Materials Science and Engineering, 48 (1981) 35 - 39
The Relation between Hydrogen Desorption and the Surface Conditions of High
Purity Aluminium
.~. CSAN.~DY and K. PAPP
AL UTER V-FKI, Research, Engineering and Prime Contracting Centre of the Hungarian Aluminium Corporation,
H-1389 Budapest, P.O. Box 128 (Hungary)
E. P~,SZTOR
KFKI, Central Research Institute of Physics, H-1525 Budapest, P.O. Box 49 (Hungary)
(Received September 16, 1980)
SUMMARY
The role o f the surface oxide layer in the
outgassing process o f hydrogen was studied.
Different surfaces were prepared by heat
treatment, 24Mg+ implantation and etching.
We observed that hydrogen enrichment
occurred in the surface oxide layer o f the
magnesium-implanted samples and in samples
heat treated in air. During outgassing in the
temperature range 648 - 823 K the surface
oxide layers were changed but no continuous
crystalline oxide layer was grown. From
calculations o f Do and Q it was shown that
the effect o f the surface layer was eliminated
to the largest extent in implanted surface
layers because o f their high permeability.
1. INTRODUCTION
There are some contradictions in the
literature as to whether surface oxide layers
(natural and/or thermal layers) may influence
the hydrogen desorption process from alu-
minium.
According to the measurements of Eichen-
auer et al. [1], in the vacuum extraction of
hydrogen in the temperature range 633 -
873 K the oxide layer has no influence on the
outgassing of hydrogen. Papp and Kov~cs-
Cset4nyi [2] explained the deviation of
several orders of magnitude in the published
values of the diffusion constant as due partly
0025-5416/81/0000-0000/$02.50
35
to oxide layers and partly to the variation in
purity of the aluminium samples investigated
[3, 4].
Recently there has been increasing interest
in barrier layers which prevent the permea-
tion of hydrogen [5]. Barrier layers may be
either metals with a low permeability or oxide
layers [6]. Although it is possible to make
calculations for metal barriers, calculations
for oxide barriers present some considerable
difficulties [7].
To solve this problem the properties of the
pure oxide-free metal, the diffusion constant,
the permeability of hydrogen into the metal
and oxide layers and the thickness and geom-
etry of the oxide layer should be known.
There are especial difficulties in the inves-
tigation of thin oxide layers such as those on
aluminium and its alloys. The properties of
these layers cannot be replaced by the charac-
teristics of the bulk oxide material. A further
complication arises because during the desorp-
tion heat treatment the structure, and hence
the permeability of the oxide layer itself, is
changed [8].
Taking into consideration the above facts,
we carried out the experiments in two differ-
ent ways.
(1) The compactness of the oxide layers was
artificially disturbed by 24Mg ions and the de-
sorption kinetics were studied.
(2) The samples under investigation were
oxidized in situ and were observed in the elec-
tron microscope under the same conditions
(i.e. the same pressure and temperature) that
were used in the desorption experiments.
© Elsevier Sequoia/Printed in The Netherlands
36
2. EXPERIMENTAL DETAILS
The desorption of hydrogen from solid alu-
minium was investigated with a Mettler
thermobalance coupled to a QMG-311 Balzers
quadrupole mass analyser. A liquid nitrogen
trap was built into the system in front of the
detector for freezing out the remaining H20
and for achieving more reliable detection. The
rate of heating was 25 K min -I in all the
experiments. The change in partial pressure
was about 10 -5 - 10 -6 Pa, i.e. much higher
than the detection limit (10 -9 Pa) of the
quadrupole mass analyser. All the samples
were made of high purity aluminium enriched
in hydrogen; these samples were carefully
turned to give d = 10 mm.
Some samples were implanted with 24Mg+
using 80 kV. The implanted quantity was
about 6.24 × 1015 ions cm -2. According to
the calculations this dose produces about 2%
Mg in a depth of 100 nm. The magnesium has
a gaussian distribution in the surface layer.
During the desorption process, magnesium
was also detected with a mass spectrometer
which verified the presence of magnesium in
the surface layer of the implanted samples.
Some of the original samples were heat
treated at 673 K for 20 min in air before de-
sorption. This heat treatment thickened the
oxide layer. For comparison, desorption
experiments using the original, the heat-
treated and the implanted samples were made
under the same experimental conditions.
The desorption curves of the original, the
heat-treated and the implanted samples
at 648 K and 723 K are given in Fig. 1 and
Fig. 2 respectively. The first maximum (peak)
is attributed to the hydrogen which is evolved
from the surface layer, while the hydrogen
which is given off slowly after the isothermal
Part.
pressure
IAr.unitl
Fig. 1. The quantity of outgassed hydrogen at 648 K: - - ,
samples heat treated at 673 K for 20 rain.
temperature had been passed is the so-called
"bulk" hydrogen.
It can be seen that in the surfaces
implanted with magnesium there is much
more hydrogen than in the surfaces of the un-
treated samples. As a consequence of the heat
treatment in air, hydrogen accumulation was
also observed (Figs. 1 and 2); this occurs
partly because of hydrogen accumulation near
the surface layer during heat treatment.
During our experiments we observed that
there was no hydrogen desorption in the
sample heat treated at 673 K for 20 min in air
before the vacuum desorption process at
648 K (Fig. 1). Further, during hydrogen
extraction at 723 K the quantity of outgassed
bulk hydrogen was less than for the untreated
sample (Fig. 2). Consequently, it is assumed
that the bulk hydrogen content decreased
during the heat treatment in air at 673 K and
that at the same time the hydrogen accumu-
lated in the neighbourhood of the surface
layer (Fig. 2).
Desorption curves for untreated and
implanted samples measured in the temper-
ature range 723 -823 K are shown in Fig. 3.
It can be seen that the initial rate of desorp-
tion is temperature dependent. From the
experimental data the energy of activation
and the pre~exponential factor were deter-
mined by a method described previously [2,
9].
During our studies on the relation between
hydrogen desorption and surface oxide layers,
some of our samples were chemically treated.
The finely turned surfaces of the samples
were first etched with a mixture of aqueous
HF and CrO3 at 353 K [1] (3.5 g CrO3 was
dissolved in 20% HF); the samples were then
treated in 3.5 N HC1 and washed in acetone.
After this procedure the samples were imme-
untreated samples; - - - , implanted samples;
 37

Part. i
pcNsu~
/Ar.unit

Tisotk~.m

Fig. 2. The quantity of outgassed hydrogen at 723 K: , untreated s a m p l e s ; - - - , implanted s a m p l e s ; - . - , sam-

pies heat treated at 673 K for 20 rain.

e_
etot lites which appear at temperatures over 623 K
tO. y 4~..41..~~,- . 4 - J" - g " m - Q
[8].
The straight lines fitted to the experimental
O.S, data are the basis for the calculations of
activation energy and pre-exponential factor
0.6-
Do.
It can be seen that the best degree of
linearity is achieved for magnesium-implanted
OA.
surface layers. There is also less scatter for the
chemically treated samples than for the un-
02" treated samples.
In Table 1 the diffusion coefficients, the
pre-exponential factors and the activation
t[se~x~ 2
energies for the untreated, the implanted and
Fig. 3. Desorption curves for untreated samples ( - - ) the chemically treated samples are listed.
and for implanted samples ( - - - ) (e/eto t is the inte- In the second series of experiments the
gral of the curve at a given time divided by the total structural changes in the oxide layers during
outgassed quantity characterized by the total integral heat treatment were studied. The oxidation of
of the curve): e, 723 K; m, 773 K; ×, 823 K.
unalloyed aluminium in vacuum {1.33 ×
10 -1 Pa) has been observed by Scamans and
diately put into the vacuum apparatus where Butler [11]. They carried out their in situ
the pumping was carried out. experiments in a high voltage electron micro-
In Fig. 4, plots of the hydrogen diffusion scope AEI EM7 HVEM operated at 500 kV.
coefficients D (calculated using a method de- For heat treatment below 748 K for 30 min,
scribed previously [2, 9] ) of the untreated, only the amorphous layer thickened. Above
the implanted and the chemically treated 748 K after 5 min crystalline oxides of
samples against temperature are shown. It can density 10 s cm -2 appeared and during
be seen that the position of the log D versus further heat treatment the crystallites grew to
1 / T curves changed owing to chemical treat- a maximum size of 100 nm. For heat treat-
ment and implantation. Because of implanta- ment at 793 K the maximum size of the
tion the magnesium particles presumably crystallites did not change; only their density
break through the oxide layer and disturb it. increased (6 × l0 s cm-2).
It is possible that magnesium changes into Our in situ experiments were carried out in
MgO [10] if the samples are heat treated; a JEOL JEM 200A electron microscope
then the hydrogen permeability of the oxide operated at 200 kV. The microscope vacuum
layer could be increased by the MgO crystal- (1.33 × 10-2 Pa) was used as the oxidation
38

~'A
~ ' ~ ~'~.
%..

x "\'~'N "~,,
%

. . . .

"1.20 11,30 1.40 1.50 x 10.3

Fig. 4. The hydrogen diffusion coefficients of untreated samples (--m--), chemically treated samples ( - - o - - ) and
implanted samples ( - . - ~ - . - ) vs. temperature.

TABLE 1
The values of D O and Q for high purity hydrogen-enriched aluminium samples

Material Characterization o f the surface D O (cm 2 s-1) Q (eV)

99.999% Al Turned (1.27 ± 0.4) X 101 0.7 -+ 0.09

99.999% Al Turned, polished and implanted (8.5 -+ 1.4) × 10 ° 0.66 ± 0.01
99.999% AI Turned, chemically treated (2.3 -+ 2) × 100 0.61 ± 0.03

atmosphere; the same pressure was used in the

Mettler microbalance. The heat treatment was
carried out in the sample holder of the micro-
scope. Crystalline oxide particles were already
observed at 673 K after 18 min, but the
density and dimensions of the particles were
not significant compared with those of the
total surface. At 723 K, crystalline particles
were already observed after 5 min but, after
28 min, only a small part of the surface was
covered by crystalline particles (Fig. 5). At
848 K after 30 min there was still no contin-
uous layer of crystallites, as shown in Fig. 6.
In spite of the pressure that we used (which
is one order of magnitude lower than that of
Scamans and Butler [11] ), the m a x i m u m Fig. 5. Electron micrograph of the crystallineoxides
dimensions of the crystallites are the same as grown at 723 K after 28 rain in a vacuum of 1.33 ×
those (100 nm) that they observed. 10 -2 Pa.

Fig. 6. Electron micrograph of the crystalline oxides
grown at 848 K after 30 rain in a vacuum of 1.33 ×
10 - 2 Pa.
The in situ observations in the electron
microscope showed that the oxidation of the
surface due to the outgassing processes carried
out above 823 K in vacuum for short times
changed the surface significantly; a large part
of the surface became covered with oxide
crystallites. Presumably the outward diffusion
of protons is hindered but not blocked by
these crystallites which are situated between
the amorphous oxide and the metal [12].
The structural effects of magnesium
implantation cannot be observed directly. It
can be assumed that the oxide layers are
similar to those on alloys with a magnesium
content. The oxide layer of these alloys is
permeable because of the MgO developed in it
[8,111.
3. C O N C L U S I O N S
(1) Hydrogen enrichment occurred near the
oxide layer of the magnesium-implanted
samples; this is in contrast with the untreated
samples.
(2) Hydrogen enrichment was also observed
near the surface in samples heat treated in air
before outgassing. A definite quantity of
39
hydrogen belongs to the oxide layer and this
quantity increased owing to heat treatment.
(3) The hydrogen content of the samples
decreased during heat treatment in air at
673 K.
(4) During outgassing, the surface oxide
layer changed but no continuous crystalline
oxide layer was grown.
(5) From previous calculations [2, 9] of
Do and Q and taking the errors into consider-
ation we can conclude that there is no signif-
icant difference between samples with differ-
ent surface layers.
(6) The error in the evaluation of Do and Q
is smallest for implanted samples; this means
that the effect of the surface layer is elimin-
ated to the largest extent in this case.
ACKNOWLEDGMENT
The authors wish to thank Mrs. E. Kov~cs-
Csetdnyi for valuable discussions.
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