Journal of Nuclear Materials

North-Holland,
Amsterdam

CHEMICAL
STAINLESS

DECONTAMINATION
STEEL

T. HIRABAYASHI,
Department
Received

179

136 (198.5) 179-185

M. SAEKI

and

OF THE TRITIUM-SORBING

SURFACE

OF TYPE 316

E. TACHIKAWA

of Chemrst~~. Japan Atomic Energy Research Institute, Tokai, Iharaki 319 -11.Japan

15 April 1985: accepted

29 July 1985

The chemical decontamination

of Type 316 stainless steel surfaces exposed to gaseous tritium has been examined by using a
technique of combined thermal desorption and chemical treatment with corrosive solutions. With the finding that the tritium
sorbed at the various sites on the stainless steel surface can selectively be eliminated by treatment with a particular corrosive
solution, the distributions
of sites and their properties
have been elucidated.
On the basis of the results, it has been
demonstrated
that a two-step chemical treatment, i.e., the dipping in dilute HCl for the whole surface corrosion and then in a
CuSO,-H*SO,
solution for intergranular
corrosion, leads to an almost complete removal of tritium sorbed on the stainless
steel surface with minimized dissolution of the bulk. It is also shown that the non-oxidizing
acids like HCl accelerate the sorbed
tritium to release in the form of HT, while the oxidizing acids like HNO, allow it in the form of HTO.

1. Introduction
Any handling of a large quantity of gaseous tritium
of high specific activity will produce various kinds of
tritium-contaminated
wastes such as tools, measuring
instruments
and apparatus,
which gradually but continuously release tritium from their surfaces. This makes
it necessary to establish a practical means for removing
tritium from the surface, and the necessity has raised
interest in the study of the interaction between gaseous
tritium and material surfaces.
In a series of experiments [l-3], the sorption-desorption phenomenon
of tritium on stainless steel was
studied and the gaseous tritium was found to be readily
sorbed on the surface of type 316 stainless steel, i.e.,
tritium contamination.
It has also become clear that
there are at least four distinct sorbed states of tritium
on the stainless steel surface [2].
In the present study, an attempt has been made to
find out an effective chemical method for removing the
tritium sorbed at various sites on the surface of type 316
stainless steel. For this purpose,
the tritium-sorbing
surface of stainless steel was chemically
treated by
dipping into various corrosive solutions which are known
to cause intergranular corrosion, pitting or whole surface
corrosion and are often used as corrosion-resistance
test
solutions.
During the treatment
measurements
were
made on both the amounts of tritium released and the
0022-3115/85/$03.30

(North-Holland

0 Elsevier Science Publishers

Physics Publishing Division)

metallic elements dissolved. Furthermore,

the thermal
desorption
spectra of tritium from the stainless steel
were measured before and after the chemical treatment.
Each solution was evaluated on the basis of the results
on removal of tritium. A two-step process - chemical
treatment in the solution for whole surface corrosion,
followed by the solution for intergranular
corrosion has been concluded
to be effective for the chemical
decontamination
of a stainless steel surface exposed to
gaseous tritium. With the present experimental
approach, furthermore,
the distributions
and the properties of sites sorbing tritium have also been elucidated.

2. Experimental
2.1. Muterials and preparation

of tritium-sorbing

specimen

A specimen (30 X 10 X 1.25 mm3) was cut from a

cold-rolled
sheet of austenitic type 316 stainless steel
and its chemical composition
was 0.06% C, 0.56% Si,
1.63% Mn, 0.024% P, 0.007% S, 13.10% Ni, 16.60% Cr,
0.0009% B, 0.026% N and 2.24% MO with the balance of
Fe. Tritium, purchased from New England Nuclear, was
diluted by purified protium to a concentration
of 59.06
TBq mol. - (T : H = 1 : 35.2) and the diluted tritium gas
(HT gas) was stored as hydride in a trap of metallic
uranium powder.

B.V.

ix0

T. ~irabay~s~i et at. / The tntium -sorbing surface qf Qpe 316 stain/es steel

Table 1
List of solutions

used for chemical

treatment

Solution

of the

tritium-sorbing

specimens

Composition

Type of
corrosion

Dilute H,SO,
Dilute HCI
C&O,-H,SO.,
CuSO,-H,SO,-Cu

5% H,SO,
5% HCl
5.5% CuSO, + 15.7% H2S0,
5.5% cuso,
+ 15.7% H,SO,
10% H&,0,
6% FeCI, +O.lS% HCI
65% HNO,

H J,O,
FeCl,-HCl
Cont. HNO,
H 2C20,

causes intergranular

corrosion

of stainless

+cu

expected

Whole surface
Whole surface
intergranular
Intergranular
(Intergranular)
Pitting
Intergranular

steel. when used as electrolytic solution.

The tritium-sorbing
specimen used in this experiment was prepared
in a similar manner to that described earlier (I]; the stainless steel specimen,
the
surface of which was mechanicaily
ground and finally
polished with a suspension of alumina (0.05 pm in grain
diameter), was baked out in a vacuum ( < 10 mPa) for 2
h at 573 K, and then exposed to HT gas of 13.3 kPa for
7 days at 298 K, followed by evacuation for 20 min at
room temperature.
The tritium still remaining on the
surface of the specimen after the procedures described
above is defined as sorbed tritium in this paper. The
total amount of sorbed tritium was (67 f 24) kBq cmmm2.
In table 1 are listed the compositions of the solutions
used for the chemical treatment of the tritium-sorbing
specimens, together with the type of corrosion expected.
These solutions are generally known as test solutions for
corrosion resistance of stainless steel; dilute H2S0, is
used for whole surface corrosion, dilute HCl for surface
etching, CuSO,-H,SO,(
-Cu)
and cont. HNO,
for
intergranular
corrosion
and FeCl,-HCl
for pitting.
H ,C,O, is used as a screening solution.
2.2. Release of sorbed tritium
The sorbed tritium was forced to release by two
methods: (1) dipping into solution, (2) thermal desorption. The process of the release experiment
was given
below.
The sorbed tritium was partially released, when the
specimen was dipped in 60 ml of various solutions listed
in table 1 for 2 or 24 h at 333 K. The release rates of
tritium in the forms of HT and HTO were measured by
means of a gas proportional
counter and a liquid scintillation counter, respectively,
in a similar manner as
previously reported [I]. The metallic elements dissolved
into the solutions were quantita~vely
analyzed by the
use of an Inductively Coupled Plasma Quantrorecorder
(Shimadzu ICPV-1000).

The tritium still remaining in the specimen after the

treatment with solutions was thermally released by using
the same apparatus as described in the previous paper
121; the specimen was heated in an He flow (30 ml
tin-)
under a constant heating rate (5.0 K min-) in
the temperature
range of - 300-1173 K and the thermal desorption rates of tritium in the forms of HT and
HTO were measured as a function of heating temperature to provide the thermal desorption
spectra of tritium.

3. Results
Three specimens sorbing tritium were first prepared
and the effect of whole surface corrosion on the removal
of sorbed tritium was examined;
the first one, was
dipped in dilute H,SO, for 2 h at 333 K and the second
one for 24 h, and then all the specimens including the
third one, which was not dipped, were individually
heated under the conditions
described above, for obtaining thermal desorption
spectra of tritium in the
forms of HT and HTO, Fig. l(A) represents the relationship between the release rate of tritium and the
dipping time of a specimen in diiute H,SO,,
and fig.
l(B) shows the thermal desorption
spectra of HT and
HTO desorbing from the specimens; the spectra (a), (b)
and (c) in figure (B) were obtained from the specimen
before and after dipping for 2 h and 24 h. respectively.
The spectra (a) were employed as a reference for comparison of spectral change, which were well reproducible and compatible
with those reported elsewhere [2].
The four distinct peaks which appeared at about 430,
540, 750 and 970 K in the spectra are designated here as
peaks HT-I, HTO, HT-lf
and HT-ijI,
respectively.
The relative amount of tritium desorbing thermally from
the specimen was (10 f 0.8)% as HT and (89 rt 0.8)% as
HTO, and the former can be further fractionated
into

T. Hirabayashi et al. / The tritium-sorbing surface of Type 316 stainless steel

8
Dipping

12
time

16

20

24

( h )

Fig. 1. The effect of whole surface corrosion on the removal of

sorbed tritium; figure (A): the release rates of tritium (0. HT;
shaded parts, HTO) from the specimen by dipping in dilute
H,SO,;
figure (B): the thermal desorption
spectra of tritium
desorbing from the specimens before [spectra (a), ----- HT; -. HTO] and after dipping in dilute H,SO, for 2h [spectra (b), 0
HT; 0 HTO] and 24 h [spectra (c); A HT; A HTO].

(4.7 f 0.2)%, (1.7 k 0.2)% and (3.7 f 0.5)% for the respective peaks HT-I, HT-II and HT-III.
Assuming a
uniform dissolution of the specimen from the surface in
dilute H,SO,,
the mean depths dissolved were estimated from the weight loss of the specimens to be 0.18
pm cm -2 for 2 h of dipping and 0.74 urn cme2 for 24
h. This means that the rate of dissolution
becomes
slower with elapse of dipping time due to the lowering
of the corrosive activity of the solution used. It is seen
in figs. l(A) and (B) that the dipping into dilute H,SO,
resulted in a release of sorbed tritium and, consequently, in a decrease in intensity of every peak, particularly the peak HT-I, in thermal desorption spectra. The
respective
amounts of tritium in the forms HT and
HTO released by dipping for 2 h in dilute H,SO, were
found to be 21 and 41% by direct measurement,
while

181

they were evaluated to be 9 and 53% from the reduction

in intensity of thermal desorption spectra.
The release behaviors of tritium in other types of
solutions were also examined. Table 2 summarizes the
results, including the data for dilute H,SO,. The dipping into dilute HCl led to a marked weight loss of the
specimen due to surface etching, through which the
sorbed tritium was effectively removed. The dipping
into FeCl,-HCl
caused an extreme weight loss of the
sample due to pitting, but it could remove no more than
50% of the sorbed
tritium.
In the case of the
CuSO,-H,SO,(-Cu)
solution, the sorbed tritium was
appreciably removed without significant weight loss. In
the table it is also noticed that the observed amounts of
HT and HTO always differ from those evaluated from
the reduction in peak intensities in the thermal desorption spectra, indicating the chemical form of released
tritium being determined
not only by the sorbed state
but also by the oxidizing property of acid used. The
dipping in dilute HCl had a tendency to make the
sorbed tritium release as HT in preference to HTO, and
hence the amount of HT observed was much more than
that evaluated from the spectral change. The dipping in
cont. HNO,, on the contrary, made the sorbed tritium
release as HTO. so that the amount of HT became
negligibly small.
In order to infer the metallic elements responsible
for the sorption of tritium, the metals dissolved by
dipping in various solutions were quantitatively analyzed
by inductively coupled plasma atomic emission spectroscopy. The results obtained are represented
in fig. 2
as proportions
of the dissolved amounts of five elements, of which the type 316 stainless steel was mainly
made up. Data with cont. HNO, were excluded from
the figure, since the amounts of metals dissolved were
too small to be exactly determined. The composition
of
the bulk of the specimen used in this experiment
is
shown in the figure for comparison. As shown in fig. 2,
the proportion of metals dissolved in the dilute H,SO,,
dilute HCl, H,C,O,
or FeCl,-HCl
solution appears to
be roughly the same as that of the bulk component of
the specimen,
while
the dissolution
in CuSO,
-H2S04(-Cu)
is characterized
by a marked increase in
the relative amount of molybdenum
accompanying
a
decrease of chromium.
With a view to obtaining information
on the relationship between the type of corrosion and the removal
of tritium sorbed at various sites, the tritium still remaining on the specimen after the chemical treatment
was thermally released to observe any change in the
thermal desorption spectra of HT and HTO before and
after the treatment.
It became apparent that the peak

T. Hiruhuyashi

et al. / The trrtium -sorbing surjace of Type 316 stumless .sieel

SUS 316 bulk

dil. t-MO4

dil.HCl

HzC204

FeCla-HC(

20
Proportion

40
of metals

60

80

dissolved

100
(wt%)

Fig. 2. The proportion

of metallic elements dissolved by dipping in various solutions for 2 h at 333 K.

HT-I in the spectra was easily eliminated by dipping

irrespective of the kind of solution used, whereas the
other peaks were considerably
altered in intensity. depending upon the solution used. Figs. 3 and 4 show two
of the most characteristic
changes of the thermal desorption spectra, which were obtained from the specimen dippped
for 2 and 24 h in dilute HCl and
CL&O,-H,SO,.
As can be seen from fig. 3, the dipping
for 2 h in dilute HCl led to a marked decrease of peak

400

700

Temperature

1000

(K 1

Fig. 3. Thermal desorption

spectra of tritium desorbing from
the specimens before [spectra (a), ---- HT; -.
HTO] and after
dipping in dilute HCI for 2 h [spectra (b), 0 HT; 0 HTO and
24 h [spectrum (c), A HTO].

T Hirabayashi et al. / The tritium -sorbing surface of Type 316 stainless steel

400

700

Temperature

1000

( K1

Fig. 4. Thermal desorption

spectra of tritium desorbing from
the specimens before [spectra (a), ---- HT; - .- HTO] and after
dipping in CuSO,-H,SO,
for 2 h [spectra (b), 0 HT; 0 HTO]
and 24 h [spectra (c), A HT; A HTO].

HT-IZZ

as well as peak HT-Z but to a very small

of peak HT-ZZ that disappeared
eventually
when the dipping was prolonged up to 24 h. The peak
HTO also decreased in intensity with elapse of dipping
time in dilute HCl but still remained faintly after dipping for 24 h. On the other hand, it is clear from fig. 4
that the dipping in CuSO,-H,SO,
resulted in a marked
decrease of peak HT-ZZ but in only a small decrease of
peak HT-ZZZ. The peak HTO decreased more slqwly in
CuSO,-H,SO,
than in dilute HCl.
Furthermore,
an attempt was made to remove the
sorbed tritium by two steps of chemical treatment; after
being dipped for 2 h in dilute HCl, by which the tritium
corresponding
to peaks HT-ZZ and HTO was not yet
completely removed as predicted from fig. 3, the specimen was further dipped for 24 h in CuSO,-H,SO,.
This two-step treatment resulted in an almost complete
removal of tritium (62% as HTO-form
and 34% as
HT-form) with a minimized weight loss (2.45 mg cmm2)
of the sample.
decrease

4. Discussion

The distribution
of tritium
stainless steel has already been
autoradiography
and observed
neous at ambient temperature
ously [2], there are four distinct

dissolved in cold-rolled
examined by the use of
to be definitely heteroge[4,5]. As reported previsorbed states of tritium

183

on the surface of stainless steel. In this work, it has been

found that the tritium sorbed in each state can selectively be eliminated by chemical treatment with a particular corrosive solution. This result will provide information on the distribution
of the sites. Table 3 summarizes the results on the distribution
of the sites sorbing tritium and the type of corrosion effective to remove
sorbed tritium, together with the related information
reported in the preceding papers [2,3]. In the following,
the distributions
and the properties
of sites sorbing
tritium are discussed.
Theoretical studies [6-81 have recently predicted that
the d electron of nickel causes a dissociation
of a
hydrogen molecule with little or no activation barrier.
This is due to the interaction between the antibonding
orbitals of hydrogen
molecules and the lobe-shaped
orbitals of the d electrons of nickel [6]. Another calculation [9] has shown that the interaction energies between
hydrogen and the transition
metal surfaces are dominated by the degree of filling of the d orbitals. Since
type 316 stainless steel consists of transition metals, the
d electron on the surface of stainless steel also seems to
play an important role in the dissociation of tritium into
atomic species. The tritrium dissociated
will subsequently be trapped on the various sites as described
below.
The peak HT-ZZZ in the thermal desorption spectra
diminished
to a significant extent as a result of whole
surface corrosion (figs. 1 and 3), but only to a limited
extent by intergranular
corrosion (fig. 4). This implies
that the sites sorbing tritium for peak HT-ZZZ do not
exist on the top of surface metal but between or under
and that they are distributed
the surface
atoms,
throughout the whole surface layer. It has been recently
revealed [lO,ll] that the hydrogen dissociated by the d
electron as mentioned
above can be trapped at subsurface sites of nickel, where the bonding is predominantly with a free-electron-like
s electron. This type of
bonding, namely subsurface bonding, is different from
either to the hydride bond and the low-temperature
hydrogen
bond [lo]. Such a bonding has also been
reported to exist with other transition metals such as
niobium [12] and is expected to be markedly stronger
than normal chemisorption.
The nickel site of stainless
steel [2,3] seems to be similar to the subsurface site of
pure nickel with regard to the trapping of tritium. The
sorption-desorption
behavior of tritium on the nickel
site of stainless steel can be understood in the following
manner. The tritium first dissociates at d electrons on
the surface and subsequently
interacts with the subsurface site of nickel in the surface layer of stainless
steel, forming a strong subsurface bonding. The bound

184

T. Hirabayashi et al. / The tritium-sorbing surface of Qpe 316 stainless steel

tritium corresponding
to peak HT-III.
thus. is thermally desorbed with a higher activation energy than the
other types of sorbed tritium [2].
From the results shown in figs. 2 and 4, it seems that
the sites sorbing tritium for peak HT-II are distributed
along the intergranule,
where molybdenum
segregates.
It is generally known that some particular
metallic
elements tend to segregate along the intergranule and to
have a scavenging
action for impurities,
especially
carbon. Among the major constituent metals of stainless
steel, the affinities for carbon decrease as follows:
Mo>Cr>Mn>Fe>Ni.
Molybdenum
having the strongest affinity for carbon
may form a certain molybdenum
carbide in the intergranule, such as Mo,M,,C,
Mo,M,C
or Mo,M,C
(M = Fe, Cr, Ni, Mn) [13-151, due to the configurational restriction
of molybdenum
having the largest
atomic radius of the major constituent metals. It is also
known that the intergranule, unstable due to the formation of such a carbide, is easily attacked by the moderate oxidizing power of Cu2+ contained in the solution
of CuSO,-H,SO,,
but the other stable surface is passivated [16]. Thus, when the tritium is sorbed along the
intergranule in an interaction with such a molybdenum
carbide, an intergranular
corrosion leads to the destruction of the sites sorbing tritium, resulting in an effective
removal of tritium for peak HT-II as seen in fig. 4.
The peak HTO in the spectra was not completely
eliminated
by either the intergranular
or the whole
surface corrosion, but efficiently by applying both corrosion processes. This experimental
fact suggests that
the sites sorbing tritium for peak HTO are distributed
not only on the surface but also along the intergranule.
As commonly accepted [17,18], O*- and OH- ions will
exist in metal oxides on the surface and along the
intergranule. Thus the tritium dissociated and sorbed on
this type of site will form an OT- ion by combining
with an O*- ion or by an isotopic exchange reaction
with protium existing as an OH- ion. This tritium will
thermally desorb in the form of HTO by the mechanism
as previously postulated [2].
The tritium for peak HT.1 was very easily eliminated
by dipping the specimen for a short time in any solution. Further, the previous experiments [2] revealed that
no dissociation
of H-T bonding was involved in the
sorption of tritium for peak HT-I. These suggest that
the tritium for peak HT-I is weakly adsorbed on the
topmost surface in the form of molecular species such as
the HT+ ion. In other words, the molecular tritium
cannot penetrate into the bulk unless dissociated, though
the size of the HT+ ion on the surface can be estimated

T. Hirabayashi et al. / The tritium -sorbing surface of Type 316 stainless steel

to be smaller than that of the T- ion [19]. This is

consistent with the results pointed out by Ransom and
Ficalora [20] that the hydrogen is chemisorbed
on iron
ion. Such a molecular species is possibly
as a Hl
trapped on the strongly chemisorbed species such as the
OT- ion, or the OH- or 0 *- ions existing intrinsically
on the surface layer, and consequently,
distributes
all
over the surface of stainless steel.
On the basis of a detailed knowledge of the properties and the distributions
of sorption sites, it has been
experimentally
demonstrated
that the complete decontamination of a stainless steel surface exposed to gaseous tritium requires two steps of chemical treatments
for the whole surface and intergranular
corrosion. The
apparent effectiveness of this two-step process has been
evidenced
The
dominated

at the end
chemical
by

the

of section

form
oxidizing

of

3.
the

property

tritium
of the

released
acid

185

intergranule;
those for peak HT-Z (430 K) all over
the top of surface.
(2) Two-step chemical treatment with the solutions for
whole surface and intergranular
corrosion leads to
an almost complete removal of tritium sorbed on
the surface with a minimized dissolution.
(3) The non-oxidizing
acids like HCl assist the sorbed
tritium to release in the form of HT, while the
oxidizing acids like HNO, allow it in the form of
HTO.
Acknowledgments
The authors wish to thank Mr C. Sagawa for analyses
by inductively coupled plasma atomic emission spectroscopy.

is
solu-

used (table 2), though that in thermal desorption is

determined primarily by the sorbed state. Non-oxidizing
acids like HCl assist the sorbed tritium to release in the
form of HT. This may be because the tritium combines
with nascent hydrogen, generated in the dissolution of
stainless steel, forming HT, even though the tritium was
mostly sorbed on an oxygen-containing
site and mostly
released as HTO in themral desorption.
On the other
hand, the oxidizing acids like HNO, seem not only to
stabilize the formed OT- ion but also to oxidize the
tritium in the forms of atomic and molecular species,
and hence almost all of the sorbed tritium is removed in
the form of HTO. As reported previously [3], the relative proportion
of HT and HTO in thermal desorption
agrees with that released in the etching treatment by the
acid solution, having a composition
of 2.4% HNO,,
3.2% HCl and 94.4% H,O corresponding
to a 1%:10
dilution of aqua regia. This may be because of the
balanced action of HNO, and HCl at this concentration. Thus the chemical forms of tritium released could
be controlled to a certain extent by selecting a suitable
acid among various oxidizing and non-oxidizing
acids.
tion

5. Conclusions
The following conclusions have been obtained from
the results:
(1) The sites sorbing tritium, which give the peak HTZZZ (970 K) in the thermal desorption
spectra, are
distributed throughout the whole surface layer; those
for peak HT-ZZ (750 K) along the intergranule,
where molybdenum
segregates; those for peak HTO
(540 K) not only on the surface but also along the

References
and M. Saeki, .I. Nucl. Mater. 120 (1984)
PI T. Hirabayashi
309.
M. Seaki and E. Tachikawa,
J. Nucl.
PI T. Hirabayashi,
Mater. 126 (1984) 38.
M. Seaki and E. Tachikawa,
J. Nucl.
131 T. Hirabayashi,
Mater. 127 (1985) 187.
[41 G.W. Powell, J.D. Braun, K.F. Chaney and G.L. Downs,
Corrosion-Nate
26 (1970) 223.
T.S. Elleman and K. Verghese, J. Nucl.
151 P.M. Abraham,
Mater. 73 (1978) 77.
161 C. Satoko and M. Tsukada, Surface Sci. 134 (1983) 1.
[71 C.F. Melius, J.W. Moskowitz, A.P. Mortola, M.B. Bailhe
and M.A. Ratner, Surface Sci. 59 (1976) 279.
181 H. Deuss and A. van der Avoid, Phys. Rev. B8 (1973)
2441.
S. Holloway and J.K. Nerskov,
Surface
[91 P.,Nordlander,
Sci. 136 (1984) 59.
F. Greuter and E.W. Plummer, Phys. Rev.
WI W. Eberhardt,
Lett. 46 (1981) 1085.
1111 M. Lagos, Surface Sci. 122 (1982) L601.
WY M. Lagos and I.K. Schuller, Surface Sci. 138 (1984) L161.
Bull. Japan Inst. Metals 1
[I31 Y. Imai and T. Masumoto,
(1962) 411 and 466 (in japanese).
A. Baumel
and E. Schmidtmann,
Arch.
[I41 H. Thier,
Eisenhuttenw.
40 (1969) 333.
Metall. Trans. 11A (1980)
[I51 A. Inoue and T. Masumoto,
739.
Designation
A-393-55,
Conducting
Acidified
[161 ASTM
CuSO, Test for Intergranular
Attack in Austenitic Stainless Steel (1955); Fed. Test Method, Std. No. 151, Metals
Test Method (1956).
P71 R.O. Adams, J. Vat. Sci. Technol. Al (1983) 12.
[181 J.E. Castle and C.R. Clayton, Corrosion Sci. 17 (1977) 7.
[I91 R.W. Pasco and P.J. Ficalora, Surface Sci. 134 (1983) 476.
PO1 C.M. Ranson and P.J. Ficalora, Met. Trans. 11A (1980)
801.