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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
I NTRODUCTION
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
PROCEDURE
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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.) - - . -
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592 E A R L A. G U L B R A N S E N
RESULTS
1060
I
I
IL
SCALE
108C R E A D I N G i
FINAL EVAPORATION
WT. G A I N
1120 INITIAL I
EVAPORATION
I
VAC -lO'6mmH~
l IOXIDATIO' i
i 14C
~15 HRS.
IrE
TIME (MII~'-~
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
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OXIDATION AND EVAPORATION OF MAGNESIUM 593
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
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
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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
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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
0 , I 0 I I I ~ I 1 I i t
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)
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59~ EARL A. GULBRANSEN
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
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