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3, 1971

S. Mrowec* and A. StokIosa*

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

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

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.

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.

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

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

( 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

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

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)

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

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

Literature (kcal/mole) (~

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

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

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).

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

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 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

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

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

.1/,

(~ (atm) (cm2 sec- 1)

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

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

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

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

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

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

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

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)

t

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

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

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Oxidation of Copper at High Temperatures 311

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22. A. Briickman, Corrosion Sci. 7, 51 (1967).

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24. D. L. Dougiass, Oxidation of Metals 1, 127 (1969).

25. B. Lichter and C. Wagner, J. Electrochem. Soc. 107, 168 (1960).

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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).

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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).

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