ~ l , ) (11)
ghieXZ2
r162
The above equation may be simplified, if the measurements of kp were
performed at pressures considerably above the oxidant pressure at the
Me-MeX boundary (Px >> Pr) :

t! --
A~-zl
kp ~2 3 Donpx/" (12)
VMeXZ2
An analogous equation was reported much earlier by Wagner 37 in a
discussion of the possibilities of simplifying the solution of his general
equation. However the simplification used by Wagner has a form identical to
Eq. (9), and hence it does not define the proportionality coefficient of this
equation. This excludes the possibility of employing this relation for the
calculation of other physicochemical parameters, in particular in determin-
ing D o and 1In.
Because the kinetics of copper oxidation were determined at pressures
considerably higher than the oxygen pressure at the C u - C u 2 0 phase
boundary, the function
log kp = f(log Po2) (13)
was obtained by the least-squares method, and then the values of D o and
1/n were calculated from the constants obtained. Substituting these data
304 Mrowec and Stokt'osa

Table IlL Self-Diffusion of Copper in Cuprous Oxide

Temperature Pressure range Dc. = ~0vo~n


.1/,
(~ (atm) (cm2 sec- 1)

900 6.6- 26.3 Dcu = (6.8 • 0.1) x 10-8pl/2(4"~176


950 6.6- 39.3 Dcu = (1.10 • 0.02) x 10-Tp~/~ 3"9-+0"1)
980 6.6- 79.5 Dcu = (1.39 • 0.03) x 10-Tp~ 3'9-+~
1000 6.6-105 DCu = (1.55 • 0.03) x 10-Tp~ 3"9+-~
1050 6.6-400 Dc. = (2.27 +
--
0.09) x 10 -7-1/(3"9-+~
/vO 2

into Eq. (13) we o b t a i n e d the e m p i r i c a l f o r m u l a s for the self-diffusion co-


efficients of c o p p e r in C u 2 0 as a function of o x y g e n pressure. T h e results of
the c a l c u l a t i o n s a r e given in T a b l e III. T h e values of D c , c a l c u l a t e d b y the
F u e k i - W a g n e r m e t h o d are c o m p a r e d with t h o s e o b t a i n e d b y the m e t h o d
d e s c r i b e d a b o v e ( c o l u m n s 1 a n d 2 of T a b l e IV). G o o d a g r e e m e n t (within the
limits of e x p e r i m e n t a l error) b e t w e e n the t w o sets of values is observed.
H o w e v e r , the e r r o r m a d e in the c a l c u l a t i o n s with the F u e k i - W a g n e r m e t h o d
is c o n s i d e r a b l y h i g h e r t h a n t h a t o b t a i n e d with the p r e s e n t a u t h o r s ' m e t h o d .
T h e l a t t e r m e t h o d m a y be used o n l y for pressures which a r e c o n s i d e r a b l y
h i g h e r t h a n the o x i d a n t p r e s s u r e at the m e t a l - s c a l e p h a s e b o u n d a r y . O n e

Table IV. Self-Diffusion Coefficients of Copper in


CU20 at 1000~ (Calculated by Various Methods
from Kinetic Data of Copper Oxidation as a Function
of Oxygen Pressure)

Self-diffusion coefficient
Pressure Dcu x lOs cm z sec-I
Poz • 103
(atm) Values derived with equations

(8) (12) (19)

6,6 4.6 4.3 4.2


13,2 5.4 5.2 5.2
26.3 6.1 6.2 6.3
39.5 7.3 6.8 8.9
53.8 7.6 7.4 7.5
79.5 8.0 8.1 8.3
100 8.3 8.6 8.7
ErrorADcu • • --
Oxidation of Copper at High Temperatures 305

may thus conclude that the Fueki-Wagner method is more general, and the
results may be equally accurate when the measurements are carried out over a
suitably wide pressure range. If this is not possible, however, the method
proposed by the present authors appears to yield more accurate results.
To compare the results of calculations of Dcu with the values obtained
by Moore and Selikson 11 by radioisotope methods, the results of the present
work were extrapolated to an oxygen pressure of 1.3 x 10 . 4 atm making
use of the equations given in Table III. Moore and Selikson determined the
diffusion coefficients of copper in C u 2 0 in the temperature range 800-
1050~ at only one value of oxygen pressure (1.3 • 10 -4 atm). In Fig. 7 the
results of the present work and the data obtained by Moore and Selikson are
presented graphically. As already mentioned, the results obtained with the
radioisotope method show considerable scatter of the experimental points
which may be due to serious experimental difficulties resulting from the
short half-life of radiocopper. As seen from the plot, the results of the present

r'c
i

0
-7.6
8 o .
g o o

8 ~
O~

176 ~gO I
O,84 I
O,00
~. . 10 3 oK

Fig. 7. The temperature dependence of the self-diffusion coefficient of copper at Po2 = 1.3 •
10 -'~ atm. Open circles denote the experimental values obtained from radioisotope measure-
ments; open triangles are the values extrapolated from the results of the present work.
306 Mrowec and Stok]'osa

calculations are essentially in agreement with the results of the isotopic


studies. It should be noted, however, that the value of the activation energy
of copper diffusion in Cu20, 36 kcal/mole, reported by M o o r e and Selikson is
considerably higher than that obtained in the present work, 24 _+ 2 kcal/mole,
the latter value being practically independent of the oxygen pressure over
the pressure range studied (Fig. 8). Although the pressure range in our
experiments was relatively narrow, it seems improbable that a further
decrease of pressure of one order of magnitude could cause such a marked
increase in the activation energy of diffusion. In addition, the temperature
dependence of Dcu (Fig. 7) cannot be determined accurately from the Moore
and Selikson data as the scatter of experimental points is too large.

T ~
1060 9 tO00 * 950 ~ 900 o

-7,0

-7,~

-76

-7,8

i -- i __ i
~TG 0,80 O.B/~

-lr.lOJ oE
Fig. 8. The temperature dependence of the self-diffusion coefficient of
copper in Cu;O. Curves 1-5 correspond, respectively,to 6.6 x 10-3 atm,
1.3 x 10 2atm, 2.6 x 10-2atm, 3.9 x 10-2atm, and 7.9 x 10-Zatm.
Oxidation of Copper at High Temperatures 307

The activation energy of copper self-diffusion in C u 2 0 is the sum of the


energy of formation of cation vacancies and the energy of movement of these
vacancies. By studying deviations from stoichiometry in C u 2 0 as a function
of oxygen pressure and temperature, Moore and O'Keeffe 2~ found the
following relationship between the concentration of cation vacancies and
oxygen pressure :
,,1/3J
y = const zo2 (14)

The exponent in Eq. (14) is very close to 1/4, implying that the cation vacancies
are practically nonionized. The latter conclusion follows from considerations
on the defect equilibria in the crystal lattice of cuprous oxide. 45'46
This conclusion is in agreement with the results of investigations on the
rate of copper oxidation as a function of oxygen pressure, shown in Fig. 5,
which is the basis for calculations of self-diffusion coefficients of copper in
cuprous oxide. It has been found that the pressure dependence of the para-
bolic rate constant is described by
kp = const p ~ (15)
where the exponent 1/n varies, depending on the temperature, between
1/3.9 and 1/4. An analogous dependence was obtained for the self-diffusion
coefficient of copper in C u 2 0 (Table IV and Fig. 8).
Bearing in mind the fact that the exponent of Eq. (10) has a value close
to 1/4, the general relationship between the coefficient of self-diffusion of
copper in C u 2 0 and temperature and the oxygen pressure may be described
as

Dcu = const p ~ e x p { [ - ( A H f + AHm)?/RT} (16)


where A/-/m is the energy for the movement of defects. It follows from Fig. 8
that the temperature dependence of the self-diffusion coefficient obeys the
Arrhenius law and may be described by the equation:
Dcu = const p ~ e x p ( - E/RT) (17)
where E is the experimental activation energy of diffusion. Comparison of
Eqs. (16) and (17) shows that the measured activation energy of diffusion of
24 _+ 2 kcal/mole is the sum of the heat of defect formation in the crystal
lattice of C u 2 0 and the energy of the defect motion :
E=AH z +AH m (18)
The " t r u e " activation energy of diffusion of cation vacancies in the
crystal lattice of C u 2 0 is thus equal to the difference between the value of E
and the activation energy of the defect formation (AHf). Results of Moore
and O'Keeffe 2~ give the value of 21.7 kcal/mole for AHf. On the other hand,
308 Mrowec and Stoldosa

Wagner and Hammen 6 report the value o f A H I as 13 kcal/mole at an oxygen


pressure of 6.6 x 10 .3 atm. Such discrepancies in these values make it
impossible to evaluate the energy for the movement of cation vacancies.
Nevertheless, it may be stated with a high degree of certainty that the energy
for defect motion in cuprous oxide is markedly smaller than the energy of this
process in other transition metal oxides. If the value obtained by Wagner
and H a m m e n is substituted into Eq. (18), then AH,, = 11 kcal/mole, whereas
substitution of the value of Moore and O'Keeffe yields AH m = 3 kcal/mole.
Both these values are considerably smaller than the energy of defect motion
in oxides of iron, nickel, and cobalt, which like C u 2 0 are metal-deficit,
p-type semiconductors. AH mfor the latter oxides is about 28-30 kcal/mole. 47
The cation vacancies in these oxides are, over the range of pressures and
temperature in which A H m was determined, singly ionized. In the case of
cuprous oxide, as it follows from the above discussion, the activation energy
was determined for the case in which the majority o fvacancies were un-ionized.
It can then be supposed that the low energy of defect motion in C u 2 0
can be related to the absence of ionization of cation vacancies. The problem
requires further studies ; in particular it is necessary to measure the activation
energy of diffusion and the heat of formation of defects at low oxygen
pressures, at which pressures ionized vacancies may occur.
Making use of the Pettit theory, 48 the kinetic data were used to deter-
mine the oxygen activity gradient in the scale during growth at various
temperatures and pressures. The results obtained, supplemented by results
of studies on deviations from stoichiometry in C u 2 0 obtained by Moore and
O'Keeffe, 2~ were then employed to determine the distribution of cation
vacancies in the oxide. These calculations proved that the gradient of the
defect concentration was linear (Fig. 9). Analogous results were obtained
by Pettit 48 and Mrowec 42'43 for other systems.
The linear distribution of the concentration of cation vacancies in the
scale indicates that the self-diffusion coefficient of defects, D v, is independent
of defect concentration.
It is also possible to derive the self-diffusion coefficient of copper in
C u 2 0 from kinetic data by making use of the modified M o t t - G u r n e y
equation 49 :

t
kp = (p + 1)Die (19)

where kp is a parabolic rate constant for the reaction in cm 2 sec- 1 and p is


t

the degree of defect ionization.


As already mentioned, the dependence of the cation vacancy concentra-
tt
tion in C u 2 0 on the oxygen pressure [Eq. (14)J and the dependence kp
f(Po2) [Eq. (15)1 imply that the vacancies in the cation sublattice are probably
Oxidation of Copper at High Temperatures 309

I
f
I
/
I
/I
/
I
/
I"
/

//
/
111 "+

x
xo

Fig. 9. Defect concentration gradient in Cu20 during oxidation at 1000~

un-ionized, and thus p = 0. The value obtained is in good agreement with


those derived from Eqs. (8) and (12). The results of these calculations are
given in column 3 of Table IV.
The agreement of the values of Dcu calculated from Eqs. (8), (12), and
(19) confirms the hypothesis stated earlier, according to which cation
vacancies in Cu~O are un-ionized. If the singly ionized vacancies were
predominant, then one should substitute p = 1 in Eq. (19) which would
double the value of Dcu obtained from Eqs. (8) and (12).

CONCLUSIONS
The results of studies on the kinetics and mechanism of copper oxidation,
under conditions for which the formation of a single-phase scale of cuprous
oxide forms, allow us to formulate the following conclusions.
1. The oxide scale on copper, formed over a range of oxygen pressures
below that of the dissociation pressure of CuO, is compact and adheres
310 Mrowec and Stokt~osa

closely to the metal on the flat portions of the sample. Growth of the scale,
consisting solely of Cu20, occurs by the outward diffusion of the metal. The
rate-determining step of oxidation is the diffusion of cation vacancies in the
scale.
2. When interpreting kinetic data, one should take into account the
changes in surface area of the metal during oxidation. Neglecting this factor
may give rise to erroneous conclusions, with respect to the rate law followed
and the absolute values of the rate constants of this process.
3. Under the conditions for which CuzO is the sole product of oxidation,
the rate of copper oxidation increases with an increase in oxygen pressure
according to the assumptions of t h e Wagner theory. It follows from this
dependence that in the temperature range 900-1050~ and at pressures
close to 1 atm, cuprous oxide contains mainly un-ionized cation vacancies.
This conclusion is confirmed by the results of calculations of Dco performed
with the use of Eqs. (8), (12), and (19).
4. The activation energy of copper oxidation when a single-phase
scale forms is different than that observed when a duplex scale forms (Table
II). This difference is due to the dependence of the rate of growth of C u 2 0
phase on oxygen pressure.
5. The self-diffusion coefficient of copper in cuprous oxide as a function
of oxygen pressure and temperature was derived from kinetic data by the
Fueki-Wagner method as well as by the new method proposed in the present
work. The agreement between the results obtained with these two methods is
good. This agreement is observed also between calculated results and data
obtained by M o o r e and Selikson who used radioisotopes.
6. The defect concentration gradient in the growing scale was analyzed
by the Pettit equations. This distribution was linear (Fig. 9). This enabled
us to employ the modified M o t t - G u r n e y equation [Eq. (19)] to calculate the
self-diffusion coefficients of copper in C u 2 0 as a function of temperature and
oxygen pressure. The agreement between values obtained in these calcula-
tions and those derived by other methods (Table IV) enabled the degree of
ionization to cation vacancies in C u 2 0 to be determined.

REFERENCES

1. O. Kubaszewskiand B. E. Hopkins, Oxidation of Metals and Alloys (Butterworths,London,


1962).
2. K. Hauffe, Reaktione in und an fksfen StoJfen (Springer-Verlag,Berlin, 1966),pp. 180, 640.
3. K. Hauffe,Oxydation yon Me~atlen und Metallegierungen (Springer-Verlag,Berlin, 1956).
4. H. Dunwald and C. Wagner, Z. Physik. Chem. B 17, 467 (1932).
5. J. Gtinderman, K. Hauffe,and C. Wagner, Z. Physik. Chem. B 37, 148 (1937).
6. C. Wagner and H. Hammen, Z. Physik. Chem. B 40, 197 (1938).
7. C. Wagner and K. Griinewald,Z. Physik. Chem. B 40, 455 (1938).
Oxidation of Copper at High Temperatures 311

8. A. Ronnguist and H. Fischmeister, J. Inst. Metals 89, 65 (1960-1961).


9. R. Tylecote, Metallurgia 53, 191 (1956).
10. F. Maak, Z. Metallk. 52, 538 (1961).
ll. W. J. Moore and B. Selikson, J. Chem. Phys. 19, 1539 (1951); 20, 927 (1952).
12. J. Bardeen, W. Brattain, and W. Schockley, J. Chem. Phys. 14, 714 (1946).
13. E. Engelhard, Ann. Phys. 17, 501 (1933).
14. H. Mtiser and Schilling, Z. Naturforsch. 7a, 211 (1952).
15. R. S. Toth, R. Kilkson, and D. Trivich, Phys. Rev. 122, 482 (1961).
16. M. O'Keeffe and W. J. Moore, J. Electrochem. Soc. 35, 1324 (1961).
17. W. J. Moore, Y. Ebisuzaki, and J. A. Sluss, J. Phys. Chem. 62, 1438 (1958).
18. J. P. Baur, W. D. Bridges, and W. M. Fassell, J. Electrochem. Soc. 103, 273 (1953).
19. D. W. Bridges, J. P. Baur, G. S. Baur, and W. M. Fassell, J. Electrochem. Soc. 103, 475
(1956).
20. M. O'Keeffe and J. Moore, J. Chem. Phys. 36, 3009 (1962).
21. S. Mrowec and A. Stoktosa, J. Thermal Anal. 2, 75 (1970).
22. A. Briickman, Corrosion Sci. 7, 51 (1967).
23. S. Mrowec, Corrosion Sci. 7, 563 (1967).
24. D. L. Dougiass, Oxidation of Metals 1, 127 (1969).
25. B. Lichter and C. Wagner, J. Electrochem. Soc. 107, 168 (1960).
26. J. Romafiski, Corrosion Sci. 8, 67 (1968).
27. N. Pilling and R. Bedworth, J. Inst. Metals 29, 529 (1923).
28. S. Mrowec and A. Stoktosa, Werkstoffe Korrosion 21, 934 (1970).
29. R. F. Tylecote, J. inst. Metals, 78, 300 (1950).
30. G. Valensi, Pittsburgh International Conference of Surface Reactions, Pittsburgh, 1948,
p. 156.
31. P. Kofstad, Nature 179, 1382 (1957).
32. L. Czerski, S. Mrowec, and T. Werber, Roczniki Chem. 38, 643 (1964).
33. O. Kubaszewski, E. Evans, and C. B. Alcock, Metallurgical Thermochemistry (Pergamon
Press, Oxford, 1967), p. 421.
34. C. Landolt and A. Muan, J. lnorg. Nucl. Chem. 31, 1319 (1969).
35. G. C. Charette and S. N. Flangas, J. Electrochem. Soc. 115, 796 (1966).
36. L. R. Bidwell, J. Electrochem. Soc. 114, 30 (1967).
37. C. Wagner, Atom Movements (ASM, Cleveland, 1951), p. 153.
38. W. J. Moore and M. T. Shim, Ann. Physik Soc. 131st Mtg (1957), Abstract 47 R.
39. K. Fueki and J. B. Wagner, Jr., J. Electrochem. Soc. 112, 384 (1965).
40. H. Engell, Acta Met. 6, 439 (1958).
41. H. Rickert, Z. Physik. Chem. 23, 355 (1960).
42. S. Mrowec, T. Walec, and T. Werber, Bull. Acad. Polon. Sci. Ser. Sci. Chim. 14, 179 (1966).
43. S. Mrowec, Roczniki Chem. 42, 1913 0968).
44. S. Mrowec, Bull. Acad. Polon. Sci. Set. Sci. Chim. 15, 287 (1967).
45. J. Bloem, Philips Res. Rept. 13, 167 (1958).
46. A. Kr6ger, The Chemistry of Imperfect Crystals (North-Holland, Amsterdam, 1964), p. 577.
47. P. Kofstad, High-Temperature Oxidation of Metals (John Wiley, New York, 1968), p. 94.
48. E. S. Pettit, J. Eleetrochem. Soc. 113, 1249 (1966).
49. N. Mott and R. Gurney, Electronic Processes in Ionic Crystals (Oxford, London, 1948),
p, 257.