NUCLEAR SCIENCE AND ENGINEERING: 160, 75–97 ~2008!

Corrosion of Materials by Liquid NaK Coolant

in a Nuclear Power System

J. Zhang,* R. Kapernick, and T. F. Marcille

Los Alamos National Laboratory, International Nuclear System Engineering Group, MS K-575
Los Alamos, New Mexico 87545

Received May 24, 2007

Accepted January 12, 2008

Abstract – Corrosion of the primary coolant structural materials in a nuclear power system is a potential
concern when liquid metal is used as the coolant. For the current space reactor design, liquid sodium-
potassium eutectic (NaK) has been selected as a candidate for the primary coolant and stainless steel as
the structural material, so whether or not corrosion is a problem for this system must be determined. This
paper documents a first step to understanding the extent of corrosion in the selected candidate design.
Data available in the literature have been compiled and are analyzed, factors affecting corrosion are
assessed, and a theoretical basis of the corrosion mechanisms by liquid metals is presented. This study
provides some useful information for the design of NaK coolant systems and some recommendations for
what additional experimental and theoretical work is needed to understand the corrosion mechanisms and
limitations of using NaK as a primary coolant.

I. INTRODUCTION on corrosion by liquid NaK are not plentiful, and most of

Corrosion of structural materials by liquid-metal cool-
ants such as sodium, lead, bismuth, potassium, and their
alloys is an important concern and potential limitation in
their use in nuclear power systems. Studies have shown
that corrosion by liquid metal can be a physical or a
chemical process, or both. When steel is exposed to liq-
uid metal, some of its constituents can dissolve into the
liquid and may or may not react with the impurities in
the liquid. Also, the liquid can penetrate into the steel
along the grain boundaries or other defects, which changes
the microstructure, composition, and surface morphol-
ogy and thus the properties of the material to some depth
into the material. Such changes can become significant
with time and may eventually lead to material failure.
Recently, liquid sodium-potassium alloy ~NaK!,
which had been used as the coolant in the EBR-I and
SNAP-8 reactors, has been selected as a candidate cool-
ant for a next-generation space reactor because of its low
melting point and relatively high heat transfer capacity.
Compared with liquid sodium, which has been used as a
coolant in many terrestrial fast breeder reactors, studies
*E-mail: jszhang@lanl.gov
them for its use as a nuclear reactor coolant were carried
out prior to 1970. Despite these shortcomings, we have
compiled and assessed available data and studies to pro-
vide some understanding of the corrosion by NaK and to
determine what further experiments and studies are
needed to answer this concern.
II. LIQUID-METAL CORROSION MECHANISM
Compared to corrosion by aqueous media, which
has been found to be primarily an electro-chemical pro-
cess, corrosion by liquid metal is a physical or physical-
chemical process involving the dissolution of material
constituents into the coolant, transportation of these con-
stituents in the liquid and solid phases, and reactions
between the corrosion products and impurities. The cor-
rosion can be described in terms of the thermodynamics
and kinetics of the several interactions that lead to trans-
port of the corrosion products into and through the liquid-
metal medium. The driving forces for such corrosion
mechanisms are states of nonequilibria such as the solu-
bility of metals and nonmetals in the liquid and their

75
76 ZHANG, KAPERNICK, and MARCILLE
interactions both in the liquid and solid surfaces in con-
tact with the liquid metal.1 The corrosion types and mech-
anisms of liquid-metal corrosion are shown briefly in
Fig. 1 and described below.
II.A. Solution Corrosion
The driving force for solution corrosion is the chem-
ical potential for dissolution of solid surfaces in contact
with the liquid. It can be simply expressed by
A ~solid metal! b A ~in liquid metal! .
Solution corrosion is primarily a function of the solubil-
ity of the solid in the liquid, which is a function of tem-
perature. The dissolution process of solid metal will
continue until the chemical potential of the dissolved
solid metal has the same chemical potential in the two
phases. The corrosion rate by this mechanism depends
on both the dissolution rate at the liquid-solid interface
and the transport rate in the liquid.
There are several types of solution-corrosion pro-
cesses, as shown in Fig. 1. Uniform solution corrosion is
an even rate of surface recession with a complete lack of
subsurface effects.2 It occurs only in high-purity elemen-
tal materials and is quite rare in practice. Intergranular
solution corrosion is much more common in engineering
practice. It occurs in the deposited phases at the grain
boundaries in the material, which are much less resistant
to the liquid metal than the grain body.2 Further, if the
Fig. 1. Corrosion types and mechanisms of liquid-metal corrosion.
NUCLEAR SCIENCE AND ENGINEERING
dissolution rates in various crystal directions are differ-
ent, crystalline facets are expected to be developed.3
For alloy or steel materials, there will be a leaching
solution corrosion that results from the selective disso-
lution of the alloy constituents. The leaching solution
corrosion has been described as a combination of disso-
lution and chemical reaction mechanisms. It removes
alloy constituents at various rates, which results in a com-
position change of the surface layer. If the layer contin-
ues to develop and the removal of the alloy constituents
exceeds a specific minimum threshold level, the layer
will become a new phase layer.4 For example, a ferrite
layer has been observed on Type 316 stainless steel
~SS316! after being exposed to liquid sodium.5
Stress corrosion is another important concern in
liquid-metal corrosion. The combination of the dissolu-
tion and mechanical stress can cause cracking of the ma-
terials, which has been observed at bends in a liquid
sodium-potassium ~NaK! loop.6
Solution corrosion results in weight loss, surface re-
cession, and phase changes and in the potential for the
development of cracks and cracking propagation and con-
tamination of the liquid. All of these phenomena are po-
tentially serious problems for materials in liquid-metal
systems. For example, decarburization resulting from the
loss of carbon from low-alloy steel by liquid sodium
causes significant property changes of the steel at the
operation temperature for short times, which may lead to
mechanical failure of the components containing the
liquid-metal coolant.
VOL. 160 SEP. 2008
 CORROSION BY NaK COOLANT
II.B. Penetration Corrosion
Penetration corrosion results from the diffusion of
liquid metal into the material lattice. It can proceed uni-
formly or intergranularly. The intergranular penetration
can be accelerated in austenitic stainless steels because
of sensitization. The austenitic steel becomes sensitized
when chromium and carbon combine to form chromium
carbide, which is subsequently precipitated in the grain
boundaries. Therefore, sensitization is a function of the
activity and distribution of carbon and chromium, and
some evidence indicates that sensitization occurs more
readily in carbon-contaminated sodium than in other
media.7
Penetration of liquid metal into the material depends
in part on the surface tension. It occurs when the grain
boundary interfacial energy is greater than twice the solid-
liquid interfacial energy.8 If the material is stressed, pen-
etration may occur when liquid lowers the surface energy
of the solid. The liquid penetrates into the solid through
various paths: grain boundaries, specific crystallographic
direction, vacancies and pores, formed defects, etc. The
liquid penetrates into the solid metal in the areas where
defects reach the surface, and then the corrosion front
moves along grain boundaries or defects. The impurities
in the liquid diffuse into the solid materials, and the im-
purities in the solid diffuse into the liquid, resulting in
the impurities’ redistribution in the two phases. The dif-
fusion direction of the impurities can be determined from
the coefficients of equilibrium distribution.9
Penetration corrosion may result in phase transfor-
mation and new phase formation. The inward diffusion
of liquid-metal atoms and their interactions with one or
more of the alloy components result in intermetallic com-
pounds that can precipitate on the surface. Because pen-
etration is generally coupled with chemical reactions due
to the impurities in the two phases, complex compounds
are formed within the limits of the grain boundaries.
Impurities such as oxygen and carbon are redistributed
because of their different chemical potentials in the two
phases.
II.C. Chemical Corrosion
Chemical corrosion results from reactions between
the materials of construction and the impurities in the
liquid metal. Given that some level of impurities gener-
ally exists, chemical corrosion is very common. It pro-
duces simple or complex corrosion products on the solid
material surface or in the liquid that may stimulate or
suppress interaction. The products may be soluble, loosely
or tightly adherent, and affect the net corrosion rate. Sim-
ilar to penetration corrosion, chemical corrosion can lead
to interstitial impurities’ redistribution or partition of the
impurities between the liquid solid materials. It can also
result in chemical compound formation, surface layer
deposition, and particle formation in the liquid.
NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008
77
II.D. Mass Transfer
In a static system, mass transfer is due to diffusion
only, whereas in a flowing system, mass transfer is due
to both convection and diffusion. Further, deposition of
the corrosion products, reactants, and the impurities
in the coolant may happen during the transport through-
out the loop by the liquid-metal coolant. Mass transfer
in liquid-metal systems has been categorized into two
types: 10 dissimilar-metal mass transfer or active gradi-
ent mass transfer and thermal gradient mass transfer or
temperature gradient mass transfer.
Dissimilar-metal mass transfer can occur in both
isothermal and nonisothermal systems. The driving force
for this mass transfer is the thermodynamic requirement
that the chemical potential of each element should be
equivalent in all phases; i.e., the free energy of the
system approaches its minimum value through the al-
loying of different metals. Such mass transfer can be
described briefly by the following: Atoms of metal A
dissolve into the liquid metal and are carried by the
liquid metal to the surface of metal B where the atoms
of A come out the solution, alloy with metal B, and
diffuse into metal B. It has been shown that such mass
transfer becomes increasingly important as the system
temperature increases and occurs in a system built of
different materials.
Thermal gradient mass transfer can occur only
in nonisothermal systems ~by definition!. The driving
force of this type of mass transfer is the difference in
the solubility of the corrosion products in the high-
and low-temperature sections of the system. The corro-
sion products enter into the liquid at the high-temperature
section and are transported to a low-temperature
section, where they come out of the liquid. Com-
pared to dissimilar-metal mass transfer, there is
no alloying process, and the precipitates can remain
suspended in the liquid as particles or deposited on the
surfaces.
Because most engineering systems are nonisother-
mal and the construction materials are steel or other al-
loyed materials, the overall mass transfer is generally
caused by both dissimilar-metal and thermal gradient mass
transfer.
III. FACTORS AFFECTING
LIQUID-METAL CORROSION
As discussed above, liquid-metal corrosion involves
three processes: interactions between the liquid and solid
at the solid surface and transport of corrosion products0
impurities in the liquid, and transport in the solid. Fac-
tors affecting these three processes are divided into three
groups: environmental, metallurgical, and technological,
as shown in Fig. 2.
78 ZHANG, KAPERNICK, and MARCILLE

Fig. 2. Factors affecting liquid-metal corrosion.

III.A. Environmental Factors
Liquid-metal environmental conditions include sys-
tem temperatures, liquid-metal composition, flow condi-
tions, and the flow path geometry structures. Temperatures
throughout the loop affect dissolution0chemical reaction
rates, corrosion product diffusion in both solid and liq-
uid, and liquid-metal properties such as viscosity and
density. Increasing temperature results in higher disso-
lution rates, higher solubility, higher diffusion coeffi-
cients, and smaller viscosities and thus leads to a higher
corrosion rate.
In an isothermal loop, if there is only concentration
gradient mass transfer, species concentrations eventu-
ally reach an equilibrium distribution, at which point no
further corrosion occurs. Sustained corrosion can occur
only in a nonisothermal system. With temperature gradi-
ents, elements in the steel will be dissolved in the hot
sections, transported to locations with lower tempera-
tures, and precipitate. It has been shown that as the tem-
perature difference through the loop increases, corrosion
in hot sections of the loop becomes more severe. Greater
precipitation in colder areas can accelerate corrosion in
the hot sections and may become the controlling step for
the corrosion in a nonisothermal system.
For different liquid metals and0or alloys, the thermo-
dynamics can be quite different. So the corrosion rate is
also affected by the liquid-metal composition, including
its impurities. For example, liquid lead and lead-bismuth
are more corrosive than sodium. However, the presence
of oxygen in lead and lead-bismuth may result in a pro-
tective oxide layer on the material surface, while the
oxygen in liquid sodium can accelerate the corrosion
significantly.
The flow condition ~principally flow velocity! is an-
other important environmental factor that affects the cor-
rosion rate. In a flowing system, although mass transfer
between the coolant and solid surface takes place by
both diffusion and convection, it is convection that dom-
inates the transport because convection is much faster
than species diffusion. However, the corrosion rate be-
comes independent of the velocity if the velocity is high
enough. Experimental results from liquid sodium loops
have shown that the corrosion rate in the hot leg is al-
most proportional to the flow velocity when the velocity
is not too high and is independent of the velocity if the
velocity exceeds a critical value. It appears that the crit-
ical value is in the range of 3 to 4.5 m0s ~Ref. 11!.
In a nonisothermal liquid-metal system, the corro-
sion rate is also affected by loop geometry such as the

NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008

 CORROSION BY NaK COOLANT
flow path geometry structure. It has been reported that
the corrosion0precipitation profile in a nonisothermal
lead-bismuth loop depends on the loop length, hydraulic
diameter, and flow path geometries.12 Also, the number
of different types of materials and their surface areas,
temperatures, and local flow conditions have to be taken
into account because of dissimilar-metal mass transfer
effects.
III.B. Metallurgical Factors
Metallurgical factors include the composition and
microstructure of the materials and their impurities. Dif-
ferent material constituents have different mobilities and
solubilities in the liquid, resulting in different leaching
rates. It has been shown that Ni and Cr in stainless steel
have high initial leaching rates in a sodium loop. Micro-
structure is important because it affects greatly the prop-
erties of the materials, diffusion rates of the corrosion
species in the materials, and liquid-metal penetration into
the material.
The structural material compositions of the system
also affect the transport of impurities in the liquid. For
example, oxygen concentration is almost a constant in a
sodium loop made of pure iron, while it is a function of
location in a sodium loop made of steel.13
One method for improving the anticorrosion proper-
ties of a material is by alloying the materials to form the
thermodynamically stable interstitial phases. The alloy-
ing can also increase the creep strength of the materials.
The presence of impurities such as oxygen and car-
bon in the structural materials has also been found to
enhance corrosion. The impurities can promote liquid-
metal penetration into the material as well as phase
deposition.
III.C. Technological Factors
Technological factors include the stress state, new
phase formation due to machining, welding, assembling
of structure, and surface conditions. Experimental expe-
rience in a NaK loop indicates that the crack formation
at a bend is due to its external stress.6 Therefore, the
stress state has to be taken into account when operating a
liquid-metal system. The surface condition of the struc-
tural materials also affects the corrosion rate. Through
deposition of a protective layer, the anticorrosion prop-
erties can be significantly improved. If the new phase
formed during the technological process has less corro-
sion resistance, obviously, the corrosion rate of the ma-
terials is increased.
IV. SOLUBILITY DATA
Although most common nonmetals and metals have
low solubility in liquid sodium and NaK, it has been
NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008
79
recognized that solubility plays an important role in cor-
rosion by liquid sodium and NaK. Generally, solubility
can be expressed as a function of temperature:
B
log Si ~ppm! ⫽ A ⫹ , ~1!
T ~K!
where
S ⫽ solubility of species i in the liquid at temper-
ature T
A, B ⫽ constants.
IV.A. Solubility of Nonmetals
The solubility of oxygen in liquid sodium has been
determined by several authors. The solubility data were
summarized in the book by Borgstedt and Mathews.14
The authors recommended the solubility equation devel-
oped by Eichelberger 15 :
2447
log SO ~ppm! ⫽ 6.239 ⫺ , ~2!
T ~K!
in the temperature range 373 to 828 K in sodium. The
solubility of oxygen in liquid potassium is much higher
than in sodium. Based on Williams, Grand, and Miller’s
data 16 in the temperature range 338 to 783 K, Sreedha-
ran and Gnanamoorthy 17 developed the following corre-
lation for the solubility of oxygen in liquid potassium:
876
log SO ~ppm! ⫽ 5.3015 ⫺ . ~3!
T ~K!
Using a vacuum distillation technique, Ganesan, Adel-
helm, and Borgstedt 18 reported a lower oxygen solubil-
ity in potassium in the temperature range 323 to 473 K.
The constants in Eq. ~1! are A ⫽ 4.1012 and B ⫽ ⫺774.3.
Krishnamurthy et al.19 reported that the constants are
A ⫽ 3.9702 and B ⫽ ⫺420.4 in the temperature range
343 to 675 K.
There are few data on oxygen solubility in liquid
NaK. Krishnamurthy et al.20 developed a correlation for
NaK ~55 wt% K! in the temperature range 333 to 703 K:
1101.11
log SO ~ppm! ⫽ 4.8480 ⫺ , ~4!
T ~K!
and Sakai et al.21 developed a correlation for NaK ~78
wt% K! in the temperature range 363 to 483 K:
2795
log SO ~ppm! ⫽ 7.09 ⫺ . ~5!
T ~K!
Figure 3 shows curves of the oxygen solubility as a
function of temperature. The figure indicates that the
solubility of oxygen in liquid sodium and NaK is much
80 ZHANG, KAPERNICK, and MARCILLE

Fig. 4. Oxygen solubility in NaK as a function of potas-

sium fraction.

5790
log SC ~ppm! ⫽ 7.646 ⫺ . ~6!
T ~K!
Fig. 3. Oxygen solubility in liquid sodium, potassium, and
NaK and carbon concentration in sodium. 1: Oxygen solubility As shown in Fig. 3, the solubility of carbon in sodium is
in potassium, Eq. ~3!. 2: Oxygen solubility in NaK ~55 wt% K!, much lower than that of oxygen at the same temperature.
Eq. ~4!. 3: Oxygen solubility in sodium, Eq. ~2!. 4: Oxygen
solubility in NaK ~78 wt% K!, Eq. ~5!. 5: Carbon solubility in
The solubility of nitrogen in sodium is extremely
sodium, Eq. ~6!. low. The following correlation is recommended by Borg-
stedt and Mathews 14 :
2780
log SN ~ppm! ⫽ ⫺7.17 ⫺ . ~7!
T ~K!
less than that in liquid potassium. The solubility in NaK
~78 wt% K! is almost the same as that in sodium. Krish- IV.B. Solubility of Metals
namurthy et al.20 concluded that the closeness in the sol-
ubility curves was due to the container being made of The solubility of the main constituents of steel such
stainless steel, which lowers the solubility of oxygen in as the iron, nickel, and chrome in liquid sodium and
NaK. Based on this, one can use a cold trap method to potassium has been studied extensively and summarized
purify the NaK in a system made of stainless steel. in a handbook.23 However, the solubility of iron in so-
To study the effect of the fraction of potassium on ox- dium is scattered, and there has been little effort to study
ygen solubility in a liquid sodium-potassium alloy, Krish- the solubility of these metals in liquid NaK. As recom-
namurthy et al.20 carried out solubility measurements for mended in Ref. 14, the following correlations are
a range of potassium fractions at a temperature of 473 K. proposed:
The data are shown in Fig. 4. The solubility increases with 4166
the potassium fraction when the fraction is ,40 wt%, but log SFe, Na ~ppm! ⫽ 4.720 ⫺ ~8!
when the fraction exceeds 40 wt%, the solubility is al- T ~K!
most constant. Using Eq. ~3!, the solubility in pure potas-
sium at 473 K is ;2815 ppm, which is much higher than for iron in the sodium in the temperature range 658 to
that in NaK, even for NaK-78 wt% K, which indicates that 997 K,
the oxygen properties in NaK are more similar to that in
6166
liquid sodium rather than that in liquid potassium. log SFe, K ~ppm! ⫽ 8.193 ⫺ ~9!
Carbon and nitrogen are the other two important spe- T ~K!
cies in the liquid that affect corrosion. No experimental
correlation was found for the solubility of carbon and for iron in potassium in the temperature range 900 to
nitrogen in NaK. For carbon in sodium, it is recommend 1200 K,
that the correlation developed by Ainsley et al.22 be
1570
used, which was also recommended by Borgstedt and log SNi, Na ~ppm! ⫽ 2.07 ⫺ ~10!
Mathews 14 : T ~K!

NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008

 CORROSION BY NaK COOLANT 81

for nickel in sodium in the temperature range 573 to believed to agree well with the experimental results
1173 K, ~15 ppm! considering that there are many uncertainties.
The recommended solubility curves for Fe, Cr, and Ni in
3040 liquid sodium and potassium, and the estimated solubil-
log SNi, K ~ppm! ⫽ 3.89 ⫺ ~11!
T ~K! ity curves for Fe, Cr, and Ni employing Eq. ~14! are
shown in Fig. 5. From these curves, iron is the most
for nickel in potassium in the temperature range 941 to soluble element, while chromium has the highest corro-
1328 K, sion resistance.
9010
log SCr, Na ~ppm! ⫽ 9.35 ⫺ ~12!
T ~K! V. EXPERIMENTAL RESULTS OF STAINLESS
STEEL IN LIQUID NaK
for chromium in sodium in the temperature range 948 to
1198 K, and
Liquid NaK was selected as the coolant for the SNAP
4130 reactor systems. As part of the SNAP reactor design ef-
log SCf, K ~ppm! ⫽ 4.158 ⫺ ~13! forts, experiments for the corrosion of the SNAP struc-
T ~K!
tural materials by liquid NaK were conducted by many
for chromium in potassium in the temperature range 1000 researchers. However, it has proved difficult to analyze
to 1300 K. or compare these data, not only because the test condi-
There are no correlations for the solubility of Fe, Ni, tions are very different and the test results are very scat-
and Cr in liquid NaK. Data were found from only one tered but also because critical information on the test
experiment 24 on the solubility of Fe in liquid NaK ~68 conditions is often missing. In the present discussion, we
mol% K!. The solubility at 973 K was measured to be focus on the experimental results on stainless steels, which
15 ppm. In the absence of data, the following correlation are often used as the construction materials for nuclear
is proposed: reactor systems. The compositions of the stainless steels
considered are shown in Table I, including two nickel
Si, Na Si, K steels for comparison.
Si, NaK ⫽ , ~14! Before the 1950s, most of the experiments on NaK
Si, Na MK ⫹ Si, K MNa
corrosion were carried out in static ~no flow! capsules,
where MNa and MK are the mole fractions in the NaK as discussed in a report by Kelman, Wilkinson, and Yag-
eutectic. Equation ~14! has the same form as that used to gee.25 The experimental data on stainless steel, all taken
calculate the NaK physical properties such as the density from Kelman, Wilkinson, and Yaggee’s report, are shown
and viscosity based on the properties of Na and K in Table II. As the data in Table II indicate, all the stain-
~Ref. 11!. Using Eq. ~14!, the solubility of Fe in NaK ~68 less steels that were considered displayed good perfor-
mol% K! at 973 K is calculated to be 8.8 ppm, which is mance in a NaK environment up to a temperature of

TABLE I
Compositions of Steels Considered in the Present Study

Steel Type Cr Ni C Mn Si P S

SS302 17–19 8–10 0.15 a 2a 2–3 0.045 a 0.03 a

SS303 17–19 8–10 0.15 a 2a 1a 0.2 a 0.15 a 0.6Mo or 0.6Zr,0.15Se
SS310 24–26 19–22 0.25 a 2a 1.5 a 0.045 a 0.03 a
SS304 18–20 8–12 0.08 a 2a 1a 0.045 a 0.03 a
SS316 16–18 10–14 0.08 a 2a 1a 0.045 a 0.03 a Mo 2–3
SS318
SS321 17–19 9–12 0.08 a 2a 1a 0.045 a 0.03 a 5xC min
SS347 17–19 9–13 0.08 a 2a 1a 0.045 a 0.03 a Cb ⫹ Ta 10xC min
SS430 11.5–13 — 0.12 a 1a 1a 0.04 a 0.03 a
Croloy 9M 8–10 — 0.15 a 0.6 a 1.0 a 0.03 0.03 0.9–1.10 Mo
a a a
Hastelloy N 7 Base 0.08 0.08 1 0.02 0.02 16 Mo 0.2 a Co 0.5W 0.35 Cu
Hastelloy C 22 Base 0.01 0.05 a 0.08 a — — 2.5 Co, 0.35 V, 3.0W
a
The maximal weight percent.

NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008

82 ZHANG, KAPERNICK, and MARCILLE

Fig. 5. Curves of solubility of Fe, Cr, and Ni. ~a!, ~b!, and ~c! 1, solubility in potassium; 2, solubility in NaK ~78 wt% K!;
3, solubility in sodium. ~d! Calculated results of the comparison between solubility in NaK ~78% K!.

7608C. Even at a temperature of 8258C, there is only one
case showing a weight loss, with a corrosion rate of 25.4
mm0yr. Most of the cases indicate a weight gain, attrib-
uted by Kelman, Wilkinson, and Yaggee to the formation
of an adherent Cr2O 3 film on the sample surfaces due to
a slight contamination of oxygen in the NaK. In very
pure NaK, there is very small initial weight loss, which
decreases rapidly with increasing exposure time as indi-
cated by the experimental results on Type 310 stainless
steel ~SS310! at 7608C.
Based on these pre-1950s experimental data, Kelman,
Wilkinson, and Yaggee 25 concluded that stainless steels
are extremely resistant to attack by NaK at temperatures
up to 7608C and possibly above. They also believed that
the attack of stainless steels by NaK is not influenced by
the presence of other metals in the same system nor do
the stainless steels influence the attack of other metals
by NaK. Further, they concluded that carburization would
take place if there were a carbon source in the system.
It should be noted that static experimental data can-
not be applied to a flowing system, especially a noniso-
thermal system. Further, the corrosion rates calculated
using these data are very nonconservative because the
corrosion approaches zero for long-term exposures. Cal-
culating the recession rate based on weight loss is also
misleading because the calculation is based on the as-
sumption that the weight loss is due to uniform recession
of the surface. In reality, the attack layer will be thicker

NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008

 CORROSION BY NaK COOLANT 83

TABLE II
Experimental Data on NaK Corrosion Before 1950s

Weight Change ~mg0mm 2 {yr⫺1 ! Recession

Na in NaK Temperature Time
Steel Type ~wt%! ~8C! ~h! Range Average mil0yr mm0yr Description

SS302 56 200 144 ⫺0.1 ⫺0.3 ⫺0.2 0.10 2.5 Static

56 600 144 ⫹1.0 ⫺0.1 ⫹0.3 Gain Gain Static
SS303 56 640 144 — — ⫺0.4 0.25 6.4 Static
SS304 100 500 168 Nil ⫹0.34 ⫹0.2 Gain Gain Static
100 538 500 ⫺0.5 ⫹0.5 ⫹0.05 Gain Gain Flow
100 650 165 — — ⫹2.0 Gain Gain Static
0 760 500 — — ⫹5.0 Gain Gain Static
20 760 200 ⫺2.7 ⫹1.9 ⫺0.1 0.60 15.2 Static
20 760 500 Nil ⫺0.1 Nil Gain Gain Static
20 760 1000 Nil Nil Nil Nil Nil Static
56 825 100 — — ⫹0.59 Gain Gain Static
56 825 500 — — ⫺1.0 1.0 25.4 Static
SS316 100 500 170 Nil ⫹0.16 ⫹0.1 Gain Gain Static
36 538 500 Nil Nil Nil Nil Nil Flow
56 650 144 — — ⫹0.7 Gain Gain Static
100 760 165 — — ⫹1.5 Gain Gain Static
20 760 200 ⫺0.2 ⫺0.3 ⫺0.3 0.2 5.0 Static
20 760 500 ⫺0.1 ⫺0.1 ⫺0.1 0.05 1.3 Static
20 760 1000 Nil Nil Nil Nil Nil Static
SS318 20 760 200 ⫹0.14 ⫹0.18 ⫹0.18 Gain Gain Static
20 760 500 ⫹0.5 ⫹0.5 ⫹0.5 Gain Gain Static
20 760 1000 Nil Nil Nil Nil Nil Static
SS321 20 538 200 — — ⫺0.3 0.50 12.7 Static
SS347 56 200 144 ⫺0.4 ⫹0.4 Nil Gain Gain Static
56 450 4370 Nil ⫹0.23 ⫹0.04 Gain Gain Flow
22 450 2100 — — ⫺0.01 — — Static
100 500 800 ⫺0.07 ⫹0.21 ⫹1.0 Gain Gain Static
100 500 750 ⫺0.04 ⫹0.35 ⫹0.02 Gain Gain Static
34 538 500 ⫹0.4 ⫹1.7 ⫹0.2 Gain Gain Flow
56 600 144 Nil ⫹0.4 ⫹0.1 Gain Gain Static
22 600 144 — — ⫹1.1 — — Static
100 650 165 — — ⫹2.0 — — Static
20 760 200 ⫹0.7 ⫹0.5 ⫹0.3 Gain Gain Static
20 760 500 ⫹0.5 ⫹0.5 ⫹0.5 Gain Gain Static
20 760 1000 ⫹0.1 ⫹0.1 ⫹0.1 Gain Gain Static
SS310 100 538 500 ⫺0.17 ⫹2.60 ⫹1.4 Gain Gain Flow
20 589 3000 ⫹0.01 ⫹0.057 ⫹0.013 Gain Gain Flow
54 600 144 — — ⫹0.6 Gain Gain Static
100 650 145 — — ⫹2.0 Gain Gain Static
20 760 50 — — ⫺1.6 1.0 25.4 Static
20 760 200 — — ⫺1.3 0.75 19.05 Static
20 760 500 Nil ⫺0.5 ⫺0.3 0.20 5.08 Static
20 760 1000 — — ⫺0.4 0.23 5.8 Static
20 760 1500 ⫺0.3 ⫺0.4 ⫺0.4 0.20 5.08 Static
20 760 5000 — — Nil Nil Nil Static
56 825 100 — — Nil Nil Nil Static
56 825 500 — — ⫹2.0 Gain Gain Static
20 571 200 — — ⫺0.3 0.2 5.08 Static
SS430 56 600 144 — — Nil Gain Gain Static
56 600 144 — — ⫹3.7 Gain Gain Static

NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008

84 ZHANG, KAPERNICK, and MARCILLE
than the calculated recession layer because of selective
and intergranular corrosion, decarburization, and carbu-
rization. All these phenomena can change the properties
of the steel at the surface leading to materials failure.
Pratt & Whitney Aircraft has operated several NaK
~56% K! loops built of SS316 to study the corrosion
resistance of SS316 at different operation conditions.26,27
The test conditions and test results from the two reports
are summarized in Table III. All the tests were short-
term tests, less than ;500 h.
The type NSSA loop had very high oxygen concen-
trations as indicated in Table III. The pretest oxygen
levels were in the range of 750 to 1020 ppm ~1A1! and
205 to 1575 ppm ~2A2!. Recession and deposition thick-
nesses were measured as well as the solution attack
thickness. The attacks are characterized as sparse at-
tacks. The largest recession occurred at the heater exit,
where the temperature was 904.48C, the highest temper-
ature in the loop. The maximum recession was about
two times larger in 1A1 ~which had a longer test dura-
tion! than in 2A2. The largest deposition ~71.12 mm! in
1A1 occurred at the cooler midsection, and the largest
deposition ~15.2 mm! in 2A2 occurred at the end of the
cooler. The largest solution attack thickness in 1A1 was
38.1 mm and occurred at the entrance of the cooler,
and the largest solution attack thickness in 2A2 was
25.4 mm and occurred at the heater hot isothermal sec-
tion. The differences between the results from 1A1 and
2A2 were attributed to the different oxygen concentra-
tions and exposure times. It is expected that the oxygen
in the NaK played an important role in the experimen-
tal results.
Compared with the NSSA loop, the NSSB loop had
two separated heater sections, a higher coolant velocity
at the heater, and a lower oxygen concentration as indi-
cated in Table III. The NSSB-1A1 test was run for 353 h,
and the NSSB-3A3 test was run for 459.5 h. A sigma
phase was observed along the loop, and no deposits were
found. There was no apparent solution attack. For 1A1
the attack is characterized by surface voids, while for
3A3, the attack is characterized by pitting, except at the
location downstream of the tank. The 1A1 loop had the
largest attack thickness ~101.6 mm! after the surge tank,
while at the same location in the 3A3 loop, the attack
thickness ~2.54 mm! was the smallest in the loop. In the
3A3 loop, the largest attack thickness was 20.3 mm and
occurred at the second heater exit and at the cooler. The
data from the two NSSB loops are very scattered as shown
in Table III.
The NSSC loop had the lowest oxygen concentra-
tion ~,100 ppm! and the highest temperature difference
among the three loops ~NSSA, NSSB, and NSSC!. The
report 27 on the corrosion results from NSSC is a sum-
mary, and there is no detailed information on the loop
and results. However, it was reported that the solution
attack at the hot isothermal section was up to 2.54 mm
and the thickness at the cooler zone was up to 25.4 mm.
NUCLEAR SCIENCE AND ENGINEERING
The heaviest deposition occurred at the cooler exit. Pre-
test and post-test analysis on the chemistry compositions
of the steel at the isothermal hot and cold zones revealed
a significant loss of chromium, molybdenum, carbon,
and nitrogen in the hot zone. A slight decrease in car-
bon and nitrogen and a slight increase of molybdenum
were also found in the cold zone.
Two experimental loops were built by Atomics In-
ternational.2,28 One loop had a maximum temperature of
7608C, and the other had a maximum temperature of
6508C. For both loops, the temperature difference in the
loop was 658C. The oxygen concentrations were very
low ~,20 ppm!, and the flow velocity was low ~;0.03
m0s!. The test durations were several thousand hours.
The liquid was 78% K NaK.
Table IV summarizes the test conditions and results.
Table IV indicates that there were no significant differ-
ences in corrosion attack among the three types of steels.
Intergranular0general corrosion and pitting were re-
ported at both temperatures. Decarburization was ob-
served in the tests at 7608C.
A view of the microstructure of Type 304 stainless
steel ~SS304! samples tested at 650 and 7608C is given
in Fig. 6 for comparison. At 6508C, the corrosion ap-
pears to be primarily intergranular in nature and has a
light colored second phase that often appears at the root
of the penetration.2 At 7608C, the corrosion appears to
be more general in nature, and leaching is evident. It was
also reported that the specimen at 6508C showed sensi-
tization, while the specimen at 7608C showed carbide
coalescence.2
Long-term experiments ~up to 32 600 h! were car-
ried out in an SS316 loop by Idaho Nuclear Corpora-
tion.29–31 Liquid NaK ~77.2% K! was pumped in a loop
with a maximum temperature of 7608C and a minimum
temperature of 5938C. The flow velocity was 1.7 m0s,
and the oxygen concentration was controlled in a range
of 30 to 50 ppm by a cold trap. Corrosion effects were
examined at different parts of the loop after the run. A
summary of the results is given in Table V. Results from
Ref. 30 are also included in Table V.
The Idaho Nuclear Corporation results indicate that
Type 318 stainless steel ~SS318!, Type 348 stainless steel
~SS348!, SS304, and SS316 are suitable materials of con-
struction for a nonisothermal NaK loop with a maximum
temperature of 7608C. Although there are some compo-
sition changes at the surface areas exposed to NaK such
as the loss of C and Ni at the hot isothermal section,
these changes do not greatly affect the material proper-
ties in a way that can lead to material failure. The gen-
eral corrosion depth is limited to 50.8 mm after exposure
for 32 600 h.
A sigma phase was found just below the decarburi-
zation layer when the temperature was above 5938C.
SS316, SS318, and SS348 appear to have more sigma
phase ~whose concentration increases with time! than
Type 304L stainless steel. Carbide precipitation at the
VOL. 160 SEP. 2008
 CORROSION BY NaK COOLANT 85

TABLE III
Corrosion Data of SS316 by NaK ~56% K! by Pratt & Whitney*

Time Temperature Solution Attack Deposition Recession

Loop ~h! Location ~8C! ~ mm! ~ mm! ~ mm! Description

NSSA-1A1 369 Heater entrance 832.2 20.3 10.16 38.1 to 50.8 Sparse attack and
metallic deposit
Heater exit 904.4 15.24 88.9 Concentrated surface
attack
Hot isothermal 904.4 25.4 76.2 to 88.9 Sparse attack
Cooler at 0.30 m 885 38.1
Cooler at 0.76 m 857 10.2 71.12 Sparse attack
Cooler at 1.06 m 8838 22.7 10.7 Sparse attack

NSSA-2A2 515 Heater entrance 832.2 25.4 38.1 Sparse attack

Heater exit 904.4 25.4 25.4 to 38.1 Sparse attack
Hot isothermal 904.4 25.4 25.4 to 38.1 Sparse attack
Cooler at 0.30 m 885 25.4 Sparse attack
Cooler at 0.76 m 857 7.6 Sparse pitting attack
Cooler at 1.06 m 838 15.2 15.2 Sparse attack metallic
deposit

NSSB-1A1 353 Temperature Attack Sigma Phase

Location ~8C! ~ mm! ~ mm!, Description

First heater entrance 832.2 20.3 Across the wall-660.4

Second heater entrance 887.8 25.4 Across the wall-711.2
Secondary heater exit 904.4 25.4 Across the wall-737
After the surge tank 904.4 101.6 Half way across the wall-1041.0
Before cooler 904.4 25.4 Across the wall-1371.6
Cooler entrance 904.4 15.2 Across the wall-2108
Cooler exit 832.2 17.8 Across the wall-2057

NSSB-3A3 459.5 First heater entrance o 832.2 10.2 Width-686, depth-25.4–50.8

First heater exit 887.8 10.2 Width-584, depth-25.4–50.8
Second heater entrance 887.8 12.7 Width-457, depth-25.4– 63.5
Secondary heater exit 904.4 20.3 Width-457, depth-25.4–76.2
After the surge tank 904.4 2.54 Width-1473, depth-25.4–76.2
Before cooler 904.4 20.3 Width-1219, depth-12.5–72.2
Middle of the cooler 871.1 20.3 Width-2083, depth-12.5–25.4
Cooler exit 832.2 7.62 Width-2083

On NSSB: ~1! No apparent solution attack; ~2! no deposit; ~3! for 1A1, the attack is surface void while for 3A3, the attack is pit
except the location after surge tank.

NSSC-1A1 500 Maximal solution corrosion at hot isothermal leg, 8718C 2.54 mm
Maximal deposition thickness at cooler exit, 6498C 25.4 mm

Chemical Analysis

Ni Cr Mo C N
~%! ~%! ~%! ~ppm! ~ppm!

Pretest heater 11.47 19.76 1.65 560 600

Pretest cold isothermal 11.95 19.94 1.99 860 490
Posttest heater 11.32 18.65 1.42 125 410
Posttest cold isothermal 11.95 19.81 2.18 790 370

Deposit Chemical Analysis

Fe Ni Cr
Deposit weight ~%! ~%! ~%!

0.06 g 4.91 32.5 47.2

*NSSA: Maximal temperature, 904.48C; temperature difference, 72.28C; flow velocity at heater, 5.79 m0s; flow velocity at cooler, 1.98 m0s; pretest
oxygen, 750 to 1020 ppm ~1A1! and 305 to 1575 ppm ~2A2!; posttest, 1630 ~2A2!.
NSSB: Maximal temperature, 904.48C; temperature difference, 72.28C; flow velocity at heater, 10.66 m0s; flow velocity at cooler, 3.35 m0s; pretest
oxygen, 113 to 400 ppm ~1A1! and 115 to 290 ppm ~2A2!.
NSSC: Maximal temperature, 871.18C; temperature difference, 222.28C; flow velocity at heater, 7.26 m0s; flow velocity at cooler, 4.26 m0s; oxygen
concentration, ,100 ppm.

NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008

86 ZHANG, KAPERNICK, and MARCILLE

TABLE IV
Corrosion of Various Stainless Steels by NaK ~78% K! by Atomics International

Loop description: Maximal temperature, 760 or 6508C; temperature difference, 658C; flow velocity, ;0.03 m 0s;
oxygen concentration, ,20 ppm.

Temperature 6508C Temperature 7608C

Time Attack Attack

Steel Type ~h! ~ mm! Description ~ mm! Description

SS304 1500 No apparent attack Slight decarburization

2500 35.5 Intergranular 35.6 Pitting
3500 Slight general corrosion 33.0 Intergranular
4500 38.1 Pitting 58.4 Decarburization
a
SS316 1000 66.0 General corrosion Slight general corrosion
2000 63.5 Intergranular 10.2 Decarburization
3000 25.4 General corrosion 20.3 Decarburization
SS347 1500 17.8 Intergranular 15.2 Intergranular corrosion
2500 50.8 General corrosion 10.2 Pitting
3500 48.3 Intergranular 15.2 General corrosion
4500 50.8 Pitting 63.5 Decarburization
a The high corrosion rate for SS316 at 6508C is unknown. Excess oxygen in loop. It can be considered realistic.

Fig. 6. SS304 exposed to NaK ~78% K! for 4500 h: ~a! 6508C and ~b! 7608C.

grain boundary was found. SS304 appears to have less
carbide precipitation than SS316 and more than SS348.
At welds and bends, the corrosion phenomena of the
steel seem to be similar to phenomena in pipes. Cracks
propagating both transgranularly and inner-granularly
were found at 316 fittings after ;16 000 h ~Fig. 7!, but
analysis of the cracks indicates that they were not due to
NaK corrosion but rather due to external stress. There-
fore, the effect of external stress on material failure has
to be taken into account when designing a nonisothermal
NaK loop.
Eleven experimental loops were set up at Oak Ridge
National Laboratory 32 ~ORNL! to study corrosion by liq-
uid NaK ~78% K! for materials in the primary coolant
system of SNAP-8. The total length of each loop was
;8.12 m. The experiments were carried out at three dif-
ferent oxygen levels: ,30, ;80, and .100 ppm. The
oxygen level was controlled by a cold trap method at the
beginning, followed by a hot trap method. Specimens
made of materials proposed to be used in SNAP-8
~chromized Hastelloy N, Hastelloy C, Croloy 9M, SS316,
and Type 347 stainless steel ~SS347!! were installed at

NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008

 CORROSION BY NaK COOLANT 87

TABLE V
Experimental Results of Different Geometries from Idaho Nuclear Corporation

Conditions: Maximal temperature, 7608C; temperature difference, 1678C; flow velocity, 1.7 m 0s; oxygen concentration, 20 to 30 ppm;
fluid NaK ~77.8% K!.

Steel Type Sample Geometry Test Conditions Test Results

SS316 Pipe The sample was cut from the hot leg, was in 1. 25.4-mm depth decarburization.
service for 1118 h below 5938C, and 15 174 h 2. Sigma growth across the wall beyond the
at ;5938C. decarburization layer.
3. Surface composition changed.
4. Carbide precipitation at the the grain
boundaries and concentration of up to 11%
sigma phase.
5. Hardness changed little.

Fitting Two pipe tee connectors: ~1! 3240 h of service 1. Cracks were observed in welds.
at 593 to 7608C and 360 h of service below 2. Cracks were propagated both transgranularly
5938C; ~2! 15 800 h of service at 593 to 7608C and intergranularly.
and 1150 h of service below 5938C.

Pump Located upstream from the cold trap, 20 136 h
of service at 550 to 5938C and 1295 h of
service below 5508C.
1. 127-mm depth carburization.
2. Mass deposition observed.
3. Sigma phase presented.
4. Chromium concentration changes along the
carburization region, 20 to 30% less than in the
based steel.
5. Nickel concentration was constant throughout
the region and only 80% of that in the base
steel.

Pipe ~1! 1120 h of service below 6008C and
15 180 h of service above 6008C. ~2! 300 h of
service below 6008C and 16 000 h of service
above 6008C. ~3! 1410 h of service below
6008C and 31 190 h of service above 6008C.
1. General corrosion ,50.8 mm.
2. Carbon depletion and precipitation at the grain
boundary.
3. Sigma phase observed, and its transformation
increases with increasing service time. Sample
~3! has three times more sigma phase than that
of sample ~1!.

Pipe-elbow-pipe 4397 h of service below 5378C and 9789 h of 1. No general corrosion.

service above 5378C. 2. Carbide precipitation at the grain boundary.
3. No sigma phase.
4. Embrittlement results observed.

SS304 Tee fitting 261 h of service below 6008C and 15 370 h of 1. No general corrosion.
service above 6008C. 2. Carbon depletion and carbide precipitation
observed.
3. Only trace quantities of sigma phase formation
in the cross section of the tee.
4. Sigma phase is ,1%, and carbide phase is ;2%.
5. The samples were ductile and not brittle.

Pipe-elbow-pipe 4397 h of service below 5378C and 9789 h of 1. Carbide precipitation at the grain boundary, less
service above 5378C. than SS316 but more than SS348.
2. Trace amount of sigma phase.
3. Particularly hard spot was observed.

SS348 Pipe-elbow-pipe 4397 h of service below 5378C and 9789 h of 1. Carbide precipitation at the grain boundary.
service above 5378C. 2. Appreciable concentration of sigma phase.
3. Sigma phase is in the complex chromium-
nickel-columbium austenite matrix.
4. Particularly hard spot was observed.
5. No general corrosion.

SS318 Pipe ~low-semi elliptical! 1410 h of service below 6008C and 31190 h of 1. No carbon depletion.
service above 6008C 2. Sigma phase and embrittlement observed.
3. Micro structure change.
4. No general corrosion.

NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008

 88
TABLE VI
Summary of the Test Conditions and Test Results of Corrosion by NaK ~78% K! from ORNL

Loop Test Conditions

Loop Loop 1 Loop 1A Loop 2 Loop 4 Loop 5 Loop 7 Loop 8 Loop 9 Loop 10 Loop 13 Loop 14

Tmax ~8C! 758 758 760 764 758 696 703 711 707 787 787

ZHANG, KAPERNICK, and MARCILLE

Tmin ~8C! 593 568 568 574 568 582 574 576 564 574 577
CO ~ppm! ,30 ,30 ;80 ,30 Unknown .100 ,30 .100 ,30 Unknown ;30
H 2 ~cm 30h! 0 0 0 0.57 0.5 0.63 0.58 0 0 0.55 0.28
Time ~h! 701 2608 2205 2683 5828 2705 2435 2476 1048 2000 2659

Samples’ Local Test Conditions

NUCLEAR SCIENCE AND ENGINEERING

Local Temperature ~8C!

Location V
Number Materials ~m! ~m0s! Loop 1 Loop 1A Loop 2 Loop 4 Loop 5 Loop 7 Loop 8 Loop 9 Loop 10 Loop 13 Loop 14

1 Hastelloy N 0 133 593 568.33 582 575 587 582 574 577 564 590 593
2 Hastelloy N 0.597 135 649 626.67 637 633 640 620 618 621 613
3 Hastelloy N 1.195 138.5 708 696.11 701 704 702 658 660 668 661 653 652
4 Hastelloy N 1.652 141.5 758 758.33 760 764 758 696 703 711 708 711 704
5 SS347 1.722 126 758 758.33 760 764 758 696 703 711 708 711 704
6 SS316 1.898 5.5 758 758.33 760 764 758 696 703 711 708 711 704
7 Croloy 9M 2.953 84.2 749 738.33 742 738 743 686 689 695 692 696 682
11 Croloy 9M 3.796 84 721 712.22 716 716 717 674 676 666 677 682 654
16 SS316 3.93 82.5 698 689.44 693 693 695 658 654 652 661 666 642
10 Croloy 9M 4.148 81.9 677 665.56 669 671 672 643 639 638 645 649 631
15 SS316 4.289 81.5 653 642.78 646 648 649 627 624 624 629 632 618
VOL. 160

9 Croloy 9M 4.429 81 632 619.44 622 625 627 612 609 610 613 616 607
8 Croloy 9M 4.921 80.2 605 592.22 594 598 599 595 592 598 589 598 596
12 Hastelloy C 5.027 285 605 592.22 594 598 599 595 592 598 589 598 596
13 SS316 5.87 420 599 587.78 586 583 591 588 585 593 582 593 582
SEP. 2008

14 SS316 8.015 655 593 568.33 582 575 587 582 574 577 564 574 577

~Continued!
NUCLEAR SCIENCE AND ENGINEERING

Total Weight Loss ~Measured!

Weight Loss ~mg0cm 2 !

Number Materials Loop 1 Loop 1A Loop 2 Loop 4 Loop 5 Loop 7 Loop 8 Loop 9 Loop 10 Loop 13 Loop 14

1 Hastelloy N 0.28 1.13 1.55 1.7 0.47 3.19 0.39 13.67 0.31 0.25 0.43
2 Hastelloy N ⫺0.6 ⫺0.24 0.23 ⫺0.35 ⫺1.21 0.28 ⫺0.11 2.35 ⫺0.14
3 Hastelloy N ⫺2.17 ⫺2.17 ⫺2.68 ⫺4.31 ⫺7.33 ⫺1.55 ⫺0.84 ⫺1.66 ⫺1.08 ⫺0.74 ⫺0.9
4 Hastelloy N ⫺4.08 ⫺8.11 ⫺7.91 ⫺11.5 ⫺20 ⫺5.99 ⫺2.64 ⫺7.63 ⫺3.08 ⫺2.24 ⫺2.5
5 SS347 ⫺0.66 ⫺0.97 ⫺2.99 ⫺5.22 ⫺2.3 ⫺6.28 ⫺0.82 ⫺35.14 ⫺0.76 ⫺0.97 ⫺1.46
6 SS316 ⫺0.27 ⫺0.35 ⫺0.98 ⫺1.34 ⫺0.69 ⫺2.49 ⫺0.18 ⫺16.22 ⫺0.25 ⫺0.36 ⫺0.34
7 Croloy 9M 0.2 0.32 ⫺1.46 ⫺3.01 ⫺0.38 ⫺10.24 ⫺0.03 ⫺104.6 0.11 ⫺0.4 ⫺0.13
11 Croloy 9M 0.11 0.29 ⫺0.22 ⫺0.46 0.89 ⫺2.84 0.05 ⫺33.1 ⫺0.14 ⫺0.16 0.01
16 SS316 0.09 0.2 0.11 ⫺0.21 0.63 ⫺0.49 ⫺0.33 ⫺3.52 ⫺0.12 0.07 0.1
10 Croloy 9M 0.08 0.44 0.38 0.32 1.03 ⫺0.35 0.03 1.36 0 ⫺0.03 0.18
⫺0.37 ⫺0.03
VOL. 160

15 SS316 0.12 0.37 0.55 0.74 0.98 0.1 4.08 0.24 0.17
9 Croloy 9M 0.17 0.39 0.74 1.77 0.9 0.99 0.04 9.77 ⫺0.07 0.07 0.27

CORROSION BY NaK COOLANT

8 Croloy 9M 0.04 0.38 1.44 2.38 0.77 3.99 0.05 36 0.05 0.29 0.39
12 Hastelloy C 0.93 1.16 2.64 10.49 1.5 7.94 0.44 70.3 0.57 1.27 1.18
13 SS316 0.76 5.54 1.56 10.37 0.46 41.2 0.28 1.1 0.38
SEP. 2008

14 SS316 0.18 0.41 2.12 1.9 0.45 8.49 0.26 24 0 0.66 0.79

Recession Rate ~Calculated!

Recession Rate ~ mm0yr!

Number Materials Loop 1 Loop 1A Loop 2 Loop 4 Loop 5 Loop 7 Loop 8 Loop 9 Loop 10 Loop 13 Loop 14

1 Hastelloy N 3.94921 5.40254 6.95014 6.26468 0.7973 11.6599 1.58357 54.5869 1.53251 1.2359 1.5989
2 Hastelloy N ⫺8.4626 ⫺1.1474 1.03131 ⫺1.2898 ⫺2.0528 1.02344 ⫺0.4466 9.38399 ⫺0.6921
3 Hastelloy N ⫺30.6064 ⫺10.375 ⫺12.017 ⫺15.883 ⫺12.435 ⫺5.6655 ⫺3.4108 ⫺6.6287 ⫺5.3391 ⫺3.6582 ⫺3.3465
4 Hastelloy N ⫺57.5457 ⫺38.774 ⫺35.4681 ⫺42.379 ⫺33.93 ⫺21.894 ⫺10.72 ⫺30.468 ⫺15.226 ⫺11.074 ⫺9.2959
5 SS347 ⫺10.3096 ⫺4.6376 ⫺13.407 ⫺19.236 ⫺3.9019 ⫺22.954 ⫺3.3295 ⫺140.32 ⫺3.7571 ⫺4.7953 ⫺5.4288
6 SS316 ⫺4.27093 ⫺1.6734 ⫺4.39428 ⫺4.938 ⫺1.1706 ⫺9.1013 ⫺0.7309 ⫺64.77 ⫺1.2359 ⫺1.7797 ⫺1.2642
7 Croloy 9M 3.20421 1.52992 ⫺6.54658 ⫺11.092 ⫺0.6447 ⫺37.429 ⫺0.1218 ⫺417.69 0.54379 ⫺1.9774 ⫺0.4834
11 Croloy 9M 1.76232 1.38649 ⫺0.98647 ⫺1.6951 1.5099 ⫺10.381 0.20302 ⫺132.17 ⫺0.6921 ⫺0.791 0.03718
16 SS316 1.42364 0.9562 0.49324 ⫺0.7739 1.0688 ⫺1.791 ⫺1.3399 ⫺14.056 ⫺0.5932 0.346 0.37184
10 Croloy 9M 1.28169 2.10365 1.70391 1.17923 1.7474 ⫺1.2793 0.12181 5.43074 0 ⫺0.1483 0.66931
15 SS316 1.89819 1.76897 2.46618 2.72698 1.6626 0.36551 ⫺1.5024 16.2922 ⫺0.1483 1.1865 0.63212
9 Croloy 9M 2.72358 1.86459 3.31813 6.52263 1.5268 3.61858 0.16242 39.0134 ⫺0.346 0.346 1.00396
8 Croloy 9M 0.64084 1.81678 6.4569 8.77055 1.3063 14.584 0.20302 143.755 0.24718 1.4336 1.45016
12 Hastelloy C 13.5136 5.54597 11.8377 38.6567 2.5447 29.0218 1.78659 280.721 2.81783 6.2783 4.38767
13 SS316 3.63357 20.4155 2.6465 37.9037 1.8678 164.519 1.3842 5.4379 1.41298
14 SS316 2.84729 1.96021 9.506 7.0017 0.7634 31.0321 1.05571 95.8365 0 3.2628 2.93751

89
90 ZHANG, KAPERNICK, and MARCILLE

and measured specimen weight changes are given in

Fig. 7. Crack on inside of pipe tee connector after 15 800 h
~Ref. 29!. Fine black lines indicated with arrows are grain
boundaries outlined by etching. Black arrow shows the crack.
the different locations in the test loops. A simple dia-
gram of the loop 32 as well as the locations of the speci-
mens is shown in Fig. 8. The test conditions ~temperatures,
oxygen concentrations, and flow velocities in the loop!
Table VI. The calculated recession0deposition rates ~or
corrosion rate! based on the weight changes are also
shown in Table VI. Considering that liquid attack may
be leaching, penetration, etc., the attack rate by the liq-
uid on the materials should be greater than the recession
rate shown in Table VI. The recession rate can be treated
as a minimum estimate of the attack rate.
Examples of distributions of the specimens’ weight
changes around the loops ~loops 1A and 2! are shown
in Fig. 9. Clearly, there was material migration from
the hot sections to the cold sections. The migration
of metallic elements was in the form of particulate
matter and diffusion alloying, while the migration of
carbon was in the form of carburization and decarburi-
zation of the materials. For a low oxygen in the loops
~,30 ppm!, the migration of metallic elements was
very low compared with carbon, which was quite se-
vere. The original carbon content in Croloy 9M was
;0.11% at the hot end section ~No. 7!, and it reduced
to a range from ;0.002 to ;0.01% after the tests.
The chromized Hastelloy N had the highest corro-
sion rate, which was seven times greater than that
of SS347 and SS316. Reference 32 reports that in-
creasing the oxygen concentrations from 30 ppm to
;80 ppm increased the weight loss of SS316 and
SS347 by a factor of 3 to 4. However, the oxygen con-
centration had little effect on the corrosion rate of Hast-
elloy N.

Fig. 8. Diagram of the corrosion loop in ORNL for SNAP-8. The locations of specimens in the loop were given. The
coordinate of the specimen at the inlet of the heat was set to zero, and the coordinate increases along the streamwise direction.

NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008

 CORROSION BY NaK COOLANT
Fig. 9. ~a! Specimens’ weight change along loops 1A and 2 and ~b! the corresponding temperature; negative value represents
weight loss and positive value represents weight gain.
Phase identification studies indicate that carbide
phases and the sigma phase develop in SS347 and SS316.
Results also indicate that in SS347 the sigma phase grad-
ually decomposes as carburization proceeds across the
specimen. Analysis of deposition layers indicates that
the deposits consist mostly of nickel, chromium, and man-
ganese in low-oxygen loops and are mostly iron and chro-
mium in high-oxygen loops.
Adding hydrogen into the liquid has no effect on the
mass transfer rate for both metallic elements and carbon.
Therefore, the hydrogen in the liquid has no effect on the
corrosion rate at the hot section or on the deposition rate
at the cold section. It was also reported that the cold trap
method was an effective way to control the hydrogen
level in liquid NaK.
The weight loss given in Table VI indicates that the
corrosion rate depends on the specimen location in the
loop, as well as the specimen composition. The weight
loss increases with time and reaches a linear dependence
on the time for long-term operation.
VI. ANALYSIS AND DISCUSSION
As indicated in the experimental review in Sec. V,
all of the experimental studies on liquid NaK corrosion
were carried out before 1970. The experimental tech-
niques at that time permit only limited analysis of the
experimental results. Further, the experimental results
are very scattered, and the experimental conditions are
not well documented. Use of these data is very limited in
the design of a liquid-metal–cooled space reactor.
NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008
91
VI.A. Exposure Time Effects
As noted earlier, in a nonisothermal coolant loop
such as in a nuclear reactor, corrosion is expected to
continue throughout the duration of operation, eventu-
ally reaching a constant rate.
Figure 10 shows the corrosion0deposition rates ~ex-
pressed by both weight loss0gain per month per unit area
and recession0growth rate per year! calculated based on
the experimental data from loops 1, 1A, and 5 of ORNL.
Figure 10 indicates that the corrosion0deposition rates in
the short term are initially high and become small with
increasing exposure. The corrosion0deposition rate at
2608 h is almost the same as that at 5828 h as shown in
Fig. 10, indicating that the corrosion0deposition rates
become constant for long-term operation. The constant
rate determines the long-term behavior of the structural
materials and thus is of greatest importance.
The Atomics International data shown in Fig. 11 were
examined to check if the attack rate as a function of
exposure could be better understood. The data are too
scattered to draw any general conclusions; however, it
seems from Fig. 11 that the rate decreases with time. The
most important conclusion is that more experiments are
needed to determine long-term attack rates on materials
by liquid NaK.
VI.B. Flow Velocity Effects
At a steady-state condition ~constant corrosion 0
deposition rates!, experimental results on sodium corro-
sion indicate that the corrosion0deposition rate is almost
linear with the flow velocity when the Reynolds number
92 ZHANG, KAPERNICK, and MARCILLE
Fig. 10. Corrosion rate a function of time. Calculated based
on the data of ORNL loops 1, 1A, and 5. Oxygen concentration
,30 ppm. No. 4, Hastelloy N; No. 5, SS347; and No. 12,
Hastelloy C.
Fig. 11. Attack rate as a function of exposure time, cal-
culated based on the data from Atomics International ~Table IV!;
oxygen concentration ,20 ppm.
is ,7 ⫻ 10 4, while for higher Reynolds numbers the rate
is independent of the flow velocity.33
The dependence of the corrosion rate on the flow
velocity, calculated based on the experimental data from
ORNL, is shown in Fig. 12 for specimens at the hot
isothermal section. Clearly, the corrosion rate increases
with velocity increasing in the velocity range considered
NUCLEAR SCIENCE AND ENGINEERING
Fig. 12. Corrosion rate as a function flow velocity, calcu-
lated based on the data by ORNL. No. 5, SS347; No. 6, SS316.
by ORNL. No corrosion data for high velocity were re-
ported. But, considering that the corrosion behavior in
liquid NaK is similar to that in liquid sodium, it is ex-
pected that the corrosion rate does not depend on the
flow velocity when the velocity is very high. Figure 12
also indicates that the dependence of the corrosion rate
on the velocity is a function of the oxygen concentration.
It should be noted that specimen No. 6 is downstream of
specimen No. 5 and there are some downstream effects
on the corrosion0deposition distribution.
The maximum attack rates measured in the loops by
Pratt & Whitney as a function of the velocity are shown
in Fig. 13. Because the experimental conditions are very
different, especially the oxygen concentration, it is dif-
ficult to draw conclusions from Fig. 13. However, it ap-
pears that the attack rate does increase as the velocity
increases.
VI.C. Oxygen Concentration Effects
The ORNL report 32 concluded that “control and mon-
itoring of oxygen level was the single most important
factor in the operation of the corrosion loops.” Among
the factors that influence the corrosion rate, the oxygen
concentration does appear to be the most important fac-
tor. Oxygen is directly or indirectly related to most of the
mechanisms of corrosion by NaK. It may accelerate the
corrosion by catalyzing dissolution of the solid metal
atoms, or the oxygen itself may be the major migrating
constituent.34
Zimmerman 35 concluded that most of the effects of
oxygen on sodium corrosion can be applied to NaK cor-
rosion. Experiments by Thorley 36 concluded that the iron
corrosion rate dependency on oxygen is @O# 2 ~ @O# ⫽
VOL. 160 SEP. 2008
 CORROSION BY NaK COOLANT 93

Fig. 13. Dependence of the attack rate on the flow veloc-

ity, calculated based on data by Pratt & Whitney ~Table III!.

oxygen concentration!, for iron-based steel is @O# 1.5, and

for nickel alloy is @O# 0.
The calculated corrosion0deposition rates based on
the data from ORNL are shown in Fig. 14. For stainless
steel ~Nos. 5 and 14!, the corrosion0deposition rates in-
crease with the oxygen concentration. Fitting the data
produces a corrosion rate proportionality of @O# 1.1 and
deposition rate proportionality of @O# 1.6, consistent with
its dependence in sodium corrosion. For nickel-based
steel ~Nos. 4 and 12!, the corrosion0deposition rates de-
pend little on the oxygen concentration as shown in
Fig. 14.
The oxygen concentration also affects the corrosion0
deposition along the loop as shown in Fig. 9a. Figure 13
indicates that the attack rate increases as the oxygen con-
centration increases.
By analyzing the deposition, the ORNL report con-
cluded that the oxygen level affects the composition of
the deposit at the cold leg. For a low oxygen concentra-
tion, the deposit is composed mainly of nickel, while for
a high oxygen concentration, the deposit is composed
mainly of iron and chromium.
VI.D. Temperature and Temperature
Difference Effects
The temperature and the temperature profile of the
experimental loop are important factors that affect the
corrosion0deposition rate and distribution. The depen-
dence of the corrosion0deposition rate on the local tem-
perature is shown in Fig. 15. For No. 4 ~Hastelloy N!,
the corrosion rate increases dramatically with increasing
the temperature, while it appears that the corrosion rate
of No. 5 ~SS347! does not depend on the temperature. It
Fig. 14. Oxygen dependence corrosion0deposition rate.
No. 4, Hastelloy N; No. 5, SS347; No. 12, Hastelloy C; No. 14,
SS316.
should be noted that this conclusion is specific to this
particular loop, and one cannot conclude that the corro-
sion rate of SS347 in liquid NaK does not depend on the
temperature. Figure 15 also shows that the deposition
rate increases with increasing the temperature.
The kinetic model 12 for lead-bismuth corrosion in
a nonisothermal loop has shown that the corrosion0
deposition distribution and the local corrosion deposi-
tion rate depend strongly on the temperature profile, so
that this effect must be included when analyzing exper-
imental data from a nonisothermal loop. However, based
on current experimental data, we cannot draw any spe-
cific conclusions for the dependence of NaK corrosion
on the temperature gradient. For sodium, Thorley 36 con-
cludes that the temperature difference does not affect
the iron corrosion rate, while correlations developed by
General Electric 33 show a dependence of the deposition
rate on the temperature difference.

NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008

94 ZHANG, KAPERNICK, and MARCILLE
Fig. 15. Dependence of corrosion0deposition rate on the
location temperature, calculated based on data by ORNL.
VI.E. Downstream Effect
A downstream effect has been reported for both cor-
rosion and deposition in sodium loops. It is attributed to
the change in the chemical potential of one or more of
the corroding species in the liquid as the liquid flows
through an isothermal section in the loop.1 Figure 16
shows the corrosion0deposition rates in the isothermal
section of the ORNL loops ~loops 1A and 2! as a func-
Fig. 16. Downstream effects on the local corrosion 0
deposition rate, calculated based on data by ORNL. Corrosion
is from specimen Nos. 4, 5, and 6, and deposition is from
specimen Nos. 12, 13, and 14.
NUCLEAR SCIENCE AND ENGINEERING
Fig. 17. Downstream effects on the attack depth, data from
Pratt & Whitney, loop: NSSA.
tion of the downstream location. Figure 16 indicates that
both the corrosion rate in the hot isothermal leg and the
deposition rate in the cold isothermal leg are functions
of the downstream location, decreasing in the down-
stream direction. The corrosion rate depends more on
the downstream location than does the deposition rate as
indicated in Fig. 16. This may be due to the fact that the
dissolution process in the hot leg is faster than the depo-
sition process in the cold leg.
Considering the downstream effects and the depen-
dence on the temperature profile of the loop, we cannot
conclude that Hastelloy N ~No. 4! steel has a lower cor-
rosion resistance to NaK than SS347 ~No. 5!. The reason
may be the location where the specimen is installed.
The downstream effect on the attack depth is shown
in Fig. 17 based on the data in Table III. Although the
data are very scattered, the fitting results ~dashed and
solid lines in Fig. 17! show a decreasing trend in the
downstream direction.
VII. CONCLUSIONS AND
RECOMMENDATIONS
Based on our study, the following conclusions and
recommendations can be made:
1. Conclusion: The available experimental data are
very scattered, and it is impossible to develop reliable
general correlations for corrosion0deposition by liquid
NaK using these data. The experimental data can be ap-
plied for the design of a nuclear reactor with a liquid-
metal coolant to a very limited degree.
VOL. 160 SEP. 2008
 CORROSION BY NaK COOLANT
Recommendation: Experiments should be per-
formed ~a! to isolate separate effects and ~b! to simulate
the conditions of the nuclear coolant system condi-
tions in an operating space reactor ~demonstration test-
ing!. Theoretical studies should be performed to interpret
these experimental data and to guide the design of the
reactor.
2. Conclusion: Although the attack by NaK changes
the composition of the materials in contact with NaK,
such as sigma phase formation, decarburization, and car-
burization, no material failure due to such changes has
been reported.
Recommendation: The effects of the composition
change by attack of NaK on the substrate properties have
to be identified, especially for a long-term operation sys-
tem. A model needs to be developed to account for cor-
rosion in the reactor component and system design.
Material mechanical property testing needs to be per-
formed and factored into the component structural de-
sign assessments.
3. Conclusion: The local temperature and the tem-
perature profile have significant effects on the loop cor-
rosion and deposition. Generally, the corrosion0deposition
rate increases with the increasing temperature and gen-
erally increases with an increasing temperature differ-
ence in the loop. The temperature profile also determines
where in the loop corrosion and deposition take place.
Recommendation: Integral loop experiments should
be performed to quantify the effects of the temperature
profile on corrosion and deposition. These effects need
to be incorporated into the reactor design models and
analyses.
4. Conclusion: The corrosion0deposition rates by
NaK depend strongly on the oxygen level. Both of them
increase with the increasing oxygen. Given the limited
and scattered data at present, it is not possible at present
to develop an idea relationship between the attack rate
and the oxygen concentration.
Recommendation: Experiments with various oxy-
gen concentrations should be performed to develop a
correlation for the effect of oxygen concentration on the
attack rate by NaK and be incorporated into the reactor
design models and analyses.
5. Conclusion: A cold trap is an effective method
to control the oxygen concentration as well as the hydro-
gen concentration.
Recommendation: Designs considering iron-based al-
loys should consider incorporating a cold trap to control
oxygen. Design studies and testing need to be performed
to develop a cold trap that is reliable and effective.
6. Conclusion: The corrosion rate of nickel alloy
depends little on the oxygen concentration. Increasing
the oxygen concentration leads to high iron mass transfer.
NUCLEAR SCIENCE AND ENGINEERING VOL. 160 SEP. 2008
95
Recommendation: As noted above, the effects of ox-
ygen on the mass transfer of species should be quantified.
7. Conclusion: Mass transfer of carbon is signifi-
cant through decarburization at the hot leg and carburi-
zation at the cold leg.
Recommendation: Further studies ~test, analyses, and
model development! on the mass transfer of carbon and
its effects on the property change on the materials should
be conducted.
8. Conclusion: There are no solubility data for iron,
chromium, nickel, etc.
Recommendation: Experimental studies should be
done to qualify the solubility.
9. Conclusion: In the velocity range considered,
the corrosion deposition rate increases with increasing
flow velocity.
Recommendation: Velocity effects should be
quantified.
10. Conclusion: Loop geometry affects the corro-
sion and deposition rates.
Recommendation: The models discussed above
should be developed and used to optimize the design to
minimize the corrosion and deposition rate in the cool-
ant circuit.
11. Conclusion: Hydrogen appears to have little ef-
fect on the corrosion0deposition rate.
Recommendation: Studies on the effects of hydro-
gen and other impurities in the loop should be performed.
12. Conclusion: Radiolytic effects of liquid NaK are
not well understood in a reactor.
Recommendation: The radiation chemistry of a re-
actor cooled by liquid NaK has to be understood before
NaK is used as the coolant in a nuclear power system.
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 CORROSION BY NaK COOLANT
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