284

PLASMA-DRIVEN PERMEATION OF DEUTERIUM IN NICKEL *

R.A. CAUSEY and M.I. BASKES

Sun& Nationul Luhoruton: Liuermore, CA. USA

Key words: permeation, deuterium

The Tritium Plasma Experiment has been used to measure the temperature dependence of the plasma-driven permeation of
100 eV deuterium through nickel. Experiments were performed over the temperature range 473 K to 773 K with fluxes on the
order of 3 x 10L6D/cm2-s. In contrast to other recently reported data for hydrogen isotopes in nickel. the permeation rate
agreed with that expected from the Baskes model for the surface recombination rate coefficient. The validity of this model is
discussed. In-situ surface analysis by Auger electron spectrometry was used to measure the surface contamination during the
plasma exposure. Measurements for two samples with different amounts of carbon on the surface gave similar permeation
rates. suggesting that surface carbon does not significantly affect the deuterium surface recombination rate for nickel.

1. Introduction
2. Experimental procedures
An understanding of the permeation and reemission
of hydrogen isotopes implanted into metals is vitally All experiments were performed in the Tritium
important if calculations are to be performed on the Plasma Experiment (TPX), a gas discharge apparatus
tritium inventory and recycling for a fusion reactor. producing conditions similar to that existing at the
One factor greatly affecting these properties is the plasma edge of a magnetic fusion reactor. It has been
surface recombination rate coefficient. For tritium described in detail in another report [4].
located on or near the surface of the metal, this doeffi- High purity nickel samples 0.3 mm thick were laser
cient determines the rate at which it can recombine and yielded to flanges for attachment to the permeation
be released from that surface. If the tritium is not able section of the apparatus. They were ultrasonically
to readily recombine, there is a greater chance that it cleaned in acetone and alcohol prior to use. By having
will be sent away from the surface and remain in the the samples electrically isolated from ground, it was
metal or be released from the downstream side. Al- possible to bias them with a negative 85 V. Because the
though there is a great deal of controversy over the plasma has a space potential of positive 15 V, the
exact formula for the recombination rate coefficient, deuterium ions striking the sample surface had an en-
there is somewhat of a consensus of the effect of impur- ergy of 100 eV. The particle flux was maintained at
ities on the coefficient. Having an “unclean” surface 3 x 10’6D/cmZ-s. Sample heating was provided by a
can result in a decrease by several orders of magnitude resistance heater brazed to the back of the sample
in the recombination rate coefficient. For this reason, flange. The temperature was measured with a thermo-
results reported for the plasma-driven permeation of couple spot welded to the center of the downstream side
hydrogen isotopes in metals often differ by these quan- of the sample. The downstream side of the permeation
tities. sample was connected to a mass analyzer calibrated by
The purpose of the work described in this report was standard leaks to give the permeation rate from the
not only to provide an addition to the data base for the magnitude of the mass 4 signal. By attaching the sample
fusion community, but also to confirm or refute the and connecting downstream tubing to a rotary
data presented by Presinger et al. [l] on a study of the feedthrough, it was possible to turn the sample away
reemission of deuterium from polycrystalline nickel dur- from the plasma and in the direction of the Auger
ing implantation of 60 keV D,. Although their values electron spectrometer. This allowed the determination
disagreed by several orders of magnitude from that of the impurities on the upstream side of the sample
predicted by the model for the recombination rate coef- without exposure to air. The pressure in the plasma
ficient given by Pick and Sonnenberg [2], the slope of chamber prior to introduction of deuterium was ap-
the curve did agree. This put the results in direct proximately 1 x lo-” Pa. During the plasma discharge,
opposition to the model for this coefficient given by the deuterium pressure was maintained at 0.66 Pa.
Baskes [3]. These two models are discussed in this Pressure in the downstream line was 1 X 10 ’ Pa.
report.
3. Results and discussion

The results for a typical experiment are shown in fig.

* Supported by the United States Department of Energy 1. The deuterium particle flux on the sample was held at

0022-3115/87/$03.50 0 Elsevier Science Publishers B.V.

(North-Holland Physics Publishing Division)
 R.A. Causey, M.I. Bates / Plasma-driven permeation of deuterium in nickel 285

Time (s) 1oi5,

1 , 5pO , IO,00 , lqO0 , 20,OO , 25;O , 30,O . - High Carbon

A - Low Carbon
0 - Gas only
\ .
14
10 -

,F

E
0
0

k! 13
$ 10 -

c
.P
z

E
B
P 12
10 -

Fig. 1. Typical experiment for deuterium permeation through

nickel.
1.0 1.2 1.4 1.6 1.8 2.0 2.2 : 4

10 3 /l(K)
3 x 10’6D/cm2-s during the plasma exposure. The per-
Fig. 2. Measured and predicted permeation rates.
meation “spike” seen when the plasma was turned on
has been reported in several earlier studies [5-91 on the
plasma driven permeation of hydrogen isotopes in nickel code is quite good, it is possible that the plasma ex-
and stainless steel. The explanation given by Tanabe et posure may have caused an increase in the surface area,
al. [5] is that the radiation damage caused by the plasma resulting in an increase in the permeation rate. For the
ions create short-circuits for hydrogen to return to the plasma-driven case, the Baskes model [3] for the recom-
surface. Another, and perhaps more widely accepted, bination rate coefficient was assumed with the surface
explanation [6-91 is that the recombination rate coeffi- “cleanliness factor” equal to 1. The similarity of the
cient increases as the plasma removes impurities such as results for the two samples with different amounts of
oxygen from the sample surface. The Auger spectra carbon, and the fact that the results agree with that
recorded in this study showed the oxygen on the sample predicted by the DIFFUSE code with the surface as-
surface to be depleted during the short time required for sumed to be clean, both suggest that carbon does not
the “ spike” to occur. play an important role in determining the hydrogen
The measured permeation rates as a function of isotope recombination rate coefficient for nickel.
temperature are shown in fig. 2. Because TPX operates The DIFFUSE computer code was also used to
with a background 0.66 Pa of deuterium gas, the per- extract the recombination rate coefficients from the
meation rate for gas only was also measured and is deuterium permeation results. These results are shown
shown in the figure. For the plasma-driven permeation, in fig. 3 along with the earlier mentioned data of
two sets of data are given that correspond to different Presinger et al. [l] and the values predicted by the
amounts of carbon detected on sample surface by Auger Baskes model [3]. Also shown for comparison are results
electron spectrometry. The “low carbon” data is for a presented by Myers et al. [ll] for 15 keV deuterons and
sample where the carbon coverage of the surface was Inconel 625. Although inconel is not pure nickel, the
less than lo%%, and the “high carbon” is for a sample data are especially pertinent in that they show the effect
where the carbon coverage consistently exceeded 30%. of sputter cleaning of the surface on the recombination
The higher carbon coverage resulted from graphite ex- rate coefficient. The value reported for the sputter
periments performed prior to the nickel exposure. The cleaned sample was several orders of magnitude greater
two solid lines in the figure are the results predicted by than that for the electropolished sample. It is still below
the DIFFUSE [lo] computer code using the experimen- that predicted by the Baskes model, but was listed by
tal conditions as the input for the code. The gas only the authors as a lower limit due to the release being
runs were performed immediately after plasma ex- limited by diffusion. It is the cleanliness of the sample
posures. This was done to allow measurements with a surface that also caused the present data to agree with
clean surface. Although the agreement between the the theoretical prediction. Cleanliness here refers prin-
measured values and those predicted by the computer cipally to the lack of oxygen. The base pressure in the
 ,d,s, 6O’f.C 407’~ 30:‘~ 20:‘~ .
Tritium Plasma Experiment is comparable to that of the
other systems, but has a much higher particle flux that
continuously acts to keep the surface free of oxygen.
Myers et al. and Presinger et al. both acknowledge that
contaminant on the sample surface may have affected
their measured results.
;-:::-: The plasma-driven permeation of hydrogen isotopes
0
in nickel was also measured by Saitoh et al. [12] and
00 go o” Tanabe et al. [5]. In both of these experimental inves-
Sputter
Cleaned
tigations, emphasis was placed on the initial permeation
rate and the associated “spike”. The experiments were
not performed for sufficiently long periods of time to
get steady state permeation rates. In their study of
hydrogen permeation through nickel due to a glow
discharge plasma, Sharpov et al. [13] used a background
pressure of 4 to 15 Torr. Although they reported the
data to be plasma-driven permeation, with this pressure
and a particle flux of 3 X 10n’ H/cm*-s, the permeation
is completely dominated by the gas-driven component.
The plasma acts only to clean the surface and allow the
more rapid gas-driven permeation.

4. Theoretical model discussion

1.0 1.2 1.4 1.6 1.6 2.0 2.2 2.4 2.6

lo3 /l(K)
Fig. 4 shows a comparison of the recombination
Fig. 3. Comparison of recombination rate coefficients. coefficient calculated from the data in this report, the
curve predicted by the Baskes model [3], and the curve
predicted by the model given by Pick and Sonnenberg
[2]. In comparing the two models for the recombination
rate coefficient, there is an obvious difference in both
600-C 400-c 300-c 200-c slope and magnitude. In the Baskes model, the recom-
I I I I
bination coefficient, k,, is given by:
x - This Report
-- Baskes k = k” e(2E,-E:x)/kT
-_- r TO (1)
- Pick (1. Sonnenberg
while in the Pick and Sonnenberg model:
k, = k;) e=,/kr,
(2)
where the pre-exponent& kFo and kfb are essentially
the same, Es is the hydrogen solution energy and

Es-t% Es+E,~O,
(3)
0 otherwise,
where E, is the activation energy for diffusion. The
predicted recombination coefficients are essentially the
same for E, = 0, which is the case for most exothermic
metals. For endothermic metals, however, which is the
case of interest here, E, > 0 and the Baskes model
predicts a significantly smaller recombination coeffi-
cient in agreement with experiment.
This difference in models is due principally to the
omission of two important processes in the Pick and
Sonnenberg model. In their derivation, a balance is
assumed between the particles entering and leaving the
I I I I 1 I I

1.0 1.2 1.4 1.6 1.6 2.0 2.2 2.4 2.6 material surface. It is their assumption that atoms can
only enter the material by first being absorbed on the
lo3 m(K)
surface. It is also assumed that particles leaving the
Fig. 4. Comparison of experimental data to theoretical models. sample bulk must first reside on the surface before
 R.A. Cuusqv, M.I. Bates / Plasma-driven permeation of deuterium in mckel 281

recombining with another atom to be released. In the 5. Summary

Baskes model for the recombination rate coefficient, an
additional process is postulated, i.e. molecules can dis- The measured permeation rate of 100 eV deuterium
sociate with one of the atoms being sent directly into and deuterium gas agreed with that predicted by the
the sample bulk. In the reverse process, it is assumed DIFFUSE [lo] computer code using the Baskes [3]
that atoms from the bulk can join with atoms already model for the recombination rate coefficient. Calcula-
present on the surface and then be released. The necess- tions of the recombination rate coefficient from the
ity of these processes was first demonstrated in a report experimental data gave results that deviated signifi-
by Jwu-Shi Wang [14] in 1936. He was able to show that cantly from those reported by Presinger et al. [l] for a
at high pressures there would be a saturation of the similar study . It is believed that their results were
permeation rate and a deviation from the square root of affected by surface contamination. In agreeing with the
pressure dependence if these two processes were not Baskes model, the data disagreed with that predicted
included. Experimental evidence of continued square using the Pick and Sonnenberg [2] model for the recom-
root of pressure dependence even at high pressures was bination rate coefficient. The validity of this model is
already available at that time. questionable due to their omission of two important
More recently indirect evidence of these additional atomic transfer processes.
processes has been inferred from two experimental de-
sorption results. Comsa and David [15], using time-of-
flight measurements, found that hydrogen that had per- References
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normal than a cosine distribution. They interpreted
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their results as being due to the desorption of sub- 208.
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gen. Existence of such subsurface hydrogen has been [4] R.A. Kerst, .I. Nucl. mater. 103 & 104 (1981) 439.
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may be seen by considering a simple implantation ex-
191 A.I. Livshitz et al., from USSR contribution to INTOR
periment. In their model the desorbing flux is given by
Workshop Phase 2A (1982).
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atoms/cm*-s. Hence, simple associative recombinations Phys. Chem. 54 (1980) 1652.
[15] J. Wang, Proc. Camb. Phil. Sot. 32 (1936) 657.
as included in the Pick and Sonnenberg model is insuf-
[16] G. Comsa and R. David, Surf. Sci. 117 (1982) 77.
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[17] W. Eberhardt, F. Greuter and E.W. Plummer, Phys. Rev.
Thus we conclude that the existence of bulk related Lett. 46 (1981) 1085.
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