Importance of the surface oxide layer in the reduction of outgassing from stainless

steels
Yuichi Ishikawa and Toshihiko Yoshimura

Citation: Journal of Vacuum Science & Technology A 13, 1847 (1995); doi: 10.1116/1.579669
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 Importance of the surface oxide layer in the reduction of outgassing
from stainless steels
Yuichi Ishikawa and Toshihiko Yoshimura
Mechanical Engineering Research Laboratory, Hitachi, Ltd., Tsuchiura, Japan 300
~Received 5 August 1994; accepted 18 February 1995!
Temperature dependence of outgassing was measured for differently surface treated type 316L
stainless steel chambers in the temperature range of 25–330 °C. Based on the temperature
dependence and outgassing characteristics of major outgassing species, the mechanism of
outgassing from the stainless steel surface is discussed and the technique to produce an extremely
low outgassing surface is indicated. The following are the important findings. ~1! At temperatures
below 250 °C, the outgassing species is predominantly hydrogen, which is released by diffusive
outgassing from the bulk of the stainless steel. ~2! At temperatures above 250 °C, the contribution
from water and carbon monoxide outgassing becomes significant because of the enhanced surface
reaction to generate these gas species. ~3! The surface oxide layer formed by the oxidation in air is
predominantly iron oxide and appears to serve as a more effective diffusion barrier for hydrogen
outgassing compared with the mixed iron and chromium oxide layer formed on the fully degassed
surface. ~4! The oxidation reduces carbon contaminants on the surface which are a possible source
of carbon containing outgassing species. © 1995 American Vacuum Society.

I. INTRODUCTION
Outgassing usually limits the pressure attained in vacuum
chambers. Stainless steels are most frequently used materials
for fabricating vacuum chambers and internal hardware.
Baking and/or prebaking are currently practiced to achieve
the surface of low outgassing rate. The outgassing rates of
stainless steel surfaces are known to vary according to the
baking conditions and previous degassing history.1–5 The re-
duction of the outgassing rate with increasing baking and
previous degassing temperature is usually discussed in terms
of desorption of adsorbed gases and diffusive outgassing of
dissolved gases in the steel. In addition, the heating of stain-
less steels in vacuum or in air is known to form thin oxide
layers. Chemical composition, structure and thickness of the
oxide layers appear to be important since they alter the prop-
erties of adsorption and desorption of gas molecules on the
surface as well as the diffusion characteristics. However, the
effect of the surface oxide layer on the outgassing rate of
stainless steels has not yet been fully examined, though the
reduction of outgassing by oxidation has been reported in
several papers.2,4,6 – 8
Our particular interest was generated by the necessity for
producing extremely low outgassing chambers by a simple
and reproducible technique. The oxidation of stainless steel
surfaces seems to be the most promising technique to
achieve that goal. Figure 1 illustrates this point. It summa-
rizes the effects of oxidation on outgassing rate of stainless
steels as a function of oxidation temperature.2,4,6 – 8 Without
high temperature prebaking such as 800–1000 °C in a
vacuum furnace, it can create low outgassing surfaces as low
as 10210 Pa m/s. It has been qualitatively suggested that the
oxidation reduces carbon containing contaminants and hy-
droxide on the surface which may be the source of carbon
monoxide, carbon dioxide, methane and water, and forms the
surface oxide layer which retard the hydrogen diffusion from
the bulk.8 However, in order to lower the outgassing further,
we still don’t know how the oxide layer should be, i.e., what
should be the optimum thickness, composition, and structure.
In the present study, the mechanism of the outgassing is dis-
cussed in terms of temperature dependence of outgassing and
attempts are made to evaluate the role of surface oxide in the
reduction of the outgassing rate in stainless steels.
II. EXPERIMENT
Temperature dependence of outgassing was measured
with a test chamber and a small manifold made of vacuum
remelted type 316L stainless steel with an internal volume of
0.034 m3 and a surface area of 0.8 m2. The surface was
electropolished in phosphoric acid after buff polishing. The
system was evacuated by a 0.33 m3/s turbomolecular pump
backed by a 0.15 m3/s turbomolecular pump.
After consistently attaining a base pressure of less than
231028 Pa at 22 °C by repeated baking at 250 °C and air
exposure which is called the fully degassed surface, the tem-
perature of the test chamber was raised and lowered in the
range 25–200 °C and the total pressure and residual gas
composition changes were measured. The heating to 330 °C
was performed only on the manifold while the test chamber
was kept at 50 °C. The outgassing rate at each temperature
was estimated from a pressure buildup curve when the pump
was isolated by a gate valve. The temperature dependence of
the outgassing of each gas species was estimated from the
residual gas composition change during raising and lowering
of the temperature of the test chamber and the manifold. The
ion current increments of each gas species were obtained by
subtracting the base ion current from the measured ion cur-
rent at each temperature. The ion current measured at 25 °C
was taken as the base ion current for the test chamber mea-
surement and that at 50 °C for the manifold measurement. To
prepare the oxidized surface, the manifold was heated at
250 °C in air for 2 h followed by baking at 250 °C for 14 h.
Then the temperature dependence of outgassing for the oxi-

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 1848 Y. Ishikawa and T. Yoshimura: Importance of the surface oxide layer in reducing outgassing 1848

FIG. 1. Effects of oxidation on outgassing rate of stainless steels as a func-

tion of oxidation temperature ~summarized from Refs. 2, 4, 6, and 8!.

FIG. 2. Total pressure and ion current transients of the fully degassed surface
dized surface ~manifold! was measured similar to the fully during step cooling from 330 °C. ~The quadrupole mass spectrometer and
baked surface as described earlier. The total pressure was the gate valve were kept at 100 °C and the test chamber was at 50 °C, while
measured with a nude type Bayard–Alpert gauge calibrated changing the temperature of the manifold.!
using a spinning rotor viscosity gauge in the 1022 –1025 Pa
range using N2 gas.5 The residual gas composition was mea-
sured by a quadrupole mass spectrometer. The outgassing rate of the fully degassed surface mea-
Desorption of gases from the surface was examined by sured by the pressure buildup at 25–180 °C is compared with
thermal desorption spectroscopy and the surface chemical that of the oxidized test chamber determined in a separate
composition was measured by Auger electron spectroscopy measurement. Figure 3 shows the total outgassing rate as a
and x-ray photoelectron spectroscopy. The details of the pro- function of the inverse of absolute temperature. The data
cedures were described previously.8,9 points can be fitted by a line and the slope of the line gives
the apparent activation energy for outgassing, that is, 35.7
III. RESULTS
Figure 2 shows the total and partial pressure transients
during the step cooling of the manifold which has been kept
at 330 °C for 2 h, while the test chamber was kept at 50 °C
and the quadrupole mass spectrometer casing and the gate
valve were at 100 °C. The total pressure transient is closely
correlated with the hydrogen ~m/e52) ion current transient,
both decreasing steadily by lowering the temperature. A re-
markable difference in the ion current transients should be
noted between hydrogen and other species, that is, while
heating to 330 °C and holding at 330 °C, the hydrogen ion
current continues to increase, whereas the other gas species
show a rapid increase during temperature increase to 330 °C
and a gradual decrease during holding at 330 °C. The water
(m/e518!, carbon monoxide ~m/e528!, carbon dioxide
~m/e544! and methane ~m/e516! ion current transients
show a rather drastic decrease from 330 to 220 °C. This ap-
pears to indicate that diffusion controls the outgassing of
hydrogen while the surface reaction affects the other gas spe-
cies. This will be discussed more thoroughly later.
The similar transients were obtained for the air oxidized
surface ~the manifold only!. Although the transients show a
similar behavior, the hydrogen ion current is lower for the
oxidized surface than the fully degassed surface by a factor FIG. 3. Temperature dependence of the outgassing rate for the fully degassed
of 2. and the oxidized surfaces.

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 1849 Y. Ishikawa and T. Yoshimura: Importance of the surface oxide layer in reducing outgassing
FIG. 4. Temperature dependence of the hydrogen outgassing from the fully
degassed and the oxidized surfaces. ~Solid symbols represent the data ob-
tained from the test chamber and open symbols that from the manifold.!
kJ/mol for the fully degassed surface and 43.8 kJ/mol for the
oxidized surface, both of which are in the range of activation
energy of hydrogen diffusion in austenitic stainless steels.
This suggests that the diffusive outgassing of hydrogen con-
trols the outgassing rate of these stainless steel surfaces. The
oxidized surface shows lower outgassing rate than the fully
degassed surface, which agrees with the previous result.8 For
both surfaces the main outgassing species is hydrogen
throughout the temperature range investigated. However, at
higher temperature, above 100 °C, the evolution of carbon
containing species, especially carbon monoxide, increases
linearly with the buildup time, while the evolution of hydro-
gen appears to reach the maximum rate in several minutes
and the rate decreases with the buildup time.
Figures 4 – 8 show the temperature dependence of the out-
gassing of residual gas species expressed as the ion current
increments. For the fully degassed surface, the data obtained
from the test chamber is represented by a solid circle and that
from the manifold by an open circle. For the oxidized sur-
face, the measurement was performed only for the manifold,
which is represented by an open triangle. In Fig. 4 the hy-
drogen ~m/e52) outgassing is shown. It should be noted
that each set of data points can be fitted by a single line even
in the high temperature range and that the oxidized surface
shows lower outgassing than the fully degassed surface by a
factor of several. The apparent activation energy calculated is
38.4 kJ/mol for the fully degassed surface in 80–200 °C,
42.5 kJ/mol in 150–330 °C, 34.6 kJ/mol for the oxidized
surface in 180–330 °C. These are in agreement with the val-
ues obtained for hydrogen outgassing from the 304LN and
316L stainless steel vacuum chambers measured at 20–
500 °C by Hseuh and Cui.10 These values are close to the
activation energy for hydrogen diffusion in austenitic stain-
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1849
FIG. 5. Temperature dependence of the water outgassing from the fully
degassed and the oxidized surfaces.
less steels, 40–53.4 kJ/mol.10 It may be concluded that the
hydrogen outgassing results from the diffusive release of hy-
drogen from the bulk throughout the temperature range ex-
amined.
The water outgassing ~m/e518) is shown in Fig. 5. In
contrast to the hydrogen shown in Fig. 4, the data points
cannot be fitted by a single line for the whole temperature
range. Above 250 °C, the slope of the line changes markedly,
while below 220 °C the slope of the line is consistent for the
separate measurements. The activation energy determined is
24.6 –27.5 kJ/mol for below 220 °C and 131.8 –146.8 kJ/mol
for above 250 °C. This suggests that the water outgassing is
controlled by different mechanisms according to the tem-
perature range. The value of activation energy obtained at
high temperature agrees with the values of chemisorption
and desorption of water on the FeO surface, 125.1–134.3
kJ/mol.11 The water outgassing at higher temperature may
result from the desorption of water formed by the reaction of
surface hydroxyl groups with hydrogen.
On the other hand, the very low activation energy of about
26 kJ/mol obtained below 220 °C precludes the involvement
of any surface chemical processes in the water outgassing.
This low activation energy may suggest that a physical pro-
cess such as molecular diffusion of water through the pores
and defects in the oxide layer is operating.
Dimoff and Vijh11 discussed comparatively low values
~24.2 kJ/mol or less! of the activation energy for oxide re-
duction on stainless steels during hydrogen discharge clean-
ing in terms of a diffusion controlled physical process as the
rate determining step.
Figures 6, 7, and 8 show the outgassing of carbon con-
taining gas species, carbon monoxide, carbon dioxide, and
methane, respectively. They show the temperature depen-
dence similar to the water outgassing in which the data
 1850 Y. Ishikawa and T. Yoshimura: Importance of the surface oxide layer in reducing outgassing
FIG. 6. Temperature dependence of the carbon monoxide outgassing from
the fully degassed and the oxidized surfaces.
points are fitted by two lines with a turn at 250 °C. The
activation energy is 146.4 –158.9 kJ/mol above 250 °C and
27.1–33.4 kJ/mol below 250 °C. For outgassing of these gas
species, the same process may be involved. The higher acti-
vation energy is close to the value of activation energy for
carbon diffusion in austenitic stainless steels, 150.1 kJ/mol.12
It may lead to the suggestion that carbon diffusion from the
bulk controls the rate of outgassing of carbon containing
species. The surface reaction of carbon with chemisorbed
FIG. 7. Temperature dependence of the carbon dioxide outgassing from the
fully degassed and the oxidized surfaces.
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FIG. 8. Temperature dependence of the methane outgassing from the fully
degassed and the oxidized surfaces.
oxygen or hydrogen may be expected. The oxidation appears
to reduce the outgassing of these gas species except carbon
dioxide. This may result from the removal of carbon con-
taminants on the surface by oxidation as evidenced by the
Auger electron spectroscopy ~AES! spectrum shown later. In
the lower temperature range a very low activation energy
similar to that of the water outgassing is obtained.
IV. DISCUSSION
The outgassing measurements at elevated temperatures
clearly indicate that hydrogen is the dominant outgassing
species except above 250 °C where the contribution of car-
bon monoxide and water becomes more significant. At lower
temperatures they are minor outgassing species after thor-
ough baking. The temperature dependence of the hydrogen
outgassing can be described by a single process, that is, dif-
fusive outgassing from the bulk, while for the other major
outgassing species, the process at higher temperatures may
be different from that at lower temperatures.
Consequently, it is necessary to reduce this diffusive out-
gassing of hydrogen from the bulk in order to prepare the
extremely low outgassing surfaces. It has been reported that
prebaking at high temperatures or vacuum remelting of stain-
less steels produces the low outgassing surfaces because it
reduces the hydrogen contained in the bulk of the steel, as
demonstrated by the thermal desorption spectrum of
hydrogen.9 Hseuh and Cui10 have also demonstrated that the
hydrogen outgassing could be reduced to 1.3310210 Pa m/s
by degassing at 950 °C in a vacuum furnace.
Effects of oxidation on outgassing may be considered to
be twofold. First, the oxide layer formed on the surface acts
as a barrier for diffusion of hydrogen from the bulk. Second,
 1851 Y. Ishikawa and T. Yoshimura: Importance of the surface oxide layer in reducing outgassing
FIG. 9. AES sputter depth profiles for the fully degassed ~a! and the oxidized
~b! surfaces.
carbon contaminants on the surface may be removed by the
reaction with oxygen, thus reducing a possible source of car-
bon containing gases.
Figure 9 shows the AES sputter depth profiles for the fully
degassed and the oxidized surfaces. The surface carbon is
drastically reduced for the oxidized surface. From the depth
profiles, the thickness of the oxide layer is estimated to be
several nanometers for the oxidized surface and a few na-
nometers for the fully degassed surface.
The oxide layer of the oxidized surface is predominantly
iron oxide, while in the fully degassed surface iron oxide is
mixed with chromium oxide. The effect of the oxide layer on
hydrogen permeation behavior has been the subject of a
number of papers.13–16 It has been demonstrated that the thin
oxide layers of less than 20 nm thickness can reduce the
hydrogen permeation by several orders of magnitude because
of much lower diffusion rate in the oxide compared with that
in the steel.13 Furthermore, the layer of iron oxide ~Fe2O3!
appears to be more effective in retarding hydrogen perme-
ation than the layer of chromium oxide ~Cr2O3!, because of
its lower hydrogen diffusion coefficient.13,14 This may sug-
gest that the oxide layer of the oxidized surface can serve as
a more effective barrier for hydrogen diffusion than that of
the fully degassed surface. However, this conclusion has
been drawn from the hydrogen permeation measurements
through the layer of iron oxide formed on the iron foil and
that of chromium oxide formed on the 10-mm-thick electro-
plated chromium by air oxidation, in which cracks might
have been present. Recently, in their pursuit of superclean
technology, Ohmi and his co-workers17 have demonstrated a
procedure to prepare 100% chromium oxide layer on stain-
less steel. It is of interest to compare the hydrogen perme-
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1851
ability through the chromium oxide layer thus prepared with
the iron oxide layer prepared by air oxidation of stainless
steel. In addition, the oxide layer of the oxidized surface is
twice as thick as that of the fully degassed surface in our
case. In order to evaluate the effect of the oxide layer we
have to separate the effect of thickness from the effect of
composition, as has been done for the effect of the surface
roughness factor on outgassing from aluminum with a con-
stant oxide thickness.18
In the study of hydrogen recycling, the surface oxygen or
oxide layer on stainless steel has been found to reduce the
hydrogen permeation rate by lowering the surface recombi-
nation rate of hydrogen.19,20 However, this is not true in the
present case, because the reported activation energy for sur-
face recombination is 77.7 kJ/mol,19 almost twice as high as
what we have obtained for hydrogen outgassing.
For the gas species other than hydrogen, the outgassing
process operated at the higher temperature does not appear to
contribute to ambient temperature outgassing of vacuum
chambers. Only the lower temperature outgassing process is
of interest in the present study. The very low activation en-
ergy for the outgassing of water and carbon containing gas
species precludes any surface reaction processes and sug-
gests some physical process in operation. Although it is pre-
mature to specify the operating process, molecular diffusion
of water and carbon containing gas species through defects
and pores of the oxide layer is very plausible. Hydrogen and
carbon atoms diffusing from the bulk into the surface oxide
layer may react with the oxide and generate water and other
carbon containing gas molecules, which diffuse out to the
surface and are released into the vacuum. The formation of
thin, nonporous, defect-free iron oxide layers is expected to
further reduce the outgassing rate of stainless steels. Li and
Dylla21 have recently formulated a model for the outgassing
of water from metal surfaces with passivation oxide layers,
in which they assumed the rate of water diffusing through the
passivation oxide layer to the surface governs the rate of
outgassing. As a low outgassing surface they recommended
reduction of the adsorption area ~low surface roughness fac-
tor! and reduction of the diffusion constant ~producing a
defect-free, nonporous, passivation oxide layer!. Our direc-
tion is almost in line with theirs, but we believe that compo-
sition of the oxide layer matters as well.
V. CONCLUSION
The mechanism of outgassing from the stainless steel sur-
face is discussed in terms of temperature dependence of out-
gassing. Hydrogen is the dominant outgassing species at
temperatures less than 250 °C. Water and carbon monoxide
evolve possibly by the surface reaction at higher tempera-
tures and significantly contribute to the outgassing. However,
at lower temperatures they are not of much concern because
a thorough baking effectively reduces their outgassing. The
hydrogen outgassing can be described by a single process in
the whole temperature range. The activation energy and the
outgassing behavior of hydrogen at elevated temperatures
indicate the diffusion responsible. The oxide layer formed by
the oxidation is thicker and predominantly iron oxide, and
appears to be more effective in retarding the hy-
 1852 Y. Ishikawa and T. Yoshimura: Importance of the surface oxide layer in reducing outgassing 1852

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