ISLA2011

Improvement of compatibility of liquid metals Li and Pb-17LI

Masatoshi KONDO, Minoru TAKAHASHI b), Teruya TANAKAa), Tsisar Valentyn c) and Takeo MUROGA a) Tokai university, Japan, a)National Institute for Fusion Science a) b) Tokyo Institute of Technology, Japan c) Physico-Mechanical Institute of National Academy of Sciences of Ukraine, Ukraine
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Background -1 Fusion blanket

Japan (2003) molten salt Flibe/RAFM Dr.Sagara et al., FED Japan (2003) liquid metal Li/vanadium Dr.Muroga et al., FED

KOREA HCML-TBM (2008)Li/RAFM Dr.KIM et al

India TBM (2009) Pb-LIsolid breeder/RAFM Dr.Kumar et al FED

Liquid breeder Lithium Pure metal

Lead lithium Pb-17Li Korea USA Japan Russia Europe India china

Coating
(MHD, Ttritum .etc)

Structure

Er2O3
(DiP)

RAFM i

Al2O3

Alloy Flibe LiF-BeF2 Molten salt

Er2O3 (DiP)

Japan Toward high temperature

Vanadium alloy
Nitride treatment

Background -2 (Structural material)

Chemical composition (wt%)

wt% -1 Cr W 1.94 C 0.09 Mn 0.49 Other V: 0.2 Fe balance

Reduced activation ferritic martensitic steel is candidate structural material of blanket.

Prior austenite grain boundary

Block boundary

Some sub grains

Packet boundary
1m

Lath boundary
Chemical reaction of steels base metal (Fe), alloying elements (Cr, W) and 3 carbides with liquid metals

Corrosion of RAFM steel in liquid metals

Background -3 (Liquid breeders) Major characteristics of liquid breeders

M.P. (K) Thermal conductivity (W / (m x K)) Density (kg/m3) Viscosity (mPas)

Li
Pb-17Li Flinak (LiF-NaF-KF) Flibe (LiF-BeF2)

Alkali metal
Heavy metal Molten salt

453.7
508 727

53.7 (800K)
1.2

481 (800K)

0.344 (800K)

9568 (800K) 2146 (800K) 4.1 (900K)

Molten salt

732

1.2

1993 (800K) 7.5 (800K)

High thermal conductivity in liquid metal Liquid Li+ Lithium Free electron

High chemical stability of molten salt Flinak Li+ + F-

Already stable state by ion bonding

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Purpose

Purpose of the present study is follows;

- Establish corrosion test technology for liquid Li and Pb-Li - Make clear the corrosion characteristics of RAFM JLF-1 steel in the liquid metals - Make clear the corrosion of coating in the liquid metals - Modeling of the corrosion of RAFM steel in the liquid metals

Experimental procedure (1)

Initial impurity of liquid metals (wppm)
Fe
Li Pb-17Li 0.85 2.2

Pb-17Li provided by santoku coop.

Cr
0.12 0.17

W
0.31 0.52

Ni
0.8 1.3 Nitrogen: 65 -

Experimental condition
Temperature 600C Time(hours) Re for mixing Li Static Flowing Static Pb-17Li Flowing 250 18512 High purity 30-250-750 250 250-3000 2859 High purity, Li3N dope Li2O dope, C dope High purity High purity Material JLF-1 Er2O3 coat JLF-1 JLF-1 Er2O3 coat JLF-1

Carbon

Li2O

Li3N

Experimental procedure (2)

Static test (Simple immersion) Flowing test (Mixing vessel) Fixed specimen

Influence of flow 3cc 48mm 100cc

Width of impeller 33 Rotation speed 100 rpm Velocity around specimen v==0.17cm Re number for mixing nd 2

Re =

Analysis of corroded specimen

(a) Weight loss measurement (To estimate the corrosion (loss) rate) (b)SEM/EDX analysis for surface and cross section (To evaluate the metallurgical change of steels)

(c) Impurity analysis of liquid breeders by ICP-MS ( Fe, Cr, W, non metal impurity) (To investigate mass balance between loss in specimen and increase of metal impurity in melt )

Cleaning procedure for tested specimen Specimen in Li

Take out sample
Specimen inPb-Li

Immersion to ethanol
Li immersion at 350C

Acetone Immersion to ethanol

Acetone

Experimental results (Mass loss of specimen by corrosion in Li)

Weight loss of specimens (g/m2)

14 12 10 8 6 4 2 0 -2
Li (+0.8wt%Li2O) (Static) 750-hour Li Li Li (Pure) (+3.7wt%C) (Pure) (Flow) (Static) (Static) 250-hour 250-hour 250-hour

Li (+0.5wt%Li3N) (Static) 250-hour

- The influence of non-metal impurity (i.e. nitrogen and oxygen) in liquid Li was large on the corrosion loss. - The Influence of oxygen in Li on the corrosion was newly found.)

Experimental results (Lithium)

Phase transformation c

Phase transformation C
a a a BCT a BCC

Fe

Initial

250 hour
carbon dope

+3.7wt%

+0.8wt%Li2O oxygen dope

(Cr dissolution)
Phase transformation

No phase change

1m

1m

1m

287 hour

122 hour

780 hour

+0.5wt%Li3N nitrogen dope

(Cr dissplution)

1m

20m

20m

20 hour

120 hour

250 hour

Corrosion of Er2O3 coating in Li

100
Er concentration in Li unit: wppm (ICP-MS)

80 60 40 20 0 0
0 10

Surface color was black after the corrosion test though the color was metallic luster before the test.

600C Er2O3/JLF-1
Thermal linear expansion %

20 10 exposure20 (hour)

Peeling off

normal
Crack

Corroded (Er-Cr rich)

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 -0.1

30
Li
JLF-1

30

Er2O3
0 50 100 150 200 Temperature (C) 250

The oxide itself might be chemically stable in the liquid breeders. The damage was possibly 11 made by a large difference of the thermal expansion ratio between adhered Li and the coating during a heat up and a cool down procedure of the corrosion test when the Li was solidified.

Summery for corrosion in Li

- Nitrogen dissolved in Li has big influence on the compatibility. It was newly found that oxygen in Li can increase the corrosion of steel. The nitrogen and oxygen dissolved as non-metal impurity in Li must be removed before the use. Carbon in Li can suppress the the depletion of carbon in the steel.

- The issue for the coating of liquid blanket is the peeling of the coatings in the liquid metals.
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Experimental results (Weight loss of specimen in Pb-Li at static condition)

Corrosion was suppressed when the metal element, i.e. Fe and Cr, in Pb-17Li was saturated..
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Experimental results (Pb-17Li)

600oC 750 hours

Low mag. (x1000)

600oC 3000 hours

Low mag. (x1000)

20m

20m

High mag. (x3000)

High mag. (x3000)

5m

5m

The corrosion in JLF-1 was selective attack to some boundaries of microstructure.

Experimental results (Corrosion of Er2O3 coating in Pb-Li)

Themal linear expansion (%)
1.2 1 0.8 0.6 0.4 0.2 0 0 200 400 Temperature (C) 600 Er2O3 Li Pb JLF-1

20m

Resin Er

Pb-Li

Steel matrix

Fe

Cr 0 20 40 Depth (m) 60 80

The oxide itself might be chemically stable in the Pb-Li. The damage of the coating was possibly made by a large difference of the thermal expansion ratio between adhered Pb-Li and the coating during a heat up and a cool down procedure of the corrosion test when the Pb-Li was solidified.
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Count number

Experimental results (Corrosion in flowing Li and Pb-Li)

Flowing Li 10m Flowing Pb-17Li 10m

Internal diffusion of liquid metals

Erosion- corrosion was caused by peeling of subgrains after corrosion on surface.

(FAC)
16 (Erosion corrosion)

Corrosion modeling

V dC J h (Cs - C) S dt
Transient of metal impurity in liquid breeders Corrosion ratio

Mass balance between increase of metal impurity in liquid breeders and corrosion ratio of specimen

hSt C Cs(1 exp( )) V

Concentration of metal in liquid breeders

hSt m VCs(1 exp( )) Mass loss of specimen by corrosion V

Li (65wppm nitrogen) Solubility (Cs) wppm Molppm Fe Cr -* 52.4 (800 C) <7>~ 94.3 (600C) <12.6> Pb-17Li 47 (600C) ~<145> 10 (500C) <40> Pb 34 (600C) <126> 1 (600C) <3.7 >
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Mass transfer model in corrosion (Li)

Different corrosion device

Different geometrical factor of corrosion system Volume / corrosion surface area

Large

600oC (Li)

V/S

Small
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Mass transfer model in corrosion (Pb- Li)

600oC (Pb-Li)

19

Summery
Major conclusions are follows;
- Corrosion test technology for liquid Li and Pb-Li was established. - The corrosion characteristics of JLF-1 in static Li and Pb-Li were investigated. Then, we started to study about the corrosion in flowing condition. -Modeling of corrosion of JLF-1 in Li and Pb-Li was started. - Fundamental corrosion characteristics of anti corrosion coating in liquid Li and Pb-Li was studied. The issue is the peeling off of the coatings in liquid metals.

20

21

Corrosion of Fe-Al coating in liquid Pb-Li

10m

After 500- hour immersion in Pb-17Li at 600 degree C

Coating it self was chemically stable in liquid Pb-Li. However, the peeling off is issues for the coating. Now, study on metal plating technology is under going.

Pb-Li

Fe-Al coating

316L Pb

Fe

Al

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Background -4 Corrosion phenomena

At flowing static condition

Liquid metal corrosion

All liquid metals especially heavy liquid metal

-Dissolution of steel element into liquid metals -Diffusion of metal elements of liquid metal into steel matrix

FAC

At flowing condition

Compatibility

GB attack

Erosion- corrosion
Determined by alloying process Determined by chemical potential of non-metal impurity

Pb, Pb-Bi

Li, Na, K, Pb-Li(?)

Formation of corrosion products

(Carbides, oxides, nitrides, hydrides and so on)

Peering of corrosion products

Solubility of metal elements and chemical potential of non- metal impurity 23 in liquid metals are important parameters which determine the corrosion. 23

Effect of nitrogen on corrosion in Li

5Li 3 N Cr Li 9 CrN 5 3Li

2Li 3 N Fe Li 3 FeN 2 3Li

Solubility of Cr in Li (Nitrogen 65wppm) used in present study Solubility of Cr in Li (Nitrogen 200wppm) [11]
10000

Solubility of Fe and Cr in Lithium (wppm)

Solubility Cr in Li (Nitrogen 790wppm)[12 ] Cr in Li (Nitrogen 150wppm)[12] Solubility of Cr in Li (Nitrogen <10wppm) [11 ]

100 1 0.01

Solubility of Fe in Li (Nitrogen 500wppm)[11] Solubility of Fe in Li (Nitrogen <10wppm) [11 ]

800 900 1000 1100 1200 1300
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0.0001 700

Temperature of Lithium (K)

Experimental results (Transient of metal impurity in Pb-17Li)

After the immersion of JLF-1 in Pb-Li.

12
Concentration (wppm)

10 8 6 4 2 0 0 500

Fe Cr W Mn

1000 1500 2000 2500 3000 3500

Time (hours)

[1] M. G. Barker, P. Hubberstey, A. T. Dadd, S. A. Frankham, J. Nucl Mater., 114, 143-149 (1983). [2]V. Tsisar, M. Kondo, et al., J. Nucl. Mater, under review. H. U. Borgstedt, H. Feuerstein, J. Nucl. Mater., 191-194, 988-991. [3]N. Simon et al., Int. J. 25 Heat Mass Transfer., vol.38, No.16, 3085-3090 (1995).