Journal of Nuclear Materials 152 (1988) 139-145 139

North-Holland, Amsterdam

HYDROGEN IN 316 STEEL - DIFFUSION, PERMEATION AND SURFACE REACTION

D.M. GRANT, D.L. CUMMINGS and D.A. BLACKBURN

Oxford Research Unit, The Open University, Boars Hill, Oxford, OX1 5HR, United Kingdom

Received 3 November 1987; accepted 2 February 1988

The flow of hydrogen through 316 steel is strongly influenced by surface reactions. An experimental investigation using the
technique of pressure modulation shows macroscopic flow can be described by the diffusion and permeation coefficients:
- (6.30+0.11) x lo3
D/(m* s-l) = (7.3*0.9)X10-’ exp
T/(R) I’
-(8.19~0.08)x103
P,,,/(mol s-r m-l Pa-‘/*) = (8.1 f0.7) x10-’ exp
T/(R) I’
and a surface reaction consistent with the chemical equation
krp
HZ (gas) = ZH(solid).
k,r=

The actual rate constant values measured cover an order of magnitude at each temperature and depend on surface
preparation. The fastest reaction was on in situ hydrogen ion beamed cleaned surfaces, the surface coefficient for this case
being:

1
- (9.71*0.10) x 10s
k,/(mol s-t mm2 Pa-‘) = (3.2kO.3) x10-* exp
V(R)

1. Introduction tions limiting entry of hydrogen into the solid through

Design studies for fusion reactors call for an exten-
sive range of data on potential constructional materials.
Such requirements include information on the way in
which the isotopes of hydrogen move through the
austenitic stainless steels. In question are the rates at
which these isotopes, notably tritium, move through the
body of these materials, the quantities of isotopes likely
to accumulate in them, and the degree to which surface
conditions are likely to influence flow.
The present study represents a contribution to this
wider objective. It concerns the macroscopic flow of
hydrogen in a 316 steel and seeks to characterise it by
three coefficients: diffusion, permeation and surface
reaction. A first objective of the work was to provide
estimates of diffusion and permeation coefficients de-
monstrably independent of surface conditions. Its prin-
cipal objectives, however, were to characterise the reac-
clean surfaces, to describe them by coefficients, and
then to explore the variation in superficial rates caused
by controlled oxidation.
While permeation and diffusion coefficients are well
known, those describing surface reaction are rarely mea-
sured. Some authors have examined the reduction of
flow rates caused by superficial oxides by treating the
data as a fall in permeation rate [l-3]. Others have
avoided surface limitation of flow [4,5] by coating
surfaces with a thin layer of palladium, by sputter
cleaning, or by both. Investigations of the rates at which
gas flows through solids must ultimately include surface
coefficients since, at sufficiently low pressures, these
coefficients are the ones which limit flow.
Superficial flux limitation can be described by two
functionally related coefficients. One is the rate con-
stant for direct dissociative chemisorption: the other is
the rate constant for recombination. Perkins and Noda

0022-3115/88/$03.50 0 Elsevier Science Publishers B.V.

(North-Holland Physics Publishing Division)
140 D.M. Grunt ef al.
[7] have estimated dissociative chemisorption coeffi-
cients directly and, in a recent review, Le Claire [6]
estimated coefficients from flux-pressure data reported
by Axtmann et al. IS] and by Salmon and Randall f9].
Braun et al. [lo] were able to estimate coefficients
describing recombination rates by relating the near
surface deuterium concentration to the release rate from
a membrane by using the D(3He+, p)4He reaction to
determine surface concentration.
Relatively few studies have reported on the surface
coefficients describing the entry and exit of hydrogen
from steel. This study on a 316 steel follows a previous
one on 304 steel which described surface reactions and
provided surface independent data on bulk permeation
and diffusion coefficients. It is designed to allow a
comparative study of the surface and bulk coefficients
which describe the flow of hydrogen through these
steels.
2. Experiment
The experimental technique chosen was gaseous per-
meation through a foil specimen driven by harmonic
variation of diffusant pressure. When permeation is
diffusion limited, this type of experiment allows per-
meation and diffusion coefficients to be derived simul-
taneously from measurements of the frequency varia-
tion of the phase difference and relative amplitude of
input and output pressure modulations. It also allows
estimation of surface coefficients if experiments cover a
pressure range in which there is appreciable surface
inhibition of flow. Modulation experiments have a sig-
nificant advantage over conventional time-lag ones since,
through Fourier analysis, time averaging, and frequency
scanning, extremely precise estimates of time varying
flows become possible. It is this which makes it realistic
to attempt the assessment of flux measurements in
systems where permeation may be inhibited by surface
reactions of some complexity. The experiment has been
described in detail elsewhere [ll].
For this work three types of surface were prepared
on two different foil thicknesses. The specimens used
were:
chemically cleaned followed by in-situ irradiation of
both surfaces using a hydrogen ion beam at 4 kV,
current density 5 X lo-’ A m-’ for 100 h;
as above followed by baking in air at 0.1 kPa for 12 h
at 973 K to produce a stable oxide layer;
an intermediate treatment with chemical cleaning
followed by in-situ irradiation by a hydrogen ion
beam but for only 24 h.
Hydrogen in 316 steel
In each case both surfaces of the foil were given the
treatment specified, the experimental apparatus con-
taining a ion gun in both the input and output cham-
bers. Specimens were of thickness 0.05 mm or 0.1 mm.
The specimen described as being subject to an inter-
mediate treatment was in fact the first specimen sub-
jected to ion beam cleaning and subsequent tests showed
the irradiation to have been insufficient to produce a
properly stable condition.
3. Analysis
The propagation of modulations in flux and con-
centration of a gaseous diffusant through a solid foil is
conveniently described by linear equations in which
diffusion and solubility, as well as surface and trapping
rates, appear as constants [12,13].
The basic physical system considered here is a foil of
area y and uniform thickness f separating two experi-
mental chambers. The entry chamber contains diffusant
gas whose pressure, p, is subject to a continuous
harmonic modulation of small fractional amplitude at
angular frequency o about a central value ps. This gives
rise to pressure modulation of the exit chamber which is
pumped continuously. The exit chamber pressure p’
modulates about a central value p,’ set by the chamber
volume V pumped at fixed speed S, and is attenuated
and phase lagged with respect to the modulation of the
entry chamber.
Conditions within the foil vary with position, x, and
time t, and are discribed by the diffusant concentration,
c(x, I) and its flux J(x, f).
Positions adjacent to the entry surface are repre-
sented by x = 0 and those adjacent to the exit surface
by x = I. It is supposed that flow within the foil is by
simple diffusion, with coefficient D, and that there are
no traps.
Flow through the surfaces is described by the single
reversible reaction:
k,p
H,(gas) + 2H(solid), (I)
k2c2
where rate constants k,, k, describe the entry surface
reaction and rate constants: k;, k; describe a similar
reaction at the exit surface. Defining equations for the
fluxes are:
J(0, t) = k,p - k,c(0)2, (2)
J(I, t) = k;c(1)2 - k;p’. (3)
Experiments provide measurements of the phase lag,
tli, between p and p’ and of the modulation amplitudes
 D.M. Grant et al. / Hydrogen in 316 steel 141

] p ] and 1p’ 1 under conditions where ps, p,’ S, V, y

and I are known.
The final equations derived [13] are:
@=
etan{tanh{+f+gtan[+htanh{ ?r
arctan
(e-ftan[tanht+gtanh{-htanl 4 ’
-1
(4) D

+ g2 + h2) cash 23

+ ( e2 +f2 - g2 - h2) cos 23

‘t
0
l

+2(eg+_F) sinh2[+2(fg-eh) sin2[),

(5)
where:

e=f-l

ii
Ps- 2
)1’2(k;JJ112+
$
1
3
(6)
Pm \

1 I I I I
lo-l4
1.0 1.2 1.4 1.6 1.8 2.0

I=1
J6. Fig. 1. Variation of diffusion coefficients, D (upper curve), and
permeability, P,,,, with reciprocal temperature. Key to symbols:
In the above, K,, is the Sieverts coefficient for the (A) 1.0~ 10e4 m thickness, insufficient irradiation by ion
solubility, and J,, the steady state flux, is derived from beam, partially cleaned; (m) 5.0 X 10U5 m thickness ion beam
the equation: cleaned; (0) 5.0 x 10m5 m thickness oxidised on both surfaces.

Using these equations, data sets showing how @ and

1R I -I vary with o for different values of pS allow
evaluation of the constants D, K,,, k, and k;. The treated in a single calculation. The set consisted of pairs
constants k, and k; may also be derived using: of values for @ and I R I -’ covering, usually, 14 fre-
quencies and 6 pressures. An iterative, non-linear,
KS,= (!k)‘“- (!$)‘“, (11) simultaneous least squares fit of the three coefficients
D, P,,, and k, was made to the data for @ and I R I -’
which is a standard relationship that follows from con- versus w’/’ using eqs. (4) and (5).
sideration of steady state flows. It was found that convergence problems tend to arise
Analysis is conveniently done by least squares fitting if k; is included in the refinement procedure. For this
of curves for @ and IR I -I versus w’/*. A point to reason the values of k; were constrained by considera-
note about the analysis is that eq. (10) avoids the need tion of the symmetry of the surfaces involved. For both
to know the steady state flux, J,, so no imprecision arise the ion-beamed and oxidised specimens, entry and exit
from outgassing of the exit chamber. surface treatments were identical, and the analyses were
conducted with k, = ki.
Best fit values of diffusion and permeation coeffi-
4. Results
cients for the three samples are shown in fig. 1 and
To derive coefficients, the complete data set for a corresponding surface coefficients in fig. 2. A least
particular temperature and surface preparation was squares fit to the collected diffusion and permeation
142 D. M. Grunt et (I!. / Hydrogen in 316 steel

For the foil oxidized on both surfaces:

k,/(mol s-’ mm’ Pa--“)

1.
- (6.97 _c0.23) x IO3
= (1.3 L-0.3) X 10-j exp
T/‘(K)
(16)
Note the cleanest surface has a higher rate constant and
higher activation energy than the oxidised and inter-
mediate treatment.
At fixed temperature and frequency, a consequence
of eq. (4) is that the phase lag varies with the steady
state pressure, pS, of the entry chamber. The variation
has not been described explicitly, but is readily com-
puted for any specified combination of D, P,, k, and
k;: it is also easy to show that the total range of phase
variation is n/4 for each surface in which the sorption/
desorption reaction takes place at finite rate [13]. For a
lo-lo ’ , I , I I symmetric foil, cleaned or oxidized on both sides, the
1.0 1.2 presumption that k, = ki thus leads to the expectation
1.4 1.6 1.8 2.0
that the phase lag wiIl increase by n/2 between very
high and very low pressures.
Fig. 2. Variation of surface rate constant, k,, with reciprocal Fig. 3 shows examples of the observed variation of
temperature. For key to symbols see fig. 1. phase lag with entry chamber pressure together with

coefficients for the temperature range 502 < T/(K) <

X63 gives:
D/(m2 s- “) = (7.3 t_ 0.9) x lo-’
xexp -(6.30 LiZ0.11) X lo3 , (12)
T/(K) I
P,/(mol s.-’ m-r Pa-‘j2)
- (8.19 f 0.08~ x lo3
= (8.1 f 0.7) x lo-’ exp
T/‘(K) I’
(13)
The surface rate constant for an ion-beam cleaned
surface is best described by:

1,
k,/(mol s-’ m-’ Pa-‘)

= (3.2 rtr:0.3) X lo-* exp -(9’71$~~~’ ’ lo3

(14)
while for surfaces subjected to partial ion-beamed clean-
ing:
k,/(mol s-l my2 Pa-‘)

1.
PAW
= (1.4 f 0.1) X 10e4 exp
1 -(7*38$~~~) ’ lo3

(151
Fig. 3. Variation of phase lag, Cp, with entry pressure, ps, at
fixed frequency and temperature.
X 10e4 m and partially
Specimen thickness was 1.0
cleaned by ion beam. Key to symbols:
(A) 101 mHz; (m) 357 mHz; (e) 625 mHz, ali at 810 K.
 D.&i. Grant et al. / Hydrogen in 316 steel 143

ent ways, and had markedly different rates of surface

reaction. This is in accord with previous work on 304
steel [ll] in which the same analysis was used and
confirms that it seems genuinely to provide surface
independent coefficients.
Austin and Elleman [23] found that “types 304 and
316 stainless steel yield essentially identical results”.
This is well confirmed in the present work on diffusion
coefficients and to a lesser extent by the coefficient for
permeation. From [ll] the ratio D,,,/D,,,may be
written

1
D - (0.3 x 103)
2=1.68exp
0316
(17)
T/(K) ’

while that for P,,,3,,4/Pm,316 may be written:

P
10s 10s 104 10s m,304 = 0.596 exp (18)
P m,316
Over the experimental range, 549-965 K, therefore, the
ratio for diffusion rates is:
Fig. 4. Variation of phase lag, @, with entry pressure, ps, at
fixed frequency and temperature. Specimen thickness was 5.0 0.92 c D304/D,,,
< 1.23, (19)
x10-’ m thickness. Solid symbols ion beam cleaned, open while that for permeation is
symbols oxidised on both surfaces, partially cleaned by ion
beam. Key to symbols: (A) 101 mHz; (D) 357 mHz; (e) 62.5 0.89 < P~,~~/P~,~~~
< 0.73. (20)
mHz, all at 573 K. Collected diffusion and permeation coefficients are
shown in fig. 5 and fig. 6 respectively. Comparisons
curves computed from the best fit values for D, P,,, and
k,. Points to note are that:
the full a/2 phase shift is distributed over the pres-
sure range (IO-’ -104) Pa, a variation in pressure of
over six orders of magnitude and far beyond the
equipment range of (lo’-104) Pa;
the top curve, that for 160~second period, shows
evidence of control by both specimen surfaces since
the observed phase shift of 0.32a, while less than the
value rr/2 associated with full two-surface control, is
greater than the value 7r/4 associated with a single
surface;
even at a pressure of lo4 Pa, flows are not com-
pletely diffusion limited.
Fig. 4 shows how phase lags change when surfaces
are oxidised. Some convergence of both data and com-
puter curves may be seen towards the higher pressures
but, even at the highest pressure, the difference is sig-
nificant. This suggests that even high pressure data, 10-14,
..O 1.5 2.0 2.5
when interpreted as coming from a clean specimen
subject to diffusion limited flow, will be in error.
lo3 x [T,‘(K)]-’
5. Discussion Fig. S. Variation of diffusion coefficient, D, with reciprocal
temperature: comparison with other work. Key to symbols: (A)
A high degree of internal consistency was found various steels [21,24]; (B) 304 [19]; (C) 310 [18); (D) 309 [14];
among diffusion and permeation coefficients derived (E) 321[16]; (F) 304 [7]; (G) 304 [15]; (H) 347 [22]; (J) 304 and
from specimens whose surfaces were prepared in differ- 316 [23]; (K) this work.
144 D. M. Grunt et 01. / H_ydrogen in 316 steel

most an order of magnitude at the high temperature end

of the experimental range. Comparing this with the two
orders of magnitude span observed with the 304 stain-
less steel [ll] is interesting. It may suggest that oxidised
304 stainless steel provides a superior surface barrier to
hydrogen permeation than oxidised 316 stainless steel.
However, more data are required and other considera-
tions such as the surface oxide cracking [25,26] must be
accounted for.
Few measurements of surface coefficients have been
made so the possibilities for checking the measured
values for external consistency are limited. Graphs
showing the available data are shown in fig. 7 together
with coefficients taken for this work and that reported
earlier on 304 stainless steel [ll]. No direct comparison
for 316 stainless steel appear to be available. Measure-
ments on 304 steel by Axtmann et al. [8] and 347 steel
by Salmon and Randall [9] are close in both magnitude
and activation energy to those results given here. The
work of Perkins and Noda (71 on 304 steel is a factor of
10~x ~T/(K~~-’
Fig. 6. Variation of permeation coefficient, P,,,, with reciprocal loo
temperature: comparison with other work. Key to symbols as
in fig. 5. Dotted band corresponds to mean curve of Le Claire
]171. 10-s

with these reported works on stainless steel has been

discussed in detail for our previous work on 304 stain- 10-4
less steel [II] and as can be seen from eqs. (19) and (20)
it need not be repeated here.
A feature of the surface coefficients noted earlier is 10-s
that they show a definite Arrhenius variation with tem-
perature for every surface condition examined. It must
be emphasised therefore that this is not a spurious 10-s
consequence of the data analysis procedure. A true
simultaneous fit for D, Pm and k, was made for each
temperature and each surface condition. No variation of lo-‘0
Arrhenius type was built into the calculation of k, by
fitting residual data after best values had been found
for D and P,. Since the surface coefficients are derived lo-Is_
1.0 1.2 1.4 1.6 1.8 2.0
from data which span a factor of some lo3 in pressure,
it does seem that the simple two rate constant model
using just k, and k, to describe surface reaction gives lo3 x [T/(K)]-’
a good representation of surface phenomena over a
Fig. 7. Variation of surface rate constant, k,, with reciprocal
useful range of physical conditions.
temperature: comparison with other work. Key to symbols:
Comparisons of 316 surface rate coefficients with
[this work, 3161: (D) 5.OX1O-5 m ion beam cleaned; (E)
previous work on 304 steel [II], fig. 7, show the coeffi-
5.0 x 10m5 m oxidised both surfaces; (F) 1.0 X 1O-4 m partially
cients for ion beam cleaned surfaces, k,, for the two cleaned by ion beam; [this lab.] (A, B, C) 304 [ll]; [other
steels to be in quite close agreement. They are within a work]: (G) 304 [8]; (H) 347 [9]; (J) 304 [7]; (K) 304 [10,20]; (L)
factor of 2 of each other with k1,316/k,.3,,4 - 1.8. The theoretical values using Baskes model [28]; (M) theoretical
span of variation of k, with surface treatment covers at maximum (171:
 D.M. Grant et al. / Hydrogen in 316 steel
lo4 from those quoted here and lie comparatively close
to the theoretical maximum of Le Claire [17].
Shown also are data from the series of experiments
by Braun et al. [lo] which use direct measurement of
surface concentration to provide estimates of the surface
recombination rate, k,, for deuterium on 304 stainless
steel. Values were converted to k, by use of eq. (11).
Baskes [28] and Pick and Sonnenberg [27] have
estimated recombination rates theoretically. Baskes re-
lates the rates to the bulk coefficients D and k,, so,
using eq. (11) he also gives an estimate for the coef-
ficeint used in this paper.
Baskes theory requires that the activation energy of
k, be the sum of the activation energies for the diffu-
sion and solubility coefficients. The value thus derived,
8.2 x 103/T/(K), is acceptably close to our experiments
directly estimated value of 9.7 X 103/T/(K) as shown
in fig. 7; the Baskes theory predicts a value of k, an
order of magnitude greater than that measured here.
This can be interpreted in terms of Baskes work as due
to a sticking coefficient of about l/50 rather than the
value l/2 used’ by Baskes. The Pick and Sonnenberg
model provides no useful estimate for the coefficient k,
used here since its underlying assumption, that all arriv-
ing molecules are absorbed, implies that k, takes its
maximum value.
6. Conclusions
Pressure modulation experiments on 316 and 304
stainless steel provide data on hydrogen diffusion and
permeation of high internal consistency under a wide
range of surface conditions. Surface rates are well
described by a simple reversible reaction involving two
constants, the rates showing an Arrhenius variation
with temperature. Ion beam cleaning of surfaces pro-
vides high, and reproducible, surface rates while chem-
ical preparation gives substantially lower rates. Oxidised
surfaces are also well described by a two rate constant
model and surface coefficients show excellent Arrhenius
temperature variation. Evidence so far suggests that the
oxide on 304 austenitic steel is a more effective barrier
to hydrogen permeation than is that on 316 steel.
Acknowledgements
We wish to re ord our thanks to Cull-nun Labora-
tory, Euratom/’ &A EA Fusion Association for sup-
porting this work under contract CUL330. We wish also
to thank the Open University Research Committee for
the award of an equipment grant.
145
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