Jo~m~ofNucle~Mate~~

103&104(1981)483-488 483
Noah-Ho~~d~b~s~ngComp~y

P~~EAT~ON AND R~EMISSION OF D~UTERIU~IMP~T~D IN FIRST WALL MATERIALS

Tetsuo Tanabe, Naoki Saito, Yoshinori Etoh and Shosuke Imoto

Department of Nuclear Engineering,

Faculty of Engineering, Osaka University
(565) Suita, Yamada-oka 2-1, Osaka, Japan

The permeation rate and the reemission rate of deuterium during the
implantation of 20 keV deuteron have been measured for samples of nickel
and molybden~ with use of a quadrupole mass-spectrometer. The results
have shown that the behavior of implanted hydrogen is largely affected
by the radiation damage introduced by the bombardment in the temperature
range of 300-500°C for nickel and above 600°C for molybdenum. Some of
results, for example, a decrease of the permeation rate with prolonged
implantation, can be explained by a diffusion model including the
trapping of hydrogen in the damaged region.

1. INTRODU~TrON 2. EXPERIMENTAL

The behavior of hydrogen isotope Fig. 1 shows the apparatus of hydrogen

implanted into the first wall of CTR is
extremely important with respect to the
inventory and recycling of tritium.
Many experimental works on the behavior
of implanted hydrogen in metals,
particularly with respect to the
permeation phenomenon, have been carried
out using the ion beam method 11‘21 or
the glow discharge method [3,4]. In
these experiments, the implantation of
energetic ions induces severe radiation
damage into the material. In the
neighborhood of the projected range,
trapping sites may be formed and the
retention of hydrogen in the material
will be largely enhanced. This report
presents experimental data on the
permeation and reemission of deuterium
ions implanted into specimens of Ni and
MO at temperatures between 100 - 800°C,
and compares the results with a
diffusion model which takes the effect
of irradiation into consideration.
implantation and the measuring system
for hydrogen recycling. Deuterium ions
accelerated to 20 - 30 keV are focused
onto the target specimen after passing
through an analyzing magnet and an
aperture of 5mm in diameter. The flux
of the ion beam used was 5 - 50 x 1017
ionsfs.m2. In the chamber for measuring
the permeability(a), the analyzing
section is separated from the implanta-
tion section by the target specimen
which can be heated up to 800°C by a
molybdenum heater. The chamber was
evacuated to 1 x 10q7 Pa by a turbo-
molecular pump (TMP) with the pumping
speed of about 80 l/see for D2.
Deuterons which have permeated through
the specimen were analyzed by a
quadrupole mass-spectrometer (QMS). In
the irradiation chamber for the reemi-
ssion study(b), the shutter is made of
a molybdenum plate kept at 600°C, for
which the steady state with 100%

Fig&l Apparatus of hydrogen implantation

0022-3115/81/0000-0000~$02.75
0 1981North-Holland
484 T. Tutzubc ct 01.1 Dcuterium implanted irl fir.yt wull materials

reemission has been kept. When the ion Diffusion coefficients were also
bombardment to the specimen is initiated obtained from the evolution curves. The
by removing the shutter, the partial values obtained by curve fitting are
pressure of D2 is instantaneously also shown in Fig.3. The values both at
decreased due to the retention of a high temperaure (74OOC) and at
implanted deuterium in the material and temperatures lower than about 200°C fall
then is gradually increased with the near to or within the range between two
reemission of deuterium from the target straight lines representing the relation
specimen. TWO kinds of measurement for In D vs. l/T for the implantation and the
the permeation rate were made in most gas &arpiw. But those at intermediate
cases. One was the continuous measure- temperatures, where the decrease of
ment of Dz partial pressure during permeation rate for prolonged implanta-
the implantation of deuterium starting
with the opening of the shutter. It was
generally seen that the permeation rate
increased from zero to a maximum: this
phenomenon is hereafter called
"injection". The other measurement was
monitoring the change of permeation rate
which occurs after the beam is shut off
after nearly steady state conditions
with the beam on. This second
phenomenon is called "evolution".

The specimens used for the permeation

study were disks of 0.05 mm or 0.1 mm
thick of Ni and MO. Those for
reemission study were 2 x 2 cm plates
with thickness of 1 mm and 0.8 mm,
respectively for Ni and MO.

3. EXPERIMENTAL RESULTS

The changes in the permeation rate of

deuteron through a nickel specimen at
temperatures between 100 and 74O'C are
shown in Fig.2. Except the case for Fig.2 Permeation rate of deuterium
74O"C, a decrease of permeation rate is through Ni during 20 keV D+
observed after the increase at the implantation
initial stage, and the decrease is
particularly noticeable for the implan-
tations in the temperature range of 200
- 420°C. Such a phenomenon has never
been observed in the usual permeation 0 hJeCtl0~
1CP l Evolution
studies of nickel specimens with gaseous
q Reemission
hydrogen as the charging agent [1,51,
. . . Tambe et al.
and is possibly caused by trapping of
-‘-Gents et al
deuterium at some kind of defect i
introduced by the ion bombardment. The
persistence of high permeation rate seen
in the experiment at 74O'C suggests that
the defect is quickly annealed out at
this high temperature.

The value of diffusion coefficient, D,

has been evaluated by fitting the
initial rise of the permeation rate to
the injection curve calculated by the
simple diffusion theory [31 with a known
diffusion coefficient. The result
plotted in Fig.3 shows that the values
of diffusion coefficients thus evaluated
are in good agreement with those
obtained by the gas charge method [S],
although the value obtained from the Fig.3 Diffusion coefficient calcu-
injection curve is considered to nearly lated from injection, evolu-
correspond to the bulk diffusion tion and reemission data for Ni
coefficient of hydrogen in the material.
 T. Tanabe et al. / Deuterium implanted in first wall materials 485

tion is substantial, show large negative

deviations. At the temperatures in
question the permeation rate for the
evolution may not only be controlled by
the diffusion of mobile hydrogen but
also by the detrapping rate of trapped
hydrop,en. A calculation based on a
trap model described later shows that
the decay of the permeation rate is more
gradual where the detrapping dominates
than where permeation is controlled only
by the diffusion process.

Fig.4 shows the change of reemission

rate (Jr/Ji) of deuterium implanted
with incident energy of 20 keV into a
nickel specimen. The flux Ji was 2.5 x
lOl* D+/s*m2. Estimates of the apparent
diffusion coefficients were obtained by
fitting the data to reemission curves
calculated using Equation 1 161,
Jr/Ji = erf(r/2m)
where erf(y) means the error function
Af y and r is the projected range. The
values of apparent diffusion coeffici-
ents are shown in Fig.3 along with the
result obtained by Erents and McCracken
[61. Fig.3 clearly indicates that the
apparent diffusion coefficients deduced
from the reemission curves are extremely
low, a factor of 10 to 100 below those
from the evolution curves, and that the
linear relationship does not hold
between In D and l/T.
01’1
0
’
LO
’ ’
80
B ’
120
* ’
160
* ’
200
TIME (set)
Fig.5 Permeation rate of deuterium
(1) through MO during 20 keV D+
implantation
the evolution process are both smaller
than the bulk values and deviations from
the linear relationship between In D and
l/T are observed. In the case of MO,
however, these anomalies are observed
only in the experiments above 600°C.
This temperature is 200 - 300°C higher
than that for Ni. Since the diffusion
coefficients of hydrogen in Ni and MO
are similar values in the temperature
range in question, this difference can
be rather attributed to the difference
in self-diffusion or vacancy diffusion
between MO and Ni, for which the
activation energies are reported to be
97 kal/mol and 6% kcal/mol,
respctively 183.

It is therefore inferred that traps

which cause anomalies in permeation and
reemission of hydrogen for metals are
not directly created by the ion
TIME Isecl bombardment but are generated by some
process which involves diffusion of
Fig.4 Reemission rate of deuterium metal atoms at the damaged region.
from Ni during 20 keV D+
implantation

Experiments similar to those for the

nickel specimen were performed with a MO
plate. The changes of the permeation
rate and those of the reemission rate
with time after beam-on at different
temperatures are shown in Fig.5 and
Fig.6, respectively. The analyzed
result (Fig.71 is similar to the case of
Ni (Fig.3). The values of the diffusion
coefficients deduced from the injection
process agree well with the values
determined by Hill [71 using the gas Fig.6 Reemission rate of deuterium
charge method. On the other hand, the from MO during 20 keV D+
apparent diffusion coefficients from the implantation
reemission experiment and those from
486 T Tanabe et al. J Deuterium implanted in first wnll materiul,c

total concentration of trap Ct and the

concentration of trap saturated with
hydrogen. A definite number of traps is
assumed to be formed with single
0 Injection hydrogen implantation. The attempt
&- l Evolutcon
frequency for trap decomposition is
q Reemlsslon
denoted by U. The number of metal atom
HIII
-.. in the unit volume is An. The concent-
lo"- ration of solute atom as well as that of
trapped atom is given in (atoms/cm3),
0 while the concentration of traps is
expressed as a fraction (traps per metal
atoms). The same distribution function
G(x) as used by Wilson and Baskes has
also been utilized here, and the number
b is assumed to be 50. A case
corresponding to very thin specimen
(h=lO r) was chosen for the numerical
calculation in order to reduce the
computation time, where h denotes the
thickness of the specimen.

Fig.8 (a) shows the changes of the

permeation rate calculated with
appropriate values for constants.
A relatively large value for the
8 L I detrapping frequency (v = 40D/h2) leads
1.0 1.5 2.0 2.5 to a monotonic increase of the
lO?T(KI permeation rate. Whereas with a small
value (W = D/h')the rate is decreased
rapidly after the maximum. The fact
Fig.7 Diffusion coefficient calculated that the injection stage (before the
from injection, evolution and maximum) is hardly affected by the value
reemission data for MO of V supports the premise that the bulk
diffusion coefficient can be correctly
4. DISCUSSION deduced from the injection curve.

In this section, we examine the trapping Fig.9 compares two cases for the
model by performing some model evolution process. One is the case
calculations. The model developed by where detrapping occurs during the
Wilson and Baskes[9] has been modified evolution and the other is the case for
to take the effect of radiation damage the absence ofdetrapping. The former
into account and single trap species has case shows a slower decay of the
been assumed. The equations used are: permeation rate thzn the latter case.
Thus the two anomalies are semi-
&c/&t = D.62c/gx2 + G(x) - 6ct/6t (2) quantitatively explained by the
trapping model in whichtrapsare
6ct/6t = D.c.Ce/X2 - v*ct (3) generated by the hydrogen ion
bombardment in the neighborhood of the
An.Ce = An*Ct - ct (4) projected range. However the gap
between the reemission data and the
An.aCt/at = b-G(x) - p*An.Ct (5) calculated result appears to be very
large. The changes of reemission rate
Equation 2 is the Fick's diffusion calculated with the same ljarameter
equation involving the volume source values as Fig.8(a) are shown in
rate due to implantation G(x) and the Fig.8(b). A curve with a large value of
trapping rate, where ct is the V gives a monotonically increasing
concentration of trapped hydrogen. reemission rate, while the small value
Equation 3 describes the change of the of v that is used for the explanation of
trapped concentration as being other anomalies leads to a strong
controlled by the trapping rate of decrease of the reemission rate after a
mobile atom (the concentration is c ) maximum. This latter behavior was not
at traps (the concentration is Ce) observed in the experiments (Fig.4 and
and by the detrapping rate. Here x is 6, and [6,101). In order to clarify the
the jump distance and V is the attempt reemission behavior of implanted
frequency for thermal detrapping. The hydrogen, a more powerful theory than
effective concentration of trap Ce is the trapping model seems to be required.
expressed by the difference between the
 T. Tanabe et al. / Deuterium implanted in first wall materials 487

0 0.L a8
Dl Ih’ N/h)

(a) (b)
Fig.8 Permeation rate (a) and reemission rate (b) calculated by the trapping model
v = 40 D/h2, *-*.**. v = 10 D/h2, -.-*-...-.v = D/h2, p=v

(3) Kass,W.J., "Effect of Hydrogen on

Behavior of materials" AIME (1976)
327-335
(4) Gkorodetsky, A.E., Zakharov,A.P.,
Sharapov, V.M. and Alimov, V.Kh.,
J.Nucl.Mater. 93&94 (1980) 588-593
(5) Tanabe, T., Miyata,Y. and Imoto, S.,
Technol.Rep.Osaka Univ. 27 (1977)
389-396
M/h*
(6) Erents, K. and McCracken, G., Brit.
J.Appl.Phys.ser.2, 2 (1969) 1397-
Fig.9 Evolution curves with detrapping 1405
- ) and without detrapping (7) Hill, M.l., J.Metals 12 (1960)
;______, 725-726
(8) Weast, R.C., "Handbook of Chemistry
and Physics" 52nd ed. (Chem.Rubber
5. SUMMARY Publ., Cleaveland, 1972) F48
(91 Wilson, K.L. and Baskes, M.I.,
The permeation rate as well as the J.Nucl.Mater. 76&77 (1978) 291-297
reemission rate during the implantation (lO)Bauer, W. and Thomas, G.J., J.Nucl.
of deuteron with the incident energy of Mater. 53 (1974) 127-133
20 keV into the near surface of Ni and
MO has been measured. The permeation
rate showed a strong decrease after
attaining a maximum for prolonged
implantation in the temperature range of
300 - 500°C for Ni and above 500eC for
MO. In this temperature range, the
diffusion coefficients deduced from the
evolution curves gave smaller values
than those from the injection curves.
These phenomena are explained by the
trapping of hydrogen at traps which are
produced by clustering of defects
introduced by the hydrogen bombardment.
However the apparent diffusion
coefficients deduced from the reemission
data showed unusually small values,
which are not explained by the trapping
model presented.

REFERENCES :
(1) Perkins, H.K. and Noda, T.,J.Nucl.
Mater.71 (1978) 349-364
(2) MEller, W., Scherzer, B.M.U. and
Behrisch, R., Nucl.Instr.Methods 168
(1980) 289-294