Fusion Technology

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Hydrogen Permeability of Austenitic Steels

Proposed for Fusion Reactor First Wall

Valery V. Fedoro, Vasiliy I. Pokhmursky, Elena V. Dyomina, Marina D.

Prusakova & Natalia A. Vinogradova

To cite this article: Valery V. Fedoro, Vasiliy I. Pokhmursky, Elena V. Dyomina, Marina D.
Prusakova & Natalia A. Vinogradova (1995) Hydrogen Permeability of Austenitic Steels Proposed
for Fusion Reactor First Wall, Fusion Technology, 28:3P2, 1153-1158, DOI: 10.13182/FST95-
A30563

To link to this article: https://doi.org/10.13182/FST95-A30563

Published online: 10 Aug 2017.

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 HYDROGEN PERMEABILITY OF AUSTENITIC STEELS PROPOSED
FOR FUSION REACTOR FIRST WALL

Valery V.Fedorov Vasiliy I.Pokhmursky Elena V.Dyomina Marina D.Prusakova Natalia A.Vinogradova
Physico-mechanical Physico-mechanical Baikov Institute of Baikov Institute of Baikov Institute of
Institute, Lvov, Institute, Lvov, metallurgy, RAS, metallurgy, RAS, metallurgy, RAS,
Ukraine Ukraine Moscow, Russia Moscow, Russia Moscow, Russia
(0322)654646 (0322)654646 (09 5) 1358680 (095) 1358680 (095) 1358680

ABSTRACT steels EP-838 (0,05C-12Cr-14Mn-4Ni-Mo-Al), 316SS,

Crl2Mn20W (O,IC-12Cr-20Mn-IW) and Crl8Nil0Ti
The study of hydrogen diffusion parameters in (0,12C-18Cr-l0Ni-1Ti) were chosen.
austenitic steels EP-838, Cr 12Mn20W, 316 SS,
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l2Crl8Ni I OTi was carried out. Temperature dependences

of permeability, diffusion coefficients and hydrogen dis-
solution were determined and their variation with the
phase and structure composition of the steel were
analyzed. It is shown that change of alloy composition,
thermal treatment in hydrogen and modification of sur-
face by nitriding, oxidizing and by irradiation with H+
and N+ ions can lead to a decrease in hydrogen perme-
ability and thus reduce hydrogen isotope losses through
the thermonuclear reactor first wall.
2. EXPERIMENTAL PROCEDURE
Measurement of hydrogen permeability and hy-
drogen diffusion coefficient was carried out by Dines-
Barrer method from gaseous phase under I 05 Pa pressure
on the volume-metric equipment using McLeod manom-
eter [4]. The temperature range of measurements was 573-
1173 K.
Permeability of P was calculated by equation

l. INTRODUCTION (2)

The problem of hydrogen permeability of thermo-
nuclear reactor first wall arises in connection with the
use of tritium in prospective reactors. It is important to
minimise tritium leaks into the environment which can
be achieved by decrease of hydrogen diffusion param-
eters. The calculation of the first wall defence effect for
this isotope penetration was made with respect to the
limitation that tritium leak from I 0 3 MW power unit must
not exceed the value of l curie per day [I ,2].
Tritium permeability was calculated from data
obtained for hydrogen permeability using the experimen-
tally determined relation
(l)
where P - permeability
M - mass of corresponding isotope
It was shown [2,3] that depending on the tempera-
ture and the first wall material conditions it is necessary
to create a defence barrier to decrease real hydrogen flux
from 6 to I 0 3 times.
To achieve this purpose we considered the possi-
bilities of thermal treatment, alloying and modification
of surface by nitriding and by oxidizing and by H+ and
N+ ions irradiation. For experimental studies austenitic
where F- flux of hydrogen from disc sample
S and 8- sample area and thickness
P 1 and P 2 - gas pressure in front of and behind
the sample.
Diffusion coefficient (D) was determined by
Barrer formula
=
D 8 2/6T (3)
where T - time of hydrogen flux exit delay through
8-thick sample under constant temperature.
Solution of hydrogen in studied steels was calcu-
lated from the by relation S=P/D using experimentally
obtained data.
Nitriding of samples was carried out from nitro-
gen-hydrogen mixtures with hydrogen partial pressure
51 04 Pa and nitrogen partial pressure 510 4 Pa and from
gaseous ammonia (l0 5Pa). The gaseous mixture was in-
jected at room temperature and than samples were heated
up to 1173 K and exposed 2h at this temperature. Irra-
diation by nitrogen ions with 5 keY energy was carried
out under ion current density 6,25.1 0 1R ion/m 2 • Energy of
implanted protons was I MeV under flux density I 0 22 ion/
m 2 , temperatyre of irradiation - 340-350 K.
Oxidation of the surface of the studied steels was
made under isothermal annealing in air as well as by a!-

FUSION TECHNOLOGY VOL. 28 OCT. 1995 1153

 Fedorov et a!. HYDROGEN PERMEABILITY OF AUSTENITIC STEELS PROPOSED FOR FIRST WALL

ternate oxidation and reduction in gaseous hydrogen [2]. 973 773

This is necessary for formation of a 30 11m thick oxide
film which has homogeneous composition, is stable to
hydrogen effect in the temperature range up to 973 K
and improves steel heat resistance.
Changes of phase composition and structure of the
austenitic steels during thermal treatment were detected
by X-ray difraction, microspectral and metallographic
analyses. The hydrogen used in all experiments was
diffusionally cleaned by palladium and nickel filters.

3. RESULTS AND DISCUSSION

3.1. EP-838 and 316SS steels

According to the development plans of thermo-

nuclear reactor based on D-T plasma beginning from
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1979, joint work with the USA has been carried out to
study chromo-manganese EP-838 steei,316SS stainless 0,85 1,29 10 3!f,K
steel and reduced activation Cr-Mn austenitic steel of type
Fe-12Cr-20Mn-W -C as prospective first wall materials (a)
[5,6]. To determine the effect of thermal treatment on hy-
drogen diffusion parameters and the possibility of their
973 773 T,K
change by initiation of close-ordering or segregation proc-
esses in solid solution the temperature range of measure-
ments was extended to a higher temperatures than those
used in refs. I and 7 and a n urn ber of isothermal anneal-
ing processes with simultaneous evaluation of hydrogen
flux change were made.
The temperature dependences of P, D and S for
hydrogen in 316SS steel are presented on fig I a. These
can be described as follows:

P (mol/m· s Pa 112) = 2.7 · I 0· 7 · exp(-66.4 kJ/moi/RT), (4)

D (m 2/s) = 2.0 10·6 exp(-37.1 kJ/moi/RT), (5)
S (mol/m 3 Pa 112) = 0.14 · exp(-29.3 kJ/moi/RT), (6)

and for EP-838 steel (Fig. I b): JO·IO

P (mol/m s Pa 112) = 9.5 J0· 7 exp(-79.4 kJ/moi/RT), (7)

D (m 2/s) = 3.9 J0· 7 exp(-42.1 kJ/moi/RT), (8)
S (mol/m 3 Pa 112) = 2.4 · exp(-37.3 kJ/moi/RT), (9)
Annealing in vacuum in 573-1173 K temperature
range for 20h has practically no effect on the hydrogen
permeability of studied steels. Thermal treatment in hy-
drogen, which enhances diffusion processes in metals, [8]
leads to a great change of hydrogen flux value after 5 h of
annealing i.e. increase - for 316SS (Fig. 1a, curve 3) and
decrease below 980 K for EP-838 steel (Fig. I b, curve 3).
Changes for 316SS steel, caused by local atomic order
formation, are confirmed by X-ray analysis. Decrease of
hydrogen permeability of EP-838 steel can be explained
by formation of areas with close-atomic ordering Fe 3 Mn
0,85 1,29 10 Yf,K
(b)
Fig. I Hydrogen diffusion parameters in 316SS steel (a).
EP 838 steel (b): I - solubility; 2,3 - permeability; 4 - coefficient of
difTusion; 5- permeability after oxidation
type and by a -13 polymorphic transformation. Precipi-
tation of iron a-phase also takes place after hydrogen
treatment as opposed to vacuum treatment. Permeabil-
ity of hydrogen in a -phase is smaller than in y- phase so
the total effect from both factors leads to a hydrogen flux
decrease. Permeability of thermotreated EP-838 steel is

1154 FUSION TECHNOLOGY VOL. 28 OCT. 1995

 Fedorov et al. HYDROGEN PERMEABILITY OF AUSTENITIC STEELS PROPOSED FOR FIRST WALL

described as Formation of phases takes place in the near surface layer

P=(mol/m s Pa 1n) =1.5 J0- 7 exp(-68.7 kJ/mol/RT), (10)
The value of permeability corresponds to the necessary
value of trithum leak (as stated in the introduction [I ,2].
For 316SS steel, a positive effect can be achieved only by
oxide film deposition (Fig. Ia, curve 5).
3.2 Crl2Mn20W Steel
Crl2Mn20W steel has a greater content of man-
ganese (20%) as compared to EP-838 steel (14%) whereas
the latter contains 4% nickel. The main result of this com-
position change is a hydrogen permeability decrease of
6-8 times. Hence Crl2Mn20W steel does not need an
additional tritium barrier. This is obviously due to the
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(7-10 mkm thickness) and on grain boundaries. The for-
mation of phases with increased Mn content leads to the
decrease of Mn content in matrix and thus to the possi-
bility of iron a-phase formation in austenitic steel. The
diffraction maximums (211 ), (200) and (II 0) of the a-
solid solution were detected after thermal treatment of
samples in hydrogen at 673K for 40h similar these to for
EP-838 steel. X-ray difraction analysis of the treated sam-
ples after anodic etching shows that iron a-phase growth
begins at the surface and in I mm thick samples the
phase detected as deep as 0,12 mm (Fig.2). The same ther-
mal treatment of Cr 12Mn20W steel in vacuum does not
lead to a-phase formation, so the formation of a-phase
in steel is induced by dissolved hydrogen [I 0]. This kind
of research enables indentifying the period of a-phase
formation. The stability of restraining field is independ-

increase of ferro-manganese phases volume content [9].
The dependence of the hydrogen flux value on tempera-
ture can be described by equation
P=(mol/m s Pa 112)=9.0 J0- 8 exp(-65.2 kJ/mol/RT), (II)
X-ray microanalysis shows that the initial compo-
sition of Cr 12Mn20W steel is a solid solution of manga-
nese in iron. After annealing in hydrogen at I OOOK dur-
ing 40h phase precipitations with Mn content of up to
40% was detected.
b loying only affected the preexponential factor in the pen-
c
---;w-
Fig. 2 X-ray diagrams of hydrogen saturated samples from
Cr 12Mn20W steel after anodic etching for different depth:
a)- 0,04mm; b)- 0,10 mm: c)- 0.12 mm
ent of the phase-structural state of the first wall material
upon the expiration of the above period of time.
To obtain better mechanical, corrosion and radia-
tion properties the Cr 12Mn20W steel is alloyed with
dopings of carbon, refractory and rare-earth metals. Since
in this case, change of hydrogen permeability can take
place, diffusion parameters of hydrogen in such alloyed
steels were also measured. The chemical composition of
the steel is shown in Table I.
Experimental results showed that in 573-980 K tem-
perature range alloying with lanthanum (melt no.!) in-
creases the hydrogen flux value in comparison to the ini-
tial sample (melt no. 2). Alloying with the same volume
of scandium (melt no.3) decreases hydrogen permeability
1.5-2 times (Table 2). The activation energies of the pen-
etration process, Ep, for the initial sample and the sample
alloyed with lanthanum are practically the same, so al-
etration equation. Alloying with scandium increases Ep
due to the intensification of the phase transformation
process and the increase of structure heterogeneity in the
matrix and it correlates with the changes of the diffusion
coefficient and hydrogen solubility. The increase of car-
bon content (melt nos. 4, 5) leads to a 2-3 times decrease
of hydrogen permeability of Cr 12Mn20W steel. The in-
crease of tungsten and titanium content (melt no.4) addi-

Table 1 Chemical composition of Crl2Mn20W steel (different melts, wt.%)

Melt No. Fe Mn Cr w Si c Ti v Other elements

bal. 20,3 12,5 0,95 0,43 0,10 0,08 0,05 0,1 La

2 bal. 20,2 12,0 0,95 0,33 0,10 0,08 0,05
3 bal. 20,7 12,5 0,95 0,57 0,11 0,08 0,05 0,1 Sc
4 * bal. 20,75 11,57 2,01 O,Q2 0,25 0,22 0,10 0,006 B; 0,043 P
5 bal. 20,8 12,2 0,92 0,41 0,26 0,11 0,05 0,033P
* PCMA-21 steel [5). Heat No. 05289-9-580A (USA,Oak Ridge National Laboratory)

FUSION TECHNOLOGY VOL. 28 OCT. 1995 1155

 Fedorov et al. HYDROGEN PERMEABILITY OF AUSTENITIC STEELS PROPOSED FOR FIRST WALL

Table 2 Hydrogen permeability, coefficient of diffusion and hydrogen dissolution in Cr 12Mn20W alloyed steel

Temperature Po, Er, Do, Ed, So, H,,

Melt range, mol kJ mz kJ mol kJ
No. K m·s·Pa 112 mol s mol m3Pa11z mol

983-773 9.1 J0· 9 65.0 1.5 J0·7 39.6 6.210 2 25.4

2 983 - 573 9.0 10"9 65.2 9.0 J0· 6 67.3 4 .710' -2.1
3 983 - 673 J.J JO·B 68.1 2.0 J0· 6 58.3 5.JI0· 3 9.8
4 983 - 673 2.41 o·IO 47.0 1.2 I0· 8 18.8 2.1 10· 2 28.2
5 983-773 7.4 JO·IO 52.6 2.210· 8 23.2 3.1·10· 2 30.0

PoD o and So- preexponential factors in equations of penetration, diffusion and dissolution
Er, Ed- activation energies of corresponding processes H,- hydrogen dissolution heat

tionally decreased hydrogen flux value and affected posi- 1173 973
tively the strength properties of the steels.
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Above the critical temperature of phase transfor-

mation (980 K) the value of the activation energy of pen-
etration process in all specimens is practically equal
(65.3+2.0 kJmol· 1) . It can be explained by formation of
precipitates of one type, i.e. ferro-manganese intermetallic
precipitates. Consequently the change of hydrogen diffu-
sion parameters in alloyed Crl2Mn20W steel effects the
process of structure and phase transformation depend-
ing on nature of alloyed element. So alloying with scan-
dium, carbon and tungsten not only intensifies phase for-
mation processes and improves mechanical properties of
Cr 12Mn20W steel but also additionally decreases hydro-
gen permeability 3-5 times.
0,9 1,1 1,3 10 3ff,K

3.3 12Crl8Ni I OTi steel
The process of hydrogen penetration through
structural materials can be made more difficult by sur-
face modification. In this case adsorption-desorption
processes on metal-hydrogen interlayer or interaction of
gas with metal surface become important. Study of these
processes was carried out for 12Crl8Ni I OTi steel with
surfaces modified by nitriding, oxidizing or irradiation
with H+ and N+ ions.
The permeability for pure hydrogen through
12Crl8Ni I OTi steel shows that in 573-1173 K tempera-
ture range is described by equation
P::::(mol/m s· Pa 112)::::
::::(6.2+0.8) I 0· 7 exp(-70+2 kJ/mol/RT),
Thermal treatment ofEP-838 and 316SS steels has
practically no effect on the permeability value. Compari-
son of results obtained under different methods of
nitriding (Fig.3) shows that maximal hydrogen flux de-
crease takes place under saturation from gaseous ammo-
nia. Tritium losses through material of the 'reactor first
Fig.J Hydrogen permeability of 12Crl8Ni lOTi steel: 1 -initial;
2- after nitriding with a H, + N,(50%) mixture; 3- after nitriding
with ammonia; 4- after irradiation with N+ ions.
wall satisfies the stated requirement [I ,2]. Nitrogen atoms,
in contrast to hydrogen atoms, are immediately adsorbed
on metal surface and keep the constant value of activated
adsorption heat almost up to I 073 K [2].
The atoms of metals in multi-alloyed steels are char-
acterized by different chemical activity. Surface modifi-
cation by phases based on one particular components of
the alloy can be achieved when there is an excess concen-
tration of that element in the near-surface layer. So the
mechanisms of interdiffusion and regimes of thermal treat-
ment must be known to provide such conditions. Increas-
(12) ing the concentration of chromium, for example, in the
near- surface layer allows the creation of oxides with chro-
mium spinel structure stable to reduction in hy drogen.
The efficiency of the process depends on the structural
peculiarities of the oxide layer and is determined by al-
loying element content, temperature, and the oxidation
time and pressure of the oxidant. Thermal stability of ox-
ide films. especially in proton irradiation condition, was
not studied.

1156 FUSION TECHNOLOGY VOL. 28 OCT. 1995

 Fedorov et a!. HYDROGEN PERMEABILITY OF AUSTENITIC STEELS PROPOSED FOR FIRST WALL

Before the hydrogen permeability measurement,
samples from 12Cr 18Ni I OTi steel were electropolished and
oxidized on the inlet membrane side. Two oxidation re-
gimes were used: oxidation in the air (presure 12 Pa) for
I Oh at I 073 K and an alternating oxidation regime with
intermediate exposure to hydrogen for 2h (I 0 5 Pa) at the
same temperature (cyclic oxidation). Oxidation-reduction
process was carried out 3-5 times. The cycle duration of
first oxidation time was I 0-12h and duration of subsequent
ox-red cycles was I 5-20 minutes. After each oxidation or
reducing cycle degassing process was carried out in vacuum
I 0· 3 Pa during O,Sh. In the first case the oxide film is a
mixture of Fe and Cr oxides (FeO+Fep 3 +Crp) with
traces of cubic FeO Crp 3 spinel. After cyclic oxidation,
unstable oxides are reduced by hydrogen and thus the vol-
ume fraction of chromium spinel increases. Hydrogen en-
hances the diffusion of chromium atoms from the bulk to
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the first treatment regime increases hydrogen permeabil-
ity as compared to non-oxidized sample and that the
chromium spinel formation decreased hydrogen flux
value II 5-150 times. In both cases proton irradiation de-
creases hydrogen permeability and significantly changes
the activation energy of the penetration process (E p ). The
preservation effect of the chromium spinel on hydrogen
penetration under 873 K lasts 230-250 h. The proton ir-
radiation prolongs thermal stability up to 420-450 h
(Fig.4). This takes place due to adhesion improvement
and decrease of oxide film porosity. It is thus possible to
recommend the thermal treatment including joint effect
of cyclic oxidation and proton irradiation as the way to
control physico-mechanical properties of chromium
austenitic steels.
CONCLUSIONS

the surface and after the third oxidation-reduction cycle

only oxides with FeO (Fe,Cr)p 3 structure were found on I. To minimise tritium loss through first wall materials
sample surface. to the given level, it is necessary to modify their surfaces.
The results show (Table 3) that the oxide film obtained by For austenitic stainless steels this is achieved by nitriding,
oxidation or ion implantation ( 12Cr 18Ni I OTi and
316SS); for low activation chromo-manganese steels by
Table 3 Effect of oxidation and proton irradiation on
thermal treatment in hydrogen and alloying by carbon
hydrogen permeability of 12Cr 18Ni I OTi steel
and refractory metals (EP-838 and Cr 12Mn20W).
2. Hydrogen dissolved in metals enhances diffusion proc-
Surface Tempterature Permeability parametres
esses and leads to an intensification of atomic close-or-
treatment range, mol kJ
P0 , E -- dering and precipitation of iron a -phase in chromium-
m-s-Pa112 P' mol
manganese austenitic matrix.
3. The combined use of gaseous hydrogen and proton
Initial sample 1073-573 6.710·' 68.5
5.4 1Q·7
irradiation on oxide film formation increases their film
Oxidation in the air 973-573 60.8
homogeneity, improves their adhesion and thermal sta-
Oxidation in the air
bility and decreases their hydrogen permeability by up
+ irradiation by H+ 973-673 1.2 I 0· 8 64.7
Cyclic oxidation I 073-673 3.310·11 41.6 to 2 orders.
Cyclic oxidation
+irradiation by H+ I 073-673 8.210" 12 38.8

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