Influence of Liquid Sodium on

Mechanical Properties of Steels,

Refractory Alloys and Ceramics
Hans Ulrich Borgstedt
Formerly Section Head
Inst. of Materials Research of FZK
Head of Liquid Metal Laboratory
Part 1: Corrosion and Reactions with
Impurities Dissolved in Sodium
1.Corrosion mechanisms
2.Influence of impurities dissolved in liquid
sodium
3.Sodium corrosion of reactor materials
4.Corrosion of some ceramic materials
5.Methods of corrosion studies
 Corrosion and Reactions with Impurities
Dissolved in Sodium

1. Corrosion mechanisms

1.1 Corrosion in stagnant liquid sodium

1.2 Corrosion in turbulent liquid sodium flow
1.3 Selective leaching of alloy components
 Corrosion Mechanisms

Na corrosion is based on dissolution !

The dissolution rate S/t is ruled by the
difference of the chemical activities in the
solid phase, a(s) , minus that in the liquid
phase, a(l)
• S/t = ß [a(s) - a(l)] (1)
• Based on the work of Epstein and of Weeks
 Corrosion Mechanisms

• Corrosion in stagnant liquid sodium is

characterized by the fact, that the difference
of the activities, a(s) - a(l), is dependent on
time. The activity of the solute, a(l),
increases from very low values at the
beginning of the process to values close to
that in the solid phase, a(s),,thus, corrosion
rate approaches zero
 Corrosion Mechanisms

• Corrosion in turbulent liquid sodium flow is

determined by equation (1)
• Flow and temperature gradients keep the
difference of activities as and ad on its level
• Dissolution is influenced by the apparent
solubility that can be different from the
physical one
 Corrosion Mechanisms

• Chemical activity in the bulk stream in non-

isothermal flowing systems is orders of magnitude
lower than saturation.
• Its value can be neglected, when the temperature
gradient is in the order of 100 K. The corrosion
rate becomes proportional to the activity at
saturation :
• S/t = ß asat(2)
• ß is the corrosion constant
• asat can be influenced by side reactions
 Corrosion Mechanisms

• ß depends on the hydraulic parameters of the flow. Epstein

and Weeks published equation (3):
• ß = ShDdH-1(3)
• Sh = Sherwood number, D = diffusion coefficient and dH =
hydraulic diameter of the test tube.
• The Sherwood number is related to the flow velocity via
the Reynolds & Schmitt number:
Sh = 0.0481  Re0.75Sc0.42(4)
• Re is the Reynolds number Re = v  dH  -1 (v is the flow
velocity and  the viscosity)
• and Sc the Schmitt number Sc =   D-1
 Corrosion Mechanisms

• ß depends on temperature through viscosity 

and diffusion coefficient D. Corrosion rates
are further related to temperature via the
solubility as a function of temperature.
• With the knowledge of ß and asat one can
estimate the Na corrosion rate (using equs.
1-4)
• Confirmed by corrosion experiments with Ni
in Na circuit and solubility data
 Saturation concentrations of steel components in
liquid sodium at 773 and 973 K

Steel component Csat [mol%] at 773 K Csat [mol%] at 973 K

Fe 3.5 10-5 2.7 10-4

Ni 4.3 10-5 1.1 10-4

Cr 2.2 10-7 5.6 10-4

Mo 9.9 10-7 4.0 10-4

 Selective leaching of alloy
components
• Different apparent solubilities cause selective
leaching of alloy components
• Stainless steels form surface layers depleted in Cr,
Ni and Mn
• Fe and Mo are enriched in surface layers
• Austenitic structure is changed to ferritic one
• Grain boundaries are depleted to larger depth
Surface layer depletion zone
Ferritic layer and grain boundaries
 Corrosion and Reactions with Impurities
Dissolved in Sodium

2. Influence of impurities dissolved in liquid

sodium
2.1 Sodium oxide
2.2 Carbon
2.3 Analytical procedures to determine Na2O
and C
 Influence of impurities in liquid sodium

• Thorley and Tyzack exhibited the influence of

oxygen on the Na corrosion of a group of steels in
a systematic study
• log S = 2.44 + 1.5 log cO –18000/2.3RT (with mass
loss S in mils/y, cO in ppm and T in K
• Their results are shown in the following figure
• Na corrosion of stainless steels can be significally
reduced by decreasing the oxygen content of
sodium
Corrosion results of Thorley and Tyzack (1967)
 Stability of sodium chromite in Na
Influence of temperature and O concentration

• Na chromite stable at moderately high temperature and

high oxygen concentration in Na
 Influence of carbon on Na corrosion of
stainless steel
• The formation of chromium carbides acts as
barrier against depletion of Cr in the surface layers
• However, the formation of chromium carbides
reduces the stability of the austenitic phase
• Since C reacts with Cr to form carbides, C
decreases the chemical activity of Cr in steel
Analytical procedures to determine Na2O
and C
• Oxygen
• Online with electrochemical cells using solid electrolytes
(ThO2/Y2O3)
• Vacuum distillation technique, alkalimetric measurement
• Carbon
• 18/8 steel foil equilibration technique
• Electrochemical cell using molten salt electrolyte
• Diffusion cell, C diffuses through Fe membran into gas
phase, subsequent gas analysis
Corrosion and Reactions with Impurities
Dissolved in Sodium
3. Sodium corrosion of reactor materials

3.1 Corrosion of iron base alloys

3.2 Corrosion of nickel base alloys
3.3 Corrosion of some refractory alloys
 Na Corrosion of Reactor Materials

• Core materials have to withstand sodium at highest

temperature and flow velocity
• Life time of these materials is limited to about 2 years
• Cladding materials are stabilized or unstabilized austenitic
stainless steels
• Structural materials are exposed to sodium of lower
temperature and flow velocity
• Life time is in the order of more than 30 years
• Austenitic steels 304 and 316 are used
Schematic view on corrosion effects of
cladding tubes
Corroded surface of steel 1.4970 after 5000 h
in Na at 700 °C
Bright spots are Mo rich particles on ferritic surface grains
 Downstream effect of mass loss

• Corrosion is influenced by the position in the tubes

• The geometric factor L/D (tube length of specimen
position over hydraulic diameter) was introduced by
Zebroski:
• R = v 0.884 cO1.156 exp [12.845 –13300/T – 0.00676 L/D +
2.26/(t+1)]
• (R = rate of metal removal in mg/dm2/month , V = sodium
velocity in ft/sec, cO = concentration of oxygen in ppm, t =
time in months, T = sample temperature in K)
Downstream effect reported by Suzuki and Mutoh
(steel 316 at 700°C, 2 ppm O & 4 m/s, cw and st)
 Na Corrosion of nickel base alloys

• Inconel 600 and Nimonic were already studied by Thorley

and Tyzack (1967)
• Corrosion rates at 650°C were 3 times higher than with
steel AISI 316
• There was no influence of the oxygen activity on corrosion
rates
• Increasing flow velocity of sodium increased corrosion
rates significantly
• Surface layers were not changed in their composition
 Corrosion of refractory metals

• Mo, W, and Re have extremely low solubility in

Na
• Alloys based on these metals are well compatible
with Na
• Mo alloys are sensitive to oxidation in Na with
oxygen concentrations close to saturation
• Such alloys may be used for particular high
temperature applications
 Corrosion of vanadium alloys

• Solubility of vanadium in sodium is very low

• V alloys react with non-metals (C,N,O) present in
sodium
• They are oxidized in cold trapped sodium
• V-Ti-Cr alloys are corroded by internal oxidation
• V alloys have been considered as alternative fuel
element clads
• Hardened surface layers are formed
• Depths of such layers depends on the composition
 Corrosion of vanadium alloys

• formation of hardened layers through internal oxidation

• V-1Ti-15Cr (1), V-2Ti-15Cr (2), V-3Ti-15Cr (3), 1000 h
at 600 °C
 Corrosion and Reactions with
Impurities Dissolved in Sodium
• 4. Corrosion of some ceramic materials
(structural and functional ceramics, graphite
core catcher minerals and concrete)
 Corrosion of some ceramic materials

• Materials satisfying the thermodynamic stability

criterion for sodium compatibility:
• Alumina, beryllia, magnesia, thoria, zirconia are
compatible oxides
• Compatibility depends on the purity of the
ceramic materials
• Unsufficient purity causes intercrystalline
corrosion and desintegration of samples
 Corrosion of some ceramic materials

• Basalt and concrete that are proposed as core

catcher material are poorly compatible
• Their humidity causes violent reactions
• Functional ceramics as ThO2-Y2O3 are compatible
up to 400 °C
• Graphite as getter material for radioactive cesium
is compatible to high temperatures
 Corrosion and Reactions with Impurities
Dissolved in Sodium

• 5. Na Corrosion studies
• 5.1 Corrosion studies in stagnant and
isothermal liquid metal
• 5.2 Corrosion studies in flowing liquid Na
and thermal gradients
 Na Corrosion studies
- tests in stagnant sodium

• Corrosion tests in stagnant liquid sodium are performed in

sealed capsules
• Capsule material should not be different from specimen
material
• Capsules to be filled in inert atmosphere glove boxes
• Closure by vacuum tight flanges or welding
• Purity of sodium is not always well defined in capsules
• Oxygen meters allow studies of chemical reactions
between Na, materials and oxygen in capsules
Na Corrosion studies
- testing in sodium loops

• Simple figure-of-eight
corrosion loop (Klueh)
• Hot part separated from cold
one by heat exchanger
• Heat exchanger acts as
economizer
• Test sections in hot part, pump
& flow meter in cold one
• cold trap in by-pass
• Expansion tank is an important
component of a Na loop
• Auxiliary inert gas circuit
 Conclusions concerning Na corrosion

• Corrosion of clad and duct materials under present core

conditions is within the allowable range
• Corrosion in the core must be minimized to reduce
activation of the cooling systems
• Mass loss and formation of corrosion layers does not lead
to problems in piping and vessels
• Selection of steels should avoid mass transfer due to
different chemical activities
• Minimized corrosion demands for low oxygen activities
• Downstream effect restricts effects in components
 Conclusions concerning Na corrosion

• Materials tested in the work referred are limited to

700 °C in the core and 600 °C in the pipes and
vessels
• Advanced materials for higher temperature have to
be studied in respect to their behaviour in contact
with Na
• The possibility of mass transfer has to be
considered
 Thanks to the Pioneers of Na corrosion

• Pioneer work in 50th and 60th mainly in USA,

UK, France, Russia, Japan, Germany
• DeVan, Epstein, Weeks, Zebroski (USA)
• Champeix (France)
• Thorley (UK)
• Furukawa, Suzuki (Japan)
• Ivanovski, Ioltukhovsky (Russia)
Thanks to colleagues of the SNR & EFR
projects
• Casteels, Tas, Grosser, Menken, Hissink and
Kolster in the co-operation for the SNR 300
project
• Debergh, Horton, Huthmann, Wood in the EFR
co-operation
• Drechsler, Frees, Peric, Schneider, Wittig in the
sodium work at KfK
• The former Fast Breeder Project of KfK as
generous supporter of our work