REPORT for MAT-02- Task Agreement 2013

Fusion Materials Topical Group:

Reference:
MAT-02-01-01

Document: Report: Corrosion properties of RAFM steels: A literature review

Author(s): Teresa Hernández

Date: 12-12-2013
M. Porton Co-Chair of the Fusion Materials Topical Group
Distribution list:
E. Gaganidze
S. M. González de Vicente CSU Garching Responsible Officer
G. Federici. Head of PPP&T Department

Content:

Abstract
I. Introduction
II. Compatibility Breeders/Low Activation Steels
2.1 Corrosion in LiPb
2.2 Corrosion behavior in Li-Ceramics
2.3 Corrosion behavior in Molten Salts
III Databases
IV Conclusions
V Recommendations
VI Experiments at CIEMAT
References
Annex I Corrosion data base

Revision No: 0 Changes:

Written by: Revised by: Approved by:

Name
Teresa Hernández Name
Abstract

Tritium is produced by the reaction between lithium and neutron in a component known
as breeding blanket for the operation of a fusion reactor with DT cycle. The European
Union has developed 2 Test Blanket Modules (TBMs): Helium Cooled Lithium Lead
(HCLL) and Helium Cooled Pebble Bed (HCPB). The structural material is RAFM steel
EUROFER and the breeding materials are eutectic lead-lithium or lithium ceramic
pebbles or lithium salts. The compatibility of structural materials in both liquid and
solid breeders is an essential issue of fusion research. The objective of this report is a
systematic review of corrosion susceptibility of structural materials in liquid and solid
breeders. Secondary, it will be depicted the corrosion experiments carried out at Ciemat
to study the compatibility between EUROFER and lithium silicate. Finally some
recommendations for the future work will be presented.

A lot of lead-lithium testing loops are built to perform corrosion tests most of which are
in dynamic condition. The main corrosion mechanism is dissolution of steel alloying
elements into liquid lead-lithium. The corrosion rate is dependent on temperature, flow
velocity and magnetic field, and, of course, irradiation. At the required temperature the
reduction of flow velocity decreases the corrosion rate. The magnetic field enhances the
corrosion rate and forms furrow structure on the steel surface that may change the
mechanical properties. Application of corrosion resistant coatings is one possible way to
reduce the corrosion rate.

The study of corrosion behavior of structural material in solid ceramic breeder is very
limited so far. The corrosion mechanism is complex and still needs to be studied clearly.
The analyses of lithium ceramic pebbles show the contamination of steel alloying
elements on the surface. Different spatial distributions of alloying elements are in
accordance with the expected formation of oxidation products. The surface color of
EUROFER sample changes after the corrosion tests carried out at Ciemat. The analyses
of tested EUROFER sample show the formation of two oxidation layers with different
morphology on the surface.
 I. Introduction

1.1. Fusion Materials

In fusion reactors, the plasma facing (first wall, divertor) and breeding blanket
components will be exposed to plasma particles and electromagnetic radiation and will
suffer from irradiation by an intense flux of 14 MeV neutrons. The high-energy fusion
neutrons will produce atomic displacement cascades and nuclear transmutation
reactions within the irradiated materials. They also will suffer from strong magnetic
field, high heat flux and mechanical loads.

The first wall will consist of a structural material attached to a plasma facing (or armor)
material. The breeding blanket will consist of a neutron multiplier, a tritium breeding
material, one or several coolants, and a structural material to separate and contain the
different materials. The divertor will consist of a structural material (heat sink)
containing a coolant and supporting a plasma facing (or armor) material. Three types of
materials are of primary concern: the plasma facing materials, which will serve as an
armor for the underlying materials; the functional materials, which will have one or
several particular functions (e.g. tritium breeding, neutron multiplication, optical
transmission, etc); and the structural materials, which will support the basic structure of
the reactor. The main candidate materials for fusion are listed in Table 1 [1]

Table 1: Main candidate materials for fusion.

Function First wall Breeding blanket Divertor

Plasma facing W-based alloy, W- W-based alloy, W-
material coated coated
ODS steel,owing SiC/ SiCf , owing
liquid liquid
metal Li metal Li, Ga, Sn,
Sn-Li

Neutron multiplier Be, Be12Ti,

material Be12V, Pb

Tritium Breeding Li, eutectic Pb-Li,

material Li-
based ceramic
material
(Li2O, Li4SiO4,
Li2TiO3,
Li2ZrO3, LiAlO2)

RAFM steel, ODS RAFM steel, ODS ODS steel, W-

Structural steel, steel, based alloy
material V-based alloy, SiC/ V-based alloy, SiC/
SiCf SiCf
RAFM steel, ODS RAFM steel, ODS
steel, V-based steel, V-based
alloy, SiC/ SiCf alloy, SiC/ SiCf

Coolant Water, Helium, Water, Helium

eutectic
Pb-Li, liquid metal
Li

1.1.1 Structural materials

The qualification of structural materials is a fundamental challenge. They will be

exposed to high temperatures and high levels of neutron irradiation, as well as to high
mechanical and thermo-mechanical stresses. In addition, the thermal efficiency of a
reactor, according to the Carnot cycle, is proportional to the difference between the
outlet temperature of the coolant and the inlet temperature of the coolant. These
temperatures are mainly limited by the temperature window for use, i.e. the window of
operation of the structural materials, which is mainly limited by their mechanical
properties under irradiation.
Candidate structural materials have a chemical composition that is based on low
activation chemical elements (Fe, Cr, V, Ti, W, Si, C), including Reduced Activation
Ferritic/Martensitic (RAFM) steels, Oxide Dispersion Strengthened (ODS) RAFM and
ODS Reduced Activation Ferritic (RAF) steels, tungsten based alloys, vanadium-based
alloys and fiber reinforced SiC/SiCf ceramic composites. Each alternative alloy class
exhibits specific problems arising from their intrinsic properties and from their
resistance to radiation damage. For the time being, the most promising structural
materials for future fusion power reactors seem to be the RAFM steels for which the
greatest technology maturity has been achieved, i.e. qualified fabrication routes;
welding technology and a general industrial experience are available. Their temperature
window of use is presently about 625-825 K, the lower temperature being limited by
irradiation-induced embrittlement effects and the upper temperature by a strong drop in
mechanical strength. However, a difference of 200 K between the outlet and inlet
temperatures of the coolant should be sufficient to ensure acceptable efficiency of first
generation fusion power reactors. In Europe, Japan and Russia it has been demonstrated
that it is now feasible to produce RAFM steels on an industrial scale with sufficiently
low impurity levels. Main RAFM steels that are being investigated include the Chinese
CLAM and CLF-1 alloys, the European EUROFER 97 alloy, the Japanese F82H and
JLF-1 alloys, and the Russian RUSFER-EK-181 alloy. Their composition lies in the
following range: Fe-(7.5-12)Cr-(1.1-2)W-(0.15-0.25)V, in weight percent.
 1.1.2 Plasma facing materials

The qualification of plasma facing materials is very demanding. Plasma facing materials
will be directly exposed to the fusion plasma which means that they will be exposed to
high temperature, high heat flux of energetic particles, neutron irradiation and
electromagnetic radiation, sputtering erosion, etc. The selection of plasma facing
materials is mainly limited by their capability for absorbing heat and minimizing plasma
contamination. The main candidate plasma facing materials are refractory metals and
alloys, like tungsten-based alloys, which have the advantage of high melting point, high
thermal conductivity and high threshold for physical sputtering energy. An alternative
to the use of high-melting-point materials would consist in using owing liquid metal as
plasma facing material. Flowing liquids have high heat load capability and could allow
simultaneous heat and particle removal [1].

1.1.3 Functional materials

The qualification of functional materials is also very demanding. Their mechanical

resistance under irradiation is presently considered of no primary concern. However,
material properties like the tritium release behavior, thermal conductivity and structural
integrity after prolonged neutron irradiation are important concerns. As compared to
structural materials, orders of magnitude more hydrogen and helium isotopes will be
generated in functional materials, e.g. in beryllium-type neutron multipliers and lithium
ceramic-type tritium breeders. The irradiation resistance of other functional materials,
such as ceramic insulators, dielectric and optical windows, optical fibers or complete
sensor assemblies, is also an important concern.

The lack of adequate functional materials enabling a very high temperature design
window is an important issue for fusion power reactors. Component lifetime will be
determined by the resistance of functional materials as well as plasma facing materials
and structural materials. Unfortunately, the choice of functional materials is very
limited, as it relies mainly upon the properties require by the envisaged function [1].

1.2 ITER TBM program

A tritium breeding blanket (BB) ensuring tritium breeding self-sufficiency is a
compulsory component for DEMO, the next-step after ITER, although is not present in
ITER. Mock-ups of DEMO BB, called Test Blanket Modules (TBMs), will be inserted
and tested in ITER in three dedicated equatorial ports(#02, #16, #18) directly facing the
plasma. Each port can accommodate two TBM-Sets, therefore six TBMs and associated
independent systems can be tested in ITER. They are the principal means by which
ITER will provide the first experimental data on the performance of the BBs that is still
an open issue on the path to commercial fusion power. These activities correspond to
the so-called “TBM Program". A successful ITER TBM Program represents an essential
step on the path to DEMO for any fusion power development plan.
1.3 Test Blanket Systems

Six mock-ups of six whole DEMO-BB systems will be tested in ITER, which means
that the TBMs are connected with several ancillary systems, such as cooling systems,
tritium extraction systems, coolant purification systems, and instrumentation and control
(I&C) systems. TBMs and associated systems are called Test Blanket Systems (TBSs).
The TBSs functional characteristics are dictated by the operational conditions and
requirements expected in a DEMOBB system and, in this sense, they differ from the
other ITER components that are designed in compliance with only ITER requirements.
However, they must be fully integrated in ITER; therefore they must be compatible with
the systems and operational procedures of ITER and the ITER operating plan.

Moreover, TBS testing must not endanger ITER performances, safety and availability.
All ITER members contribute to the TBM program. At present, the following six
independent TBSs are used for the integration and interfaces de ignition in ITER:

•the Helium Cooled Lithium Lead (HCLL) TBS and the Helium Cooled Pebble Bed
(HCPB) TBS for installation in Equatorial Port #16;
•the Water Cooled Ceramic Breeder (WCCB) TBS and the Dual Coolant Lithium Lead
(DCLL) TBS for installation in Equatorial Port #18;
•the Helium Cooled Ceramic Breeder (HCCB) TBS and the Lithium Lead Ceramic
Breeder (LLCB) TBS for installation in Equatorial Port #02. The typical dimensions of
each TBM are: 1.66 m (poloidal) x 48 cm (toroidal) x50/70 cm (radial). The structural
material for all TBMs is RAFM steel, which is a ferromagnetic material and therefore
has an impact on the magnetic field close to the corresponding equatorial ports. The
lead-lithium-based concepts use the liquid metal eutectic Pb-Li with melting
temperature of 235 ºC. The ceramic-based concepts use pebble-beds of either Li4SiO4
or Li2TiO3. [2, 3, 4, 5, 6, 7 and 8]

In table 2 are listed what are used for structural, breeding material, neutron multiplier
and coolant for six TBSs designs.
Table 2: Main candidate materials for fusion.

TBM Structural Breeding materialNeutron Coolant

material multiplier
HCLL(EU) EUROFER 97 eutectic Pb-Li Eutectic Pb- Helium
(90% 6Li en- Li
richment)

HCPB(EU) EUROFER 97 Li4SiO4 Beryllium Helium

(reference, 30% pebbles
6Li
enrichment) or
Li2TiO3 (60%
6Li enrichment)
pebbles

WCCB(JP) F82H Li2TiO3 (30% Beryllium Water

6Li enrich- pebbles
ment) pebbles

DCLL(US/ F82H eutectic Pb-Li Eutectic Pb- Helium and

KR) (90% 6Li en- Li eutectic Pb-Li
richment)

HCCB(CN) CLF-1 Li4SiO4 (80% Beryllium Helium

6Li enrich- pebbles
ment) pebbles

LLCB(IN/ IN-RAFMS Li2TiO3 (30-60% Eutectic Pb- Helium and

RU) 6Li enrich- Li eutectic Pb-Li
ment) pebbles and
eutectic
Pb{Li (90% 6Li
enrichment)
II. Compatibility Breeders/Low activation Steels

Corrosion behavior in eutectic Pb-Li

The chemical compatibility of breeding materials and structural materials is essential for
safe and reliable system operation in nuclear fusion reactor. The compatibility issue is
mainly relied on corrosion behavior between breeding materials and structural
materials. Corrosion in the form of uniform or selective dissolution, inter-granular
penetration, and interstitial-element transfer can result in significant wall
thinning/wastage and deposition of corrosion products that may cause severe flow
restrictions and excessive accumulation of radioactive material in unshielded regions.
The former consequence results in a loss of mechanical integrity and the latter
phenomenon would increase requirements for pumping power, decrease the energy
conversion efficiency, and complicate system maintenance [9].

This chapter starts from the evolution of eutectic composition and a historical overview
of corrosion tests including operating parameters, kinds of structural materials and main
results in past thirty years. At last it will be mentioned the conclusions and implications of
the results shown, as well some recommendations referred to the lack of data in some
fields.

Eutectic composition

Pb-Li eutectic is possible candidate for tritium breeding, cooling, and neutron
multiplying functions in fusion reactor. Validated materials databases are needed for
progress of any R&D technology. Among them, lithium concentration of the eutectic is
a very important parameter. Lithium determines the eutectic chemical activity and the
variation of Li concentration can significantly vary the physical-chemical and solute
transport properties. Quality assurance of Pb-Li eutectic is intimately related with the
accurate determination of the eutectic chemical composition with the analysis technique
certifying at 0.1% Li and the eutectic production technique guaranteeing its short-scale
homogeneity (in order to avoid Li aggregation) [10].

The only published data pertinent to the lead-rich section of the Pb-Li phase diagram
(xLi < 25 at%) are those on which Hansen and Anderko [11] based their compilation in
1958. In their book \Constitution of Binary Alloys", they reviewed the previous work
and recommended the most extensive and comprehensive data which was 17 at% Li
(denoted as Pb-17Li) at melting point 235 ºC. Hence Pb-17Li became the choice of
alternative breeder material for the blanket designs.

Liquidus temperatures are conventionally determined by thermal analysis methods.

These methods, however, are unreliable since they suffer from the fact that, although
non-equilibrium methods, they are used to determine equilibrium data. In 1992,
Hubberstey and Sample developed a new technique to redetermine the composition of
Pb-Li eutectic. The measurement of electrical resistance as a function of temperature
under equilibrium condition overcomes such problem, since the plots relating these two
parameters, which are readily determined with a high degree of accuracy, exhibit an
abrupt change in gradient at the liquidus and a sharp discontinuity at the eutectic. In
their work, the eutectic composition corresponded to 15.7±0.2 at% (denoted as Pb-
15.7Li) at melting point 235±1 ºC [12].

As a result the Pb-17Li alloy which was chosen for the most of conceptual designs of
breeder blankets or experimental loops had been shown to lie. However, although this
chemical composition differs a little from the eutectic one (Pb-15.7Li), it is not of great
importance in practice and the alloy is still suitable for the operation of a blanket [13].
For the newest design proposal for EU HCLL TBM, the reference lead-lithium alloy is
Pb-15.7Li.

2.1 Corrosion in PbLi results

2.1.1 Experimental apparatus and loops

The testing were in both static and dynamic conditions. The dynamic conditions
included impeller/stirrer induced, thermal convection and forced circulation, etc.
Several loops also contained a magnetic/cold trap to collect and remove the corrosion
precipitates from owing liquid metal. Among them, loop types of thermal convection
and forced circulation are widely constructed by many countries.

The testing steel samples were exposed to liquid Pb-Li with various flow velocities at
different temperatures. Afterward the tested samples were usually analyzed by
measuring metal loss or length/diameter change, standard metallographic technique with
optical microscopy, and by applying SEM (Scanning Electron Microscopy) and EDX
(Energy Dispersive X-ray spectroscopy) technologies, etc. Metal loss or length/diameter
change can determine corrosion rates. Metallographic techniques can observe the
surface morphology and roughness to determine corrosion attack. SEM/EDX analyses
can investigate elements concentrations from corrosion layer to steel matrix.

1. Static Tests:

The static corrosion tests consist on the immersing specimens in a closed crucible under
an inert gas at elevated temperature. Although the tests are not realistic, are relatively
simple to perform and can give some information, especially to clarify the corrosion
mechanisms. The results obtained by different laboratories vary widely depending on
the conditions. [14],[15],[16].

2. Corrosion tests in rotatory disc apparatus

In the liquid metal blanket, corrosion of structural materials exposed to the Pb-17Li
alloy may be affected by the magnetic field. It is known that the presence of a magnetic
field can change the flow configuration of an electroconducting fluid and thus the
transport of solute from the solid to the liquid phase may also be modified. In order to
study such an effect, corrosion experiments in Pb-17Li with flows generated in a
cylindrical cavity by a rotating disk were planned. An example of these apparatus is
depicted in Figure 1.
Figure 1: Schematic diagram of the MHD PbLi loop at UCLA. Magnetic field is
perpendicular to the plane of the sketch

Although lately magnets are being incorporated to some rotatory discs apparatus, the
most data only correspond to specimens immersed in a Pb-Li17 flux without magnetic
field. There are not many data obtained by this technique and there are not very
convincing because they indicate that the magnetic field does not affect or positively
affects corrosion. The results are included in the database records from 14 to 16.
[17].[18].

3. Hydrodynamic Corrosion Tests and MHD.

The corrosion of different ferritic/martensitic steels and austenitic steels has been
studied in this loops by changing the temperature, flow rate and breeder composition.
Among all the testing loops, three typical loops in which more than one corrosion tests
were carried out are chosen to give an idea what the experimental loops look like and to
discuss main test results. Most results were achieved of the PICOLO loop, since it has
been made long-term tests.

Fusion reactor is a magnetic confinement machine, so the materials will suffer from a
strong magnetic field and the research of the effect of magnetic field on the corrosion
processes is necessary. That's because of the change of hydrodynamics of liquid metal
flow, and because of interaction of a magnetic field with a ferromagnetic steel.

Most of the corrosion tests having been done over last thirty years are without magnetic
field. However, the research of the effect of magnetic field on the corrosion processes is
ongoing recently.

a) TULIP (Loop at ENEA)

The schematic of TULIP is shown in figure 2. This is the simplest design of loop
wherein the fluid transport occurs through the thermal gradient. These square
thermal convection loops (0.5 mx0.5 m) contained about one liter of Pb-17Li alloy
and were heated along the lower horizontal leg and cooled by water jackets along
the upper horizontal leg. Corrosion samples could be located in the isothermal hot
leg and also in the heated leg.
 Figure 2: Schematic diagram of TULIP.

b) PICOLO (Loop at KIT)

The PICOLO loop was a figure-of-eight type loop with a central heat exchanger, a hot
leg and a cold leg. The cold leg contained the pump, flow meter and magnetic trap. The
whole circuit was connected to a dry argon glove box as is shown in 3.The volume of
PICOLO was about ten litres and the alloy was molten in the glove box and filled into
the loop through the expansion vessel. The test section was a tube of 16 mm inner
diameter and 440 mm length.

Figure 4: Schematic diagram of PICOLO.

 c) A forced circulation loop in USA
The forced circulation loop needs pump to force liquid alloy to flow and becomes more
complex. Early in 1980's USA had constructed a force circulation loop whose schematic
is shown in Fig. 5 The main loop consisted of a high temperature test vessel with a heat
exchanger, a cold leg, a linear induction pump and flow meter. The liquid Pb-17Li alloy
was prepared in a separate vessel and transferred into the loop. The total volume of the
loop was about two liters.

Figure 5: Schematic of USA forced circulation Loop.

d) LIFUSII (Loop at ENEA)

LIFUS II is an eight-shape loop with a cold part working at temperature of about 300 °C
and the hot part, containing the test section with the corrosion and low cycle fatigue
specimens, operated in the range of 400-500 °C. For this application, the loop is
connected with a MTS fatigue machine. The corrosion properties of different kinds of
martensitic and austenitic steels have been studied in this loop as a function of
temperature of the molten alloy and its velocity.

Figure 6 shows the schematic fatigue tests performed at LIFUSII.

Figure 6: LIFUS 2 experimental loop at ENEA Site of Brasimone

e) DRAGON I (Loop at China)

Dragon I was built by the FDS team in 2005. It is a 0.5-m × 0.5-m thermal convection
loop made of SS316L tube with an internal diameter of 22 mm. Heating along the lower
horizontal leg is supplied by shielded resistances and cooling along the upper leg by
water jackets. The expansion tank is used for the introduction of the LiPb ingot into the
loop before experiment and its tightness is ensured by flange with metallic seal and
weldable lips. The rods of cylindrical specimens were immersed in the vertical
isothermal hot leg.

Figure 7 shows the Dragon I scheme.

Figure 7: Dragon I experimental loop

f) ELLI ( MHD Loop at Korea)

ELLI loop consists of a sump tank, EM pump, and a magnet. The sump tank was
equipped with two sets of heating jackets for melting the solid PbLi breeder,
thermocouples for measuring the temperatures of the gas and liquid breeder, a pressure
gauge, and a level sensor for detecting the level of the liquid breeder.

Figure 8 shows the scheme of ELLI loop.

Figure 8: Schematic diagram of the ELLI experimental loop.

 g) Pb-17Li loop in a magnetic field of the University of Latvia

The loops consisted of two parts: a cold part and a hot part. In the cold part of the loop
(behind the heat exchanger, at the inlet of the cold trap, in the EM flow meter and in the
pump), the temperature was kept within the range of 350-400 ºC. The operating
temperature in the test section was 550 ºC and the maximum intensity of the magnetic
field in the area of test section was 1.7 T.

Figure 9: Principal schematic of Pb-17Li loop for EUROFER corrosion experiments in

a magnetic field. 1-test section; 2-liquid metal loop; 3-level meter; 4-expansion tank; 5-
heater; 6-cold trap; 7-flow adjusting valve; 8-heat exchanger; 9-expansion tank; 10-EM
flow meter; 1-supply container; 12-vacuum meter; 13-vacuum pump; 14-argon balloon;
15-magnet pole shoes; 16-device foe adjusting oil level in the heat exchanger; 17-oil
supply tank.

h) A Magnetohydrodynamic loop MaPLE in UCLA

The main components of this facility include a flow circuit, electromagnetic (EM)
pump, EM flow meter, electromagnet and a glove box. The flow circuit, including a
melting tank (also serves as a supply/drain tank) and pipelines, are made of stainless
steel SUS304. The maximum inventory of PbLi in the loop is now about 200 kg. The
style V EM conduction pump is made by Creative Engineers, Inc., USA. The pump tube
is made of stainless steel SUS316. The loop is currently operated at 350 ◦C maximum as
required by the temperature limit of the pump. The magnetic field is created by a water-
cooled electromagnet with the maximum magnetic field of 1.8 T. The magnetic field is
uniform within
a space of 80 cm (axial) × 15 cm (horizontal) × 15 cm (vertical). The whole loop, except
for the magnet, sits on a steel catch pan, which in turn is put on a four-wheel carrier,
which can be moved forward or backward [19]. The figure 10 represents the UCLA
loop.
Figure 10: Schematic diagram of the MHD PbLi loop at UCLA. Magnetic field is
perpendicular to the plane of the sketch.

i) DRAGON IV (China)
Other ambitious magnetohydrodynamics loop is under construction or are given very
early results, for example the DRAGON IV in China [20] (see figure 12).

Figure 12: Scheme of Dragon IV.

The most relevant data obtained in hydrodynamic or MHD cycles are listed in the
database and are included in the references.
[21],[22],[23],[24],[25],[26],[27],[28],[29],[30],[31],[32],[33],[34],[35],[36],[37],[38],[
39],[40],[41],[42],[43],[44],[45],[46],[47],[48],[49].
 Results

To determine the corrosion behavior, loss of sound metal was measured.

The loss of sound metal might be determined either by weight loss measurement after
complete elimination of the ferritic layer or by thickness measurement of the ferritic
layer on cross section micrographs. The corrosion rate of steel in liquid breeder is
strongly dependent on temperature, flow velocity and other thermal-hydraulics
conditions of testing loop. It was found that the sound metal loss was much greater for
316 L steel than martensitic or ferritic steels at the same temperature and flow rate of
approximately 0.1 m/s. That comes to conclusion that martensitic or ferritic steels have
better corrosion resistance than austenitic ones.

The corrosion rate for MANET I, F82H and Optifer exposed to owing Pb-17Li at 480
ºC and at flow of 0.3 m/s was 100 µm/y. The corrosion rate for EUROFER (reference
structural material for EU TBMs) tested under the same condition was 90 µm/y. As a
result, among all proposed RAFM steels, EUROFER has the best corrosion resistance
and similar to CLAM (15,2 um/y for a flow of 0.08 m/s). [50]

At the same flow velocity of 22 cm/s, there is a dramatic increase of corrosion rate from
80 to 400 µm/y at the temperature 480ºC and 550ºC. For the same temperature, the
corrosion rate is decreasing with decreased flow velocity. The results obtained in the
LIFUS II loop indicate that the corrosion rate is about 40 um / year when the flow rate
is 0.01 m / s. [51].

The most interesting phenomenon which not occurred before in experiments without
magnetic field is that the corrosion surfaces exposed to the magnetic field displayed
ordered wave-like furrow structures oriented in the liquid flow direction whereas the
surfaces were relatively smooth enough without magnetic field. These furrow structures
were observed only on the Hartmann (perpendicular to the magnetic field) surfaces [52].

The data compilation obtained in the loops can be found in the attached database.

2.2 Corrosion behavior in Li- ceramics

The use of solid ceramic breeders, despite its relatively low thermal conductivity,
presents several advantages. Among them is low chemical activity, which is important
to get a good compatibility with the structural materials and coolant [53]. The study of
corrosion susceptibility for solid ceramic breeders is limited so far. Although it is
expected that the corrosion degradation caused by solids is much lower than that due to
liquid, it is still not negligible and should be evaluated properly.

This part collects recent published research results. At last it discusses the experimental
details and results of corrosion tests carried out at Ciemat, Spain.
 Results

Not so much study about compatibility issue of structural materials with lithium
ceramics have been done so far. The published literature is very limited.

A compatibility test of ceramic solid breeders (Li2O, -LiAlO2 and Li2SiO3) with
candidate structural materials (Type 316 stainless steel, HT-9, Inconel-625 and Ti 6242)
was done at 600 ºC in a pure helium (99.99%) atmosphere for 1900 h in USA early in
1981.

The corrosion scale formation was greatest for Li2O/alloy couples typically >15 µm
thick. The scales on Li2SiO3/alloy and on -LiAlO2/alloy were comparable. Some
lithium oxides containing steel alloying element (Li5FeO4, LiCrO2) were detected in the
corrosion scale [54]. Another simple capsule compatibility tests of three lithium-
containing ceramic breeder materials Li4SiO4, Li2ZrO3 and LiAlO2 with two industrially
available SiC/SiC composites were carried out at 600 and 800 ºC under two testing
conditions (owing helium and dynamic vacuum) for 1000 h in Italy in 1994 [55]. It was
found that all three breeder materials were reactive towards the SiO2 content of the
SiC/SiC composites forming a surface layer of Li2SiO3 in owing helium.

For RAFM steels, there are some groups working in EFDA Technology Work program
to study interaction chemistry between EUROFER structural material and lithium
ceramic pebbles. A. La Barbera studied the interaction chemistry between Li4SiO4
ceramic pebble bed and EUROFER structural material in He + 0.1% H2 purge gas at
600°C [56] and found that for exposure time up to 200 hours whilst tests in the same
conditions were performed in an alumina tube by using an horizontal oven for exposure
time between 500 and 2000 hours. Parabolic kinetic constant were calculated and the
scale morphology and superficial phase composition where studied. The reactivity of
Eurofer sample in Li4SiO4 was found to be one order higher than in Li2TiO3.

The compatibility results between the RAFM steels and lithium ceramics can be found
in the attached database II.

2.3 Corrosion behavior in Molten Salts

Molten salt is an attractive liquid material due to its reduced reaction with respect to
lithium when exposed to water or air, and its significantly reduced MHD effect when
used as a coolant in a tokamak power plant [57]. There are some promising molten salts
which are all mixtures of fluorides as coolant and tritium breeder for fusion blanket
applications. One of these salts is a mixture of LiF and BeF2 (2:1 ratio, Li2BeF4) named
Flibe due to its low electric conductivity, its high chemical stability, and possibility of
utilizing as coolant material [58]. The other candidates are mixture of LiF-NaF-KF
named Flinak and mixture of LiF-NaF-BeF2 named Flinabe [59], [60].

In the fluorides molten salts blanket system, tritium fluoride (TF) is going to be formed
by neutron irradiation, which is corrosive to structural materials [61]. Other impurities
in the molten salts such as HF, H2O and O2 are possible corrosion agents as well [62].
Therefore, for the development of fusion reactor with molten salts blanket system,
compatibility of structural materials with the molten salts is one of the critical issues.
This part collects recent published research results in this area

Results

Dipping experiments

A schematic drawing of the dipping experimental system is shown in Fig. 13. Dipping
experiments were performed in a SUS316 container in flowing atmosphere. In a nickel
crucible, each steel sample was dipped in Flibe prepared by mixing LiF and BeF2 with
ratio of 2:1 at 550oC. BeF2 is hygroscopic and deliquescent. HF was generated at
elevated temperatures by the reaction: BeF2 + H2O  BeO + 2HF. Therefore, initial
Flibe contained small amounts of HF (in several ppm). Samples of ferritic steel SUS430
(Fe-18Cr) and SiC were dipped in Flibe at 550oC for 1 day, 3 days, and 10 days in
flowing pure argon gas environment. Samples of reduced activation ferritic steel JLF-1
(Fe-9Cr-2W) were dipped in Flibe at 550oC for 30 days in pure Ar or Ar + 1% O2 gas
environment. The JLF-1 samples were also dipped in Flibe at 550oC for 9 days in Ar +
82 ppm HF gas environment. After dipping experiments, samples were picked up from
Flibe and cooled down. Later they were cleansed in LiCl-KCl molten salt to remove the
Flibe solidified on the surface. Then any LiCl-KCl sticking to the samples was removed
by ultrasonic washing in water. Finally the surfaces of samples were wiped with
alcohol. X-ray diffractometry (XRD) and Rutherford backscattering spectrometry
(RBS) analyses were performed on the samples to characterize the corrosion behavior.

Figure 13: Schematic of dipping experimental system. [63].

The compatibility results between the JLF-1 steel and molten salts can be found in the
attached database III.

III Databases

They excel sheet attached as Annex contains the database that compiles by Principal
results that have been obtained to date is formed by three sub databases.

Database I: contains the results obtained in liquid breeders. The different colors
indicate the type of facility.

-Green: Static tests

-Light purple: Rotatory disc.

- Pink: Hydrodynamic loops (thermal and forced convection)

- Dark orange: Magneto-hydrodynamics loops.

-Blue: In pile tests (irradiation).

The fields contained in the data base are:

- MATERIAL ID and composition

- LABORATORY

- REFERENCE

- Responsible.person

- Treatment

- Specimen size

- Finished

- Breeder Composition

- Test Temperature (ºC)

- Time

- Conditions

- Loop

- Magnetic Field (Tesla)/irradiation dpas)

- Flow rate
- Corrosion depth

- weight loss

- Corrosion rate

- weight loss rate

Database II and III: contains the results obtained in solid breeders and molten salts
respectively.

The fields contained in the data bases are:

- MATERIAL ID and composition

- LABORATORY

- REFERENCE

- Responsible person

- Steel composition

- Treatment

- Specimen shape

- Specimen size

- Finished

- Breeder Composition

- Test Temperature (ºC)

- Time

- Environment

- Loop

- Corrosion products (layer)

- Corrosion depth (um)

- Specific weight (ug/cm2)

- Magnetic Field (Tesla)/irradiation dpas)

- Flow rate

- Corrosion depth
- Weight loss

- Corrosion rate

- Weight loss rate

IV. Conclusions

Corrosion behavior in eutectic Pb-Li

Corrosion rate is dependent on temperature, flow velocity and magnetic field. The most
important effect is the temperature.

Most corrosion data of low activation steels with Pb-Li have been conducted in
hydrodynamic loops with either thermal or forced convection. The more relevant data
were obtained in the loop “Picolo” since tests reach up 120,000 hours. Under these
conditions, the corrosion rate for EUROFER has been established on 80 µ/year for a
flow of 0.22 m / s and 480 ° C; however when the temperature rises to 550 ° C, the
corrosion rate is enhanced to 400 µm / year.

The magnetic field, although also enhances the corrosion rate, is especially important
because forms furrow structure on the steel surface that may change the mechanical
properties When magnetic field of 2 T is applied, the corrosion rate can be increased to
320 µm/year, although these results were obtained in short time tests (1000 hours) and
should be taken only as indicative.

Corrosion behavior in lithium ceramics.

There are few data regarding corrosion of low activation steels in contact with solid
breeders. The results that were obtained show that, although the corrosion is less
important than in liquid breeders, exists.

The Spanish and German groups have worked on the subject are agree that lithium
ceramics produce a double oxydic layer in the steel that is enriched in iron outside and
chrome inside. When tests are performed not in vacuum but H2/He atmosphere, the
corrosion is enhanced and the layer thickness reaches about 25 microns.

Corrosion behavior in molten salts.

In this media, the results are given by the Japanese groups with the JLF-1 steel. All tests
were carried out in static and for short times (one month maximum). The main result is
that for the same test temperature, the corrosion layer produced by Flinak is an order of
magnitude thicker than that obtained by Flibe (6 µm and 0.6 µm respectively).
V. Recommendations

After reviewing the published literature related with the compatibility between the low
activation steels with different types of breeders, some gaps in the research can be
identified.

- Respect to the liquid breeders. It seems essential to have data in more realistic
conditions including tests in MHD. The data in such conditions (with magnetic
field) are very rare and for very short times. It is necessary to obtain information
at longer times and perform a good characterization of the corrosion layers after
testing for understanding the corrosion mechanisms that take place. It would be
very interesting to carry out mechanical tests into the loops, especially creep and
fatigue.
- There is a total lack of details of the corrosion behavior of welds.
- It would be desirable to know the behavior of the coatings under irradiation.
- There are no data of corrosion in fluid flux greater than 0.5 m/s.

- Respect to the Li ceramic breeders. It could be interesting to have data at

longer times in H2/He atmosphere.
- It would be interesting to have data of the crack growth rate in the corroded
specimens.
VI Experiments at CIEMAT

6.1 Experimental setup and procedure

The experimental setup mainly consisted of a horizontal cylindrical oven, purge gas
system, a tubular 316 L stainless steel capsule. The schematic of this setup is shown in
figure 15.

Figure 15: Schematic of experimental setup at Ciemat: (a) front view, (b) side view, (c)
schematic of cross section, (d) experimental tube.

The chemical compatibility tests of four types of RAFM steels (EUROFER, F82H,
ODS EUROFER and PM2000) in lithium orthosilicate pebble bed were carried out at
550 ºC (the reference working temperature in steels in EU HCPB TBM design [4]) for
testing periods of 1, 2, 4 and 8 weeks. In the following discussion, we only focus on the
corrosion behavior of EUROFER in lithium orthosilicate.

The first experimental step is materials preparation. The ceramic pebbles of lithium
orthosilicate were obtained at Ciemat laboratory of material by spray-drying technique
followed by pyrolysis. The raw materials were the stoichiometric amounts of lithium
acetate and silicon tetra acetate respectively of analytical grade. After drying, the
powder obtained was heating at 600 ºC to reach the crystalline lithium orthosilicate
phase and preserve the adequate spherical shape [64]. The samples of EUROFER with
chemical composition (wt%) 0.1C, 9Cr, 1W, 0.12Ta, 0.23V, 0.5Mn, 0.001S, balance Fe
were cut into rectangular pieces and grinding up to 600 SiC paper-grit (equivalent to 26
µm roughness approximately) with final dimensions of 20x15x8 mm3. Before testing,
the samples were cleaned in ultrasonic ethanol bath, dried and weighted. The second
step is main test. All the RAFM steel samples (two for each type) were hung to a rod as
in Fig. 16 and the rod was inserted into the stainless steel capsule. The capsule was
filled with lithium orthosilicate powder and connected to a mixed purge gas of He/0.1%
H2 (the composition of purge gas in EU HCPB TBM design [4]) at 1 MPa. The working
temperature of the oven was set as 550 ºC. The testing periods were 1, 2, 4 and 8 weeks.

Figure 16: Samples of RAFM steels (a) before testing, (b) after testing for 4 weeks.

After finishing the test and temperature of oven decreased to room temperature, the
tested samples were taken out from the capsule shown in figure 15. All the samples
were cleaned in ethanol, measured and weighted. Then simple preparations of cutting,
mounting, grinding and polishing were done to steel cross section.

The final step is characterization of tested samples. Metallographic studies were

performed in cross section for all samples by SEM/EDX analyses (JEOL Mod. JSM
6400 EDX) and Superprobe JXA-8900 M equipped with an Electron Probe Micro
Analyzer (EPMA). The corrosion products were determined by X-ray diffraction (XRD,
PAnalytical Mod. X'Pert PRO MRD).
6.2 Results and discussions

After exposure, the surface color of EUROFER sample changed from metallic to dark
as shown in figure 16. That means there is chemical reaction occurring on the steel
surface. The mass change measurements are not accurate because surface descaling
occurs during cleaning. The approximate mass change of EUROFER samples with time
is corresponded to a logarithmic law. Figure 17 shows the SEM/EDX analyses results of
cross section of EUROFER sample surface for the exposure time of 1, 2, 4 and 8 weeks.
The corrosion layer was observed to be uniform all over the surface and thick of about
18-25 µm.

From all the SEM images, the corrosion layer was mainly formed by two layers
containing oxygen which is corresponding to oxides layer. The nearest layer to the base
material was compact. It was depleted in Fe and enriched in Cr compared to the steel
matrix. In contrast, the outer layer was very porous and exhibited lower density. The
concentration of Fe was decreased comparing to the steel matrix while increased
comparing to the inner corrosion layer. The concentration of Cr became almost
negligible in this layer. A visible gap was found between base material and oxidation
layer at the SEM images of the samples for the exposure time of 2, 4 and 8 weeks. The
possible reason is that corrosion layer became a little detached from the base material
during sample preparation. These results will be published in a short time [65].
Figure 17 SEM/EDX analyses results of cross section of EUROFER sample
surface for the exposure time of 1, 2, 4 and 8 weeks.
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