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,4 paper contributed to the Symposium on

"Electrometallurgy,'" S. Skowrouski in charge.

T H E O X I D A T I O N A N D E V A P O R A T I O N OF M A G N E S I U M
A T T E M P E R A T U R E S F R O M 400 ~ TO 500 ~ C t

By EARL A. GULBRANSEN$

ABSTRACT

A vacuum microbalance technic is used for the study of the oxidation


and evaporation of magnesium at temperatures from 400 ~ to 500 ~ C
and at several pressures. The curves obtained consist of an initial
evaporation perlod, an oxidation period, and a final evaporation period.
The oxidation curves at temperatures of 475 ~ C and higher are linear
with the time of oxidation. At temperatures of 450 ~ C and lower, the
curves follow the linear law, but, as the film builds up, the oxidation
rate diminishes. An analysis of the initial and final evaporation rates
and their relations to the oxidation curves is very interesting. Oxide
films of 700 A or more at a temperature of 475 ~ C are extremely porous
to the evaporation of magnesium. At temperatures of 450 ~ C and
lower, all of the films measured were protective to the evaporation
process. Films found to be protective to evaporation are also protective
to oxidation.

I NTRODUCTION

This paper describes the results of some experiments made on the


oxidation of pure magnesium. The experiments were carried out at
temperatures of 400 ~ to 500 ~ C and at pressures of 0.2 to 20 cm. of
oxygen. Magnesium presents an interesting metal for study since it
has the property of a high vapor pressure and also possesses a reaction
product which has a critical volume ratio of 0.84. Thus the oxide
should be of the cellular or discontinuous type and present little pro-
tective action to oxidation. The only work reported in the literature
Oll the oxidation of magnesium is that done by Pilling and Bedworth?
They reported difficulties in obtaining reproducible results with a mate-
rial of high vapor pressure. However, they did present a value for the
oxidation rate at 500 ~ C as 0.00052 g./cm.=/hr. Recently Rhines and
Leontis ~ have carried out an extensive but as yet nnlmblished study on
t Manuscript received December 8, 1944.
Research Laboratory, Westinghouse Electric & Manufacturing Co., East Pittsburgh, Pa.
XN. B. Pilling and R. E. Bedworth, J. Inst. Metals ill, 534 (1923).
ST. l.,eontis, Thesis, Carnegie Institute of Technology (1944).

589

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590 E A R L A. G U L B R A N S E N

the reaction of magnesium and its alloys with oxygen, air, nitrogen and
other gases from 475 ~ to 575 ~ C.
Unless vacuum evaporation technics are used for the preparation of
an oxide-free surface, it is necessary to carry out the experiments with-
out removing the initial oxide film. This is due to the fact that it is
impossible to remove the oxide film by hydrogen reduction under the
conditions available in the apparatus. The experiments reported here
are made with the initial oxide film present.

EXPERIMENTAL

A vacuum microbalance was used in all the measurements. The bal-


ance and method have been previously described?, ~ The balance had a
sensitivity of 1.305 micrograms/division. Each division could be esti-
mated to ~ of a division. The balance was checked for absence of
pressure and temperature effects and for the presence of a stable zero
point.
The samples were prepared and furnished by Rhines and Leontis of
the Carnegie Institute of Technology aDd were similar to the samples
they had used in their study. The specimens were of distilled magnesium
of 99.985% purity. The material was rolled to about 75% reduction
and annealed at 350 ~ C, packed in charcoal for two hours. After sawing
to the desired size the specimens were abraded. The final emery cloth
used was of 500 grit. No further treatment was given to the samples
before they were placed in the balance proper. The samples weighed
0.3656 gram and were each approximately 5.7 cmY in area.
The vacuum system in which the balance and specimen were contained
was of an all-glass construction with no stopcocks or grease joints.
A 2-stage mercury diffusion pump was used in conjunction with a
"hyvac" mechanical pump. A vacuum of 10 -6 ram. of Hg or better was
obtained with a liquid air trap. An additional liquid air trap was placed
between the balance and oxidation tube and the vacuum system. This
was to prevent any influence of the mercury vapor on the reaction. No
evidence was found for mercury vapor sensitizing the oxidation of
magnesium when the system was trapped with liquid air.
A copper block was placed around the specimen tube in the furnace
in order to minimize temperature gradients. This block consisted of a
chromium-plated copper bar 3.5 in. (89 ram.) in dialneter and 10 in.
(25 cm.) long in which a 1.5 in. (38 ram.) hole was drilled to a depth
of 9 in. (22.9 cm.). This copper mass was controlled by the tempera-
ture controller and maintained to within +--3~ C. The temperature of
the block was checked from time to time by means of a thermocouple
and a "type K " potentiometer.

PROCEDURE

The samples prepared by Rhines and Leontis were placed on the


balance beam and the system sealed off. After evacuation to 1 0 -e m m .
H g a small furnace was placed around the specimen tube. The tempera-
s Earl A. Gulbransen, Trans. Eleetrochem. Soe. 81, 327 (1942).
9 Earl A. Gulbransen, Rev. Sci. Instruments 15, 201-4 (1944).

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O X I D A T I O N A N D E V A P O R A T I O N OF M A G N E S I U M 591

ture was raised over a period of 0.5 hour to 500 ~ C. This procedure
was used on all of the samples and had as its purpose the removal of
any adsorbed or dissolved gases. The small furnace was next removed
and the large furnace containing the copper block, controlled at the
desired temperature, was placed around the specimen tube.
Readings were taken of the balance beam under vacuum conditions.
These readings represent the preliminary evaporation rate through the
initial film at the particular temperature. At the proper time purified
oxygen 8 was added to the desired pressure and readings again were
taken and the oxidation behavior determined. After completion of the
oxidation, the system was evacuated and another series of readings was
taken in order to evaluate the final evaporation rate through the final
film.

EVAC.U~Ts TO lO'~'mmH~,

86C
X-i J
,CONVECTION
CORRECTION

ss(l _SCALE /
READING /
OXIDATION~
IDI~ =1.305X ~ ~m.
/ FINAL
WT. GAIN / EVAPORATION'

ozQ S
/
940 ~NITIAL ,/
[VAPORATION / "
6,C.-10" mm H~,. ~ "

"~ L CONVECTION
I
980 [CORRECTION

.) ! ' J 0 TO 20Cm.

I0000= 40
I
80
I
120
,~o aoo a4o 28o 3zo ~6o 400
r i M E (UIN.) - - . -

F~o. 1. Oxidation and evaporation of magnesium at 475 ~ C and 20 em.O2.

One complication arose which affected the readings of the balance


beam when the specimen was surrounded by a gas atmosphere at these
temperatures. This complication was due to the convection currents of
gas m the specimen tube. It was a function of temperature, pressure,
and sample size and position in the tube. Accordingly, a correction was
introduced in all of the measurements of an individual run and was
calculated from the difference between the final reading in a vacuum
and the reading in the gas atmosphere.

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592 E A R L A. G U L B R A N S E N

A further complication arose in cases where a high evaporation rate


occurred and we had to determine the proper zero point of the oxidation.
In these measurements, in which the initial oxidation rate was very
slow, the zero point was extrapolated from the measurements.

RESULTS

A typical experiment is shown in Fig. 1. The curve A to B represents


the initial evaporation from the specimen in a vacuum of 10-6 mm.
H g at 475 ~ C. At B, 02 is admitted to a pressure of 20 cm. The large
change in scale reading is due to a convection current of gas in the

1060
I
I
IL
SCALE
108C R E A D I N G i
FINAL EVAPORATION
WT. G A I N

HO0 "EVACUATED 10"~rnrnH~

1120 INITIAL I
EVAPORATION
I
VAC -lO'6mmH~
l IOXIDATIO' i
i 14C

~15 HRS.

IrE
TIME (MII~'-~

FiG. 2. Oxidation and evaporation of magnesium at 450" C and 2.0 cm.Os.

155C
SCALE j
READING
157C f I
~/T.GAIN

I t
15go - - ~ INITIAL EVAPORATION RATE
:--~ ~-o FINA '
i EVA~P~)RATION
RATE
i

16It
~m
,i TO~ ,
t
CONVECTION"
' cORRECTiON

OXIDATION RATE IDIM=I-305 X I 0 " 6 ~ m ~ "VAC. TO IC~$rflm H~


163C , !

165C ,eo 2o0 24o 28o 320 3~o


40 80 120
TIME {M,N.~

Fro. 3. Oxidation and evaporation of magnesium at 450" C and 0.2 cm.Os.

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OXIDATION AND EVAPORATION OF MAGNESIUM 593

specimen tube. C to D represents the oxidation curve. At D, the system


is evacuated to a pressure of l0 -6 ram. Hg. Again a correction is made
for the convection currents in the system. E to F represents the final
evaporation rate. The oxidation is seen to follow a linear law after a
certain induction period. The thickness of the oxide film appears to
have no effect on the rate in this case. This would indicate a cellular or
discontinuous type of film. The film has little resistance to the diffusion
and final evaporation of magnesium. In fact the loss of magnesium is
greater for the thicker film than for the initial film.
Fig. 2 shows a plot of the oxidation and evaporation behavior at
450 ~ C and 2 cm. 02 pressure. In this case the oxidation is allowed to

IMtr
FIo. 4. Oxidation and evaporation of magnesium at 475* C and 0.2 em.O~.

proceed for 17.5 hours. Since the oxidation rate is very slow in the later
stages of the experiment, the oxide film is said to be protective. This
film is nearly impervious to the diffusion and evaporation of magnesium.
The oxidation and evaporation behavior at 450 ~ C and 0.20 cm. Oz
is shown in Fig. 3. Again a protective oxide film is obtained which, in
addition, is impervious to the diffusion and evaporation of magnesium.
Fig. 4 shows the oxidation and evaporation behavior at 475 ~ C and
0.2 cm..O,~ pressure. After following a linear law for the initial stages,
the oxidation rate diminishes as the film builds up.. This curve repre-
sents, therefore, an intermediate case in which the oxide film presents
a partial barrier to the diffusion of magnesium.
The complete oxidation and evaporation data are shown in Table I.
For each experiment the following are tabulated : (1) the initial evapora-
tion rate in micrograms/em.2/min, and in Angstroms./min.; (2) the

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594 E A R L A. G U L B R A N S E N

~c~ ~

~ 0 ~ 0 0 0 0 0
m ~! ~ Q Q Q Q ~ Q

~ 0 0 0 0 0 0

[--.4 ~
~ Q Q Q Q Q Q ~
~ 0 0 0 0 0 0 0 0

O0 O0 O0 O0

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O X I D A T I O N A N D E V A P O R A T I O N OF M A G N E S I U 3 [ 595

maximmn oxidation rate in microgralns/cm.-~ and Angstroms/rain. ;


(3) the final evaporation rate in micrograms/cm.2/min, and in Ang-
stroms/min.; (4) the thickness of the oxide film in micrograms/era. 2
and in Angstroms ; and (5) the total time of oxidation.
The calculations are based on a density of 1.785 for magnesium and
3.65 for magnesium oxide. From these values, the sensitivity of the
balance and the specimen area, the data may be interpreted approxi-
mately in Angstroms of film thickness. The proportionality constants
are as follows: (1) for MgO, 1 microgram/cm.'-' is approximately equal
to 27.4 A; and (2) for Mg, 1 microgram/cm.'-' is approximately equal
to 57.2 3,.
The oxidation rates measured at 475 ~ C and above follow a linear
law of weight-gain versus time. At temperatures of 450 ~ C and lower,
protective films were formed at the particular conditions of the measure-
merits. The oxidation followed a linear law, after the induction period,
for some time before reaching the protective stage. This is shown in
Fig. 3.

SCALE [
REAOtNG
WT. GAIN FINAL
~04C 9. EVAr-~'RAI'ION-
RATE
EVAC. TO 10-etTirrr H~
1060 I t~
'CONV'ECTION
OXIDATION R A T E ~ / CORRECTION
I OIV. = 1.305 x 1O-e~m
108C
7
INITIAL
EVAPORATION
II00 RATE '

1~2C

10"6mffl F ~ / 0 2 TO 6turn

II4C
0 ; 40 60 80 100 120 140 160
TIME (MIN

FIG. 5. Oxidation and evaporation of aluminum at 475* C and 0.6 era.O=.

The simple, linear, oxidation-rate law is given by the equation


W = K ( t - to) in which I4! is the weight gain in micrograms/cm.2/min.,
t is the time in minutes, to is the induction period in minutes, and K is
the linear rate law constant. The K values are tabulated in Table I
under the column titled "maximum oxidation rate." The maximum
is tabulated since in some cases a protective fihn is formed.
It is of interest to compare the shape of the curves obtained for
magnesium with that obtained for aluminum. The oxidation and
evaporation behavior of pure aluminum (99.985% A1) at 475 ~ C and
6 ram. of O~ pressure is shown in Fig. 5. The curve is approximately

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596 EARL A. GULBRANSEN

parabolic in shape and is similar to curves obtained [or iron and its
alloys. The curve does not have the induction period noticed with
magnesium. The essential difference may be due to the fact that, with
aluminum, the oxide layer is continuous and protective. The evaporation
rate is independent of the presence of the film. This indicates that
diffusion is not an important barrier to the evaporation process.
It can be noted from Table I and from Fig. 1, 2, 3 and 4 that the
1
linear rate law constant is a function of the temperature. A - - plot of
T

IG

1.0
~025oc-ooo~

o,,,,
cnl 0 2

0.!
K

MI~t

o
.01
\

.OOi
1.25 t.30 t.35 1.40
X I03
I
Fro. 6. L o g a r i t h m of K vs. - - .
T

the logarithm of K indicates a straight line relationship. This is shown


in Fig. 6. The data are complete only for the experiments at 20 cm.
of 02 pressure. The data obtained at 400 ~ C are not included because
of the large percentage error possible in the measurement. The plot
indicates that one or more rate mechanisms are involved in the reaction.

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O X I D A T I O N A N D E V A P O R A T I O N OF M A G N E S I U I v I 597

However, a mechanism must be established before a detailed analysis


can be made. Discussion of the rate law theory of oxidation has been
given by the author in a previous paper. 5
To establish the correlation of weight gain with growth of oxide
film, a series of experinlents was performed on the effect of inert gas

5 7.0 mm. Hg.


0 ~ I 0 i I I ~ b ,~ t L t t i

5 4.o ram. Hg.

0 , I 0 I I I ~ I 1 I i t

@ =.3 ram. Hg.

2 ~ x ~oH ram. Hg.


i - ., ' I I i I I I A I I

6 x io -2 ram. Hg.

O(.--J-,r~ . . . . . i I i t I

I I I I I

, ~ i I I I I r | I I

0 4. 8 12 16 20 24
TIME ( M I N)

l~Io. 7. Effect of argon on evaporation of magnesium at 450* C.

atmospheres on the evaporation of magnesium. Thus, if an inert gas


atmosphere retards the evaporation, it can be assumed that the mag-
nesium atoms are prevented from leaving the surface by collisions
with the inert gas molecules. If, instead of an inert gas, oxygen is
used, it is obviously improbable that evaporation will occur during
oxidation. The effect of nine different pressures of argon gas from
= Earl A, Gulbransen, Trans. Electrochem, Soc. $3, 301-I7 (1943),

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59~ EARL A. GULBRANSEN

10-" ram. of Hg to 7 into. of Hg on the evaporation of magnesium at


450 ~ C is shown in Fig. 7. For pressures below 1 ram. Hg of argon
gas, the magnesium will evaporate through the surrounding gas atmos-
phere. Above 1 1rim. Hg the tendency to evaporate is reduced. From
these experiments and a knowledge of the extreme reactivity of the
magnesium with oxygen, it can be concluded that the weight gain
measured is the weight of oxide formed.
The initial evaporation data from Table I are very scattered and are
not a direct function of the temperature. Other variables must be intro-
duced in order to explain the variations. The variables would include:
(1) surface area; (2) nature, thickness and conditions of formation of
the initial oxide fihn; (3) impurities present in the metal or occluded
on the surface ; and (4) time of exposure of the specimen to the evapora-
tion conditions. A study of these variables has not been attempted in
this work.
The final evaporation rates are also variable. A fihn formed at 500 ~ C
and 20 cm. of oxygen pressure and having a thickness of 875 A is non-
protective to oxidation and has an evaporation rate of 545 A/min.
Another fihn formed at 475 ~ C and 20 cm. oxygen pressure and having
a thickness of 718 _& is also non-protective to oxidation. An evaporation
rate of 183 X/rain. is observed. A film also formed at 475 ~ C but at a
pressure of 0.2 cm. of oxygen and having a thickness of 282 A, shows
marked improvement in its protective behavior to the evaporation of
magnesium. A final evaporation rate of 7.5 A/rain. is observed. Films
formed at temperatures of 450 ~ C or lower, and at various pressures
and having thicknesses of 16 to 332 X, are both protective m oxidation
and to the evaporation of magn.esium. Thus, it can be concluded that
the films which are protective to oxidation inhibit the evaporation of
magnesium. It should also be observed that the final evaporation rates
are sometimes many times that found initially before the oxidation.

CONCLUSION

A vacuum microbalance technic was used for the study of the oxida-
tion and evaporation of magnesium.
Above 475 ~ C linear oxidation rate curves with the time of oxidation
are observed while at 450 ~ C and lower the linear rate law holds only
for the initial period of oxidation. An induction period is noticed in
some of the oxidation rate curves.
An analysis of the initial and final evaporation rate curves indicates
a wide variation of rates. Films formed at 450 ~ C and lower are pro-
tective to oxidation as well as to evaporation, while those formed at
475 ~ C and higher are protective neither to oxidation nor to evaporation.

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O X I D A T I O N A N D E V A P O R A T I O N OF M A G N E S I U M 599

Resumen del art~culo: "La Oxidaci6n y Evaporaci6n de Magnesio


a T e m p e r a t u r a s e n t r e 400 ~ y 500 ~ C . "

Empleando una ,nicrobalanza en el vacio se ha estudiado la velocidad


de evaporacidn de magnesio a varias temperaturas, y la velocidad de
oxidacidn a varias presiones de oxigeno (Tabla I.). En un experimento
tipico (Fig. 1) la evaporacidn inicial a 10~" mm. de mercurio se repre-
senta por la linea AB, oxidacidn a la presidn dada pot CD, y evapora-
cidn en el vacio otra vez por EF.
S e v e que la velocidad de oxidacidn, despu6s del periodo de induccidn,
depende de la temperatura (Fig. 6). A temperaturas de 450 ~ C o
menos, la pellcula de 6xido magn6sico que se forma protege contra
evaporacidn o mils oxidacidn, pero a 475 ~ C la pelicula es muy porosa.

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