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Fusion Engineering and Design 14 (1991) 309-319 309

North-Holland

Corrosion of Cr-Mn based austenitic stainless steels


by the lithium-lead eutectic Pb-17Li
V. C o e n a, H. K o l b e a, L. Orecchia a, M. Della Rossa b
Commission of the European Communities, Joint Research Centre, Ispra Establishment, a Institute for Advanced Materials,
b Safety Technology Institute, 21020 Ispra (Va), Italy

Submitted May 1990; accepted 1 August 1990


Handling Editor: G. Casini

The compatibility between the lithium-lead eutectic and different Cr-Mn steels has been studied in the temperature range
723 K in capsules in a rotating furnace for times up to 9500 h and in a thermal convection loop for 4200 h with a z~Tof 50 K.
The corroded specimens have been examined by metallographic and SEM analysis.
It is shown that the corrosion mechanism consists essentially of the dissolution of Mn in Pb-17Li with the formation of a
porous ferrite layer in which penetration of Pb and Li has been observed.
No grain boundary attack has been observed. The behaviour of the different steels is reported together with semiquantita-
tive analysis of corrosion layers.

1. I n t r o d u c t i o n alternative steels with modification to eliminate the


elements that lead to high levels of long lived activity
after irradiation with 14 MeV neutrons. One of the
Thermonuclear reactions do not intrisically lead to
requisites [1] is that post service contact-dose rate should
the generation of radioactive products but only to in-
not exceed 25 mSv. h -1 after a decay period of 100
duced radioactivity in the structural and blanket materi-
years. This means that Ni should be replaced by Mn,
als.
Mo by W and Nb by Ta.
In most conceptual design studies for fusion reactors
To decrease the production of 14C arising from N it
it is envisaged to use either austenitic stainless steel of
is also necessary to reduce the N content of the steels.
the type AISI 316, ferritic or martensitic steels as struc-
JRC-Ispra is widely involved in the characterisation
tural and blanket containing material.
of C r - M n austenitic stainless steels for possible use as
It is important for safety requirements to minimize
low activation materials in fusion application [2-6].
the problems associated with the induced radioactivity
In this study we report on the compatibility of this
of the above mentioned materials and to develop "Low
family of steels with the lithium lead eutectic Pb-17Li
Activation" materials. The term low activation is used
which is envisaged as a liquid tritium breeder in the
[1] to denote any material exhibiting a residual activity
European Fusion Technology programme.
below that of conventional stainless steels.
In order to obtain this result three route can be
followed
- Elemental substitution in existing and well-tested 2. M a t e r i a l s
materials such as steels,
- D e v e l o p m e n t of novel alloys and ceramic based 2.1. C r - M n steels
materials,
- Use of isotopically-separated elements. The different C r - M n steels investigated were devel-
The most immediate solution is the development of oped under an Ispra-Creusot-Loire collaboration.

0 9 2 0 - 3 7 9 6 / 9 1 / $ 0 3 . 5 0 © 1991 - Elsevier Science Publishers B.V. ( N o r t h - H o l l a n d )


310 1I. Coen et al. / Corrosion of Cr-Mn based austenitic stainless steels

Table 1
Main constituents of the different alloys studied

Type Cr Mn Ni Mo C N Si V W
AMCR 0033 10.12 17.50 0.10 - 0.105 0.19 0.555 - -
AMCR 0035 14.09 19.88 0.265 0.060 0.029 0.048 0.63 - -
IF-A 13.59 11.04 1.950 0.030 0.110 0.045 0.165 0.75 1.4
IF-B 12.39 10.43 0.228 0.022 0.31 0.033 0.2 0.622 1.465
IF-C 12.98 17.42 2.081 0.041 0.11 0.04 0.22 0.022 2.2
IF-D 10.20 17.51 0.132 0.025 0.305 0.07 0.445 0.03 2.1
IF-E 17.95 10.5 2.084 0.045 0.085 0.052 0.28 0.75 2.09

The alloy AMCR-0033 comes from a batch of about 3. Experimental apparatus and procedure
1600 kg, A M C R 0035 of about 500 kg and the others
from batches of about 300 kg. 3.1. Capsule tests
The composition of the various alloys is given in
Table 1. The alloys of the 00 series were delivered in the The specimens were introduced in AISI 316 L stain-
form of hot-rolled, flat bars, mill annealed at 1373 K less steel containers, filled with Pb-17Li. The capsules
for 1 h. and water quenched. A M C R 0035 contains 15 were then sealed by electron beam welding. The oper-
vol% ferrite as a second phase dispersed in an austenite
i
matrix [4].
The alloys of the series IF have optimized composi-
tions in order to minimize long lived radioactivity.
Detailed information on their fabrication and metal-
lurgical characteristics can be found in ref. [5].
Briefly: alloys I F - A and I F - C contain Ni up to 2% to
stabilize the austenite while IF-B and I F - D have a high
C content (0.3%). The composition of I F - E was bal-
anced to obtain intentionally, for purpose of compari-
-L~ 1
son, a duplex austenite + ~ ferrite microstructure.
Discs (15 mm diameter) were cut from all the alloy - 2

samples; they were then metallographically polished,


degreased with acetone and heat treated for 2 h at 873 0 1
K in a U H V furnace.

2.2. Pb-17Li
/~-3

For the Thermal Convection Loop experiment the


lithium-lead eutectic used came from a batch of semi-
industrial production (1000 kg) prepared by the C E A o
for distribution to C E A / F o n t e n a y - a u x - R o s e s , J R C /
Ispra and C E N / M o l .
Both Pb and Li used were of industrial quality. The
batch nr. D-2536 had a Li content in wt% of 0.625 _+
0.02.
' SO mm '
For the capsule experiments the P b - 1 7 L i was pre- i

pared in our laboratory starting from very pure materi-


als, the method of preparation is reported in [7]. The Li Fig. 1. Thermal convection loop (1 = Pb-17Li, 2 = sample,
content in wt% was 0.70 +_ 0.02. 3 = thermocouple).
V. Coen et al. / Corrosion of Cr-Mn based austenitic stainless steels 311

ations were carried out in a stainless steel glove box welding device. T h e c o n t a i n e r s were t h e n h e a t e d in a
which can b e o p e r a t e d u n d e r either high v a c u u m or resistance furnace, u n d e r v a c u u m ; they were frequently
pure argon a n d is e q u i p p e d with a n electron b e a m rotated.

Fig. 2a. SEM micrograph of cross-section of AMCR 0033 heat treated at 673 K in Pb-17Li for 9245 h in 316L capsule (long face).

wt% Mn Cr Pb Ni Fe Si
MATRIX
Chem. Analysis 17.50 10.12 - 0.10 71.43 0.555
POINT A
Semi-quantit. 1.5 11.5 8.4 3.4 74.5 0.8
EDX-Mieroanal.
312 V. Coen et al. / Corrosion of Cr-Mn based austenitic stainless steels

4200 h with hot and cold leg temperature of respectively


723 and 673 K. The liquid metal velocity was calculated
to be 0.1 cm s-1. The steels investigated were AMCR
0033 and 0035 and the new alloys IF-A, IF-B, IF-C,
IF-D and IF-E.
The following micrographs (Figs. 2-11) show the
result of the tests, the composition of the corroded layer
has also been determined in most cases. The thickness
of the corrosion layer appears to depend on the com-
position of the different alloys.
It clearly appears that the corrosion of the C r - M n
steels by the lithium-lead eutectic is essentially governed
by a dissolution process. Mn and, to a lesser extent, Cr
(this can be seen in the TCL results) are dissolved. Pb
and Li penetrate in the corroded layer, the presence of
Pb being evident from the wavelength dispersive X-ray
elemental distribution imaging - that of Li has not been
experimentally determined in the case of the C r - M n
steels but there is no reason why these alloys should
Fig. 2b, SEM micrograph of cross-section of AMCR 0033 heat
differ in behaviour from AISI 316 L where Li has been
treated at 673 K in Pb-17Li for 9245 h in 316L capsule (short
face). identified by ion microanalysis [7] in the regions where
Pb has penetrated.
On corrosion the surface layer looses its austenitic
structure, being transformed to ferrite essentially on
account of the disappearance of the Mn which is the
3.2. Thermal convection loop main austenite stabilizer. The analogy with the be-
haviour of AISI 316 in Pb-17Li [7,8] is striking. The
The TCL is made of AISI 316 L, fig. 1; eleven corrosion mechanism is identical with the difference
thermocouples are welded to various positions in order that while in the Ni rich steel this element dissolves in
to have accurate temperature measurement. The dimen- the lithium lead in the case of the C r - M n steels it is the
sions are such that the device can be introduced into the Mn that practically disappears from the corroded layer.
glove box through the air lock. The samples are fixed in In both cases the Cr content in the corroded zone is also
the isothermal segment of the hot leg, the TCL is filled lowered but the decrease is not of the same order of
with Pb-17Li and closed through a sealed cover. The magnitude as in the case of Mn or Ni. This is evident
loop is then removed from the glove box. The heating of from the semiquantitative analysis of the composition
the TCL is achieved through four independent resis- of the TCL corroded layers. The solubility of Mn in
tance elements controlled via electronic thermo regu- Pb-17Li, though lower than that of Ni is of the order of
lators. 500 wppm at 723 K (Ni = - 3000 wppm). The solubility
After the tests both the capsules and the TCL were of Cr at the same temperature is much lower and does
opened in the glove box, the Pb-17Li melted and the not seem to exceed the value of 10 wppm [9].
samples extracted. The specimens were then sectioned, If we compare the behaviour of the C r - M n steels in
metallographically mounted, polished and examined by Pb-17Li with that in Li, that has been extensively
Scanning Electron Microscopy, wavelength dispersive studied, [3,6] we see that the dissolution process is
X-ray elemental distribution imaging and semi-quanti- similar. The main relevant difference is that while in the
tative energy dispersive X-ray microanalysis. case of Li, nitrogen enhances grain boundary attack,
this has not been observed with Pb-17Li (Fig. 4).
In both C r - M n and AISI 316 type steels nitrogen
4. Results and discussion whether present as an impurity in the Li or as a steel
constituent promotes grain boundary penetration with
The capsule tests were carried out at 673 K for 9245 the formation of Li9frN 5.
h. The steels studied were AMCR 0033 and 0035. It has been shown that in the case of AISI 316 [10]
The Thermal Convection Loop was operated for Pb-17Li could corrode that steel at 879 K to form
V. Coen et al. / Corrosion of Cr-Mn based austenitic stainless steels 313

Li9CrN 5 only at a nitrogen partial pressure of > 1012 magnitude than that of A I S I 316. The same should thus
Pa. The free energy of the corrosion reaction, in the case apply to the nitrogen pressure above Pb-17Li.
of the C r - M n steels, should be in the same order of If we examine the corroded zones we observe that

Fig. 3. SEM micrograph of cross-section of AMCR 0035 heat treated at 673 K in Pb-17Li for 9245 h in 316L capsule (long face).

wt~ Mn Cr Pb Ni Fe Si
MATRIX
Chem. Analysis 19.88 14.09 - 0.265 65.0 0.63
POINT A
Semi-quantit. 2.5 12.5 5.6 2.9 75.7 0.8
EDX-Microanal.
314 V. Coen et al. / Corrosion of C r - M n based austenitic stainless steels

has been explained [11] in the case of type 316 stainless


steel by the use of a surface destabilization model based
on the work of Harrison and Wagner [12]. A surface
that undergoes preferential dissolution (Mn, Cr in our
case) develops a very non uniform rugged corrosion
front.
Surface destabilization is also invoked to account for
the difference in behaviour of the long and short faces
of the sample [11]. On the short face of our specimens
the superficial cold worked layer due to machining has
not been removed, during the metallographical prepara-
tion of the discs prior to the corrosion experiments.
The perturbation of the starting planar surface "trig-
gers" the destabilization and subsequent growth of an
irregnlar interface. In the wavelength dispersive X-ray
elemental distribution imaging a clear increase in the Ni
content is observed in the porous corrosion layer. This
is due to the nickel-coming from AISI 316 L capsules or
loop and dissolved in the lithium lead eutectic.
Fig. 4. SEM micrograph of cross-section of AMCR 0033 heat If we consider the ferrite thickness layer in the case
treated at 773 K for 1500 h in Pb-17Li with addition of 300
of AMCR 0033, which is the most representative of the
wppm of Li3N.
alloys studied, we can see that the value of 25 ~m after
4200 h at 723 K with a AT of 50 K is slightly less than
the attack is generally not uniform, we often find local- the value of - 33/~m for AISI 316 L corroded in Tulip
ized penetration and the corrosion zones are often 1 TCL loop for 3000 h at the same temperature with a
thicker on the short face of the sample. AT of 60 K [8]. The Pb-17Li velocity in Tulip 1 is 0.12
The localized penetration or rugged corrosion front m s-1 in our case it is estimated to be of 0.1 cm s-1.

Fig. 5. SEM micrograph of cross-section of AMCR 0033 heat treated in Pb-17Li at 723 K for 4200 h in AISI 316L TC loop. AT= 50
K (long face).
V. Coen et al. / Corrosion of Cr-Mn based austenitic stainless steels 315

Alloy 0035 which contains - 15~ of delta ferrite is dissolution of Mn and to a M ~ extent Cr, forma-
less corroded as are the other alloys of the IF series. It tion of a ferrite layer and penetration of Pb and
is interesting to note that for alloy IF-E which has a possibly Li in this layer. Cold work enhances corro-
composition balanced to obtain a duplex austenite + sion.
delta ferrite microstructure, it clearly appears that the - The behaviour of this family of steels in Pb-17Li is
zones richer in Cr are less corroded than the zones at least similar if not better than that of AISI 316.
containing less chromium. - Some of the alloys of the series IF with optimized
composition seem to be less corroded. Further sys-
tematic analysis will be carried out once one or two
5. CondMom
of these steels are selected for further study on the
The compatibility tests on C r - M n austenitic stain- basis of considerations other than corrosion be-
less steels in presence of Pb-17Li in the temperature haviour.
range of interest for fusion applications have shown - It clearly appears that in the dual austenite, delta
that: ferrite structure the phase richer in Cr is less attacked
- The corrosion mechanism is essentially based on the by Pb17Li.

Fig. 6. SEM micrograph of cross-section of AMCR 0035 heat treated in Pb-17Li at 723 K for 4200 h in AISI 316L TC loop. A T = 50
K ( a = long face, b - s h o r t f a c e ) .

wt~ Mn Cr Ni $i
MATRIX
Semi-quantitative 19.80 14.23 0.00 0.77
EDX-microanalysis
AVERAGE VALUE
CORRODED ZONE
Semi-quantitative 0.30 7.90 2.80 0.95
EDX-microanalysis
AVERAGE VALUE
316 14. Coen et al. / Corrosion of C r - M n based austenitic stainless steels

Fig. 7. SEM micrograph of cross-section of IF-A heat treated in P b - 1 7 L i at 723 K for 4200 h in AISI 316L TC loop. A T = 50 K
(a = long face, b = short face).

wt% Mn Cr Ni Si V W
MATRIX
Semi-quantit.
EDX-microanal. 11.37 13.57 2.07 0.77 0.63 2.13
AVERAGE VALUE

CORRODED ZONE
Semi-quantit.
EDX-microanal. 0.10 8.30 1.13 1.03 0.67 2.80
AVERAGE VALUE

Fig. 8. SEM micrograph of cross-section of IF-B heat treated in P b - 1 7 L i at 723 K for 4200 h in AISI 316L TC loop. A T = 50 K
(a = long face, b = short face).
V. Coen et al. / Corrosion of C r - M n based austenitic stainless steels 317

Fig. 9. SEM micrograph of cross section of IF-C heat treated in P b - 1 7 L i at 723 K for 4200 h in AISI 316L T C loop. /iT = 50 K
(a = long face, b = short face).

Fig. 10. SEM micrograph of cross-section of IF-D heat treated in P b - 1 7 L i at 723 K for 4200 h in AISI 316L T C loop. A T = 50 K
(a = long face, b = short face).
318 V. Coen et al. / Corrosion of C r - M n based austenitic stainless steels

Fig. 11. SEM micrograph of cross-section of IF-E heat treated in Pb-17Li at 723 K for 4200 h in 316L TC loop. AT = 50 K (long
face).

wt% Mn Cr Ni Si V W
MATRIX
Dark zone
Semi-quantit.
EDX-microanal. 9.25 19.60 1.55 1.30 0.95 3.55
AVERAGE VALUE
MATRIX
Light zone
Semi-quantit.
EDX-microanal. 11.85 15.70 2.50 0.75 0.60 2.05
AVERAGE VALUE

low activation C r - M n austenitie steels for fusion reactor


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