Progress in Nuclear Energy

Progress in Nuclear Energy 48 (2006) 283313
www.elsevier.com/locate/pnucene
Review
Materials development and corrosion problems in nuclear fuel

reprocessing plants
Baldev Raj *, U. Kamachi Mudali
Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, India
Received 30 January 2005; received in revised form 20 July 2005; accepted 20 July 2005
Abstract
A broad based materials development programme has been in progress worldwide towards the development of materials for
applications in spent nuclear fuel reprocessing plants. International efforts have resulted in the development of advanced materials
like nitric acid grade (NAG) special austenitic stainless steels, Ti5% Ta, Ti5% Ta1.8% Nb, CrWSi, NbW, zirconium based
alloys etc. for highly corrosive nitric acid environments. A critical review of performance of current and promising materials and
their associated fabrication technologies for manufacturing is attempted. All-titanium electrolytic dissolver, electrode materials for
electrochemical processes, dissimilar joints of titanium-type 304L stainless steel (SS), and double oxide coating on titanium for
reconditioning (DOCTOR) have been developed at Indira Gandhi Centre for Atomic Research (IGCAR) based on systematic
interdisciplinary R&D efforts. Dynamic nitric acid loop, a unique testing facility built at IGCAR is been described. Directions in
materials and components developments, corrosion assessment and challenges ahead are also discussed.
q 2005 Elsevier Ltd. All rights reserved.
Keywords: Materials; Manufacturing; Coatings; Corrosion; Reprocessing plants; Nitric acid; Advanced materials
1. Introduction
Reprocessing, refabrication and management of radioactive waste are the three major areas of activities that have
attracted focused efforts to achieve successes in the back-end of nuclear fuel cycle (Anil Kakodkar, 2000). The
integrity and availability of nuclear fuel reprocessing plants for uninterrupted operation depends on the quality and
performance of critical engineering components, vessels and piping. Any failure of the component of reprocessing
unit processes would lead to the leakage of radioactivity, and slowing down the production of useful fissile material
required for sustained operation of power plants. Materials selection, fabrication, operation, maintenance and
inspection of various components of different unit processes of reprocessing plants are of paramount importance in
meeting the requirements of uninterrupted and safe operation of reprocessing plants (Baldev et al., 2000). This
demand poses and dictates many challenges with respect to the reprocessing plants, particularly of fast breeder
reactors (FBRs) as they handle high plutonium content fuels with various fission products (FPs) and transuranium
(TRUs) elements due to significant high burn ups in fast breeder reactors. The plants are designed with the objective
of zero incident failures such as leakages in pipes, vessels and equipment since, the repair and maintenance in high
activity area is never a planned activity. High Pu content and higher burn up of the fuel (O100,000 MWd/ton) also
* Corressponding author. Tel.: C91 44 27480260; fax: C91 44 27480060.

E-mail addresses: dir@igcar.ernet (B. Raj), dirsec@igcar.ernet.in (B. Raj).
0149-1970/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pnucene.2005.07.001
284 B. Raj, U.K. Mudali / Progress in Nuclear Energy 48 (2006) 283313
demand shorter process duration in order to enable the fuel to be transferred after each operation considering the high
activity involved. Thus, the unit processes like dissolution need to be made faster by using advanced techniques like,
electro-oxidation process as compared to the conventional Purex method which has a longer dissolution time
(Palamalai, 1988). A faster dissolution process necessitates the use of a high concentration of boiling nitric acid which
is also electrolyzed for effective dissolution. For such severe conditions of dissolution, the materials of construction
and other requirements like electrodes play a major role in meeting the demand of zero failure concept and minimum
maintenance of the plants (Kamachi Mudali et al., 1993).
The Department of Atomic Energy (DAE), Government of India, is pursuing a four stage power programme
consisting of (i) operation of pressurized heavy water reactors (PHWR) and retrieval of plutonium from the spent fuel,
(ii) breeding of plutonium thus retrieved from first stage by utilizing them in fast breeder reactors, (iii) use of
plutonium to convert the vast resource of thorium to U-233, and (iv) use of U-233 for future plants. To begin the
second stage, a fast breeder test reactor (FBTR) has been operating at the Indira Gandhi Centre for Atomic Research
(IGCAR), Kalpakkam, India, since 1985. In order to reprocess the spent mixed (U, Pu) C fuel of the FBTR,
reprocessing research, development and plant activities are currently actively pursued at IGCAR, Kalpakkam. A pilot
plant has been recently built and operated for reprocessing of the spent fuel from FBTR. A large emphasis on
reprocessing feasibility is essential as the success of the second stage of the three stage power programme of DAE
depends on the successful retrieval of the plutonium from the reprocessing of the spent fuel of fast breeder reactors. As
compared to the reprocessing of spent fuel from PHWRs containing low Pu content, the reprocessing of FBR fuels
with high Pu content poses tough challenges. The ions of Pu and FPs and TRUs increase the solution potential and
oxidizing power of the nitric acid process medium and enhance the corrosion rate and failure probability of the vessels
and equipment. The reprocessing of FBR fuels demand special construction materials, as compared to the
conventional workhorse material American Iron and Steel Institute (AISI) type 304L stainless steel (SS) employed in
PUREX based reprocessing plants. The present paper highlights the development of special SS and nonferrous
materials required for the reprocessing of FBR fuels in India and in the world.
1.1. Austenitic stainless steels for nitric acid service
The most practiced process for reprocessing of spent nuclear fuel is aqueous, and a typical flow sheet adopted for a
Purex process based fast reactor reprocessing plant is shown in Fig. 1. Chemical reprocessing plants involve
equipment/vessels such as fuel dissolvers, evaporators for various purposes and high active raffinate waste storage
tanks. Nitric acid is the main process medium for reprocessing plants for spent fuel received from both water reactors
with low plutonium content, and from FBRs with high plutonium content. The acid is used in various conditions from
Fig. 1. Typical flow sheet adopted for a Purex process based fast reactor reprocessing plant.
B. Raj, U.K. Mudali / Progress in Nuclear Energy 48 (2006) 283313 285
dilute (14 N) to concentrated (1014 N), room temperature (solvent extraction) to intermediate (warm, raffinate
waste storage tanks) to boiling temperature (dissolver, evaporator). The presence of redox species (Fe3C, Pu (VI), Cr
(VI) in dissolvers, partitioners etc) is an added dimension to the corrosion behaviour of materials. AISI type 304L SS
is extensively used for fabrication of vessels, tanks, piping and equipment in reprocessing plants wherein the
concentration of the acid is below 8 N and temperature of operation is below 353 K (Kamachi Mudali et al., 1993).
The formation of a stable, adherent and self-healing passive chromium oxide (Cr2O3) film is responsible for good
corrosion resistance of the material under the operating conditions employed in the reprocessing plants. A typical
polarization curve for AISI type 304L SS in nitric acid medium shows the zones in which various equipment reside in
HNO3 medium in service (Fig. 2). In a typical reprocessing plant catering to spent fuel from water reactors with a
capacity of heavy metal output of 100 kg per year, approximately 750 tons of AISI type 304L SS is used for the
construction of the plant. In the case of reprocessing of spent fuel of FBRs for similar quantity of heavy metal output,
the requirement of AISI type 304L SS would be more than 1000 ton. In boiling 65% concentrated nitric acid, pure iron
shows a typical corrosion rate greater than 10,000 mm per year, with the addition of 4.5% Cr, the rate decrease to
about 4000 mm per year. Addition of 8% Cr shows a corrosion rate of 40 mm per year which is reduced to 3 mm per
year by increasing the Cr content to 17%. By increasing Cr to 25%, the corrosion rate decreases to 0.2 mm per year.
Apart from the typical corrosion rates of the alloys mentioned above, Fe18% Cr8% Ni alloy (AISI type 304 SS) in
solution-annealed condition shows a typical corrosion rate of 0.3 mm per year. Most stainless steels, except certain
high chromium types, exhibit an average corrosion rate of 0.13 mm per year in boiling 65% HNO3
(IAEA-TECDOC-421, 1987). The corrosion rate can also be affected by the purity of the process medium.
Several incidences of failures of components made of AISI type 304L SS have been reported in spent nuclear fuel
reprocessing plants when they were used in HNO3 medium beyond 8 N concentration, and temperatures beyond
353 K (IAEA-TECDOC-421, 1987; Shaw, 1990; Yamanouchi et al, 1997; Decours et al, 1987; Balakrishnan, 1992;
Baldev and Kasiviswanathan, 1997). The failures has been attributed to (i) intergranular corrosion due to
sensitization, (ii) intergranular corrosion due to impurities segregation at grain boundaries, (iii) transpassive
dissolution of passive films, and (iv) selective corrosion of welds. Sensitisation is the formation of chromium depleted
(!9% Cr) zones adjacent to chromium rich carbides (Cr23C6) formed along the grain boundaries while stainless
steels are either heat treated or slowly cooled through the temperature regime of 7231073 K (Cihal, 1994).
Sensitization facilitates intergranular corrosion along the chromium-depleted zones. AISI type 304L has the presence
of significant quantities of other elements (Si-1%, Mn-2%, S-0.02%, P-0.04%, B-0.005, etc.). These elements have
the possibility to segregate to the grain boundaries after solution annealing and heat treatments. Such segregation
Fig. 2. Schematic polarization diagram showing the corrosive zones seen for austenitic stainless steels in nitric acid environment in reprocessing
plants (Steele, 1986).
results in the formation of weak passive films at the grain boundaries, which rapidly dissolve leading to selective
intergranular corrosion. When the concentration of the acid increases beyond 8 N or the temperature of the acid
increases beyond 353 K, the normally protective Cr2O3 passive film gets oxidized to CrO3 with the transformation of
Cr3C ions into soluble Cr6C ions. This leads to excessive dissolution of the surface and higher corrosion rates of
stainless steels in boiling nitric acid service.
AISI type 304L SS is evaluated for the corrosion resistance as per ASTM A262 practice C (HUEY test) in boiling
concentrated nitric acid for 240 h as recommended by United States Nuclear Regulatory Commission (USNRC)
(USNRC Regulatory Guide 3.37, 1975). The alloy is permitted for application in nitric acid service if it exhibits a
corrosion rate of 18 mil per year (mpy) (0.45 mm/year) and below after sensitization at 948 K for 1 h. Even for
nonactive and utility areas of reprocessing plants, an alloy with a maximum corrosion rate of 24 mpy (0.6 mm/year) is
acceptable. However, for any critical application in nitric acid service the alloy must exhibit 18 mpy (0.45 mm/year)
and below in the sensitized condition, which can occur during welding and heat treatment. AISI type 304L SS, and its
improved varieties with extra low-carbon (AISI type 304ELC), with Nb (AISI type 347), with Ti (AISI type 321), or
AISI type 310L SS and its equivalent with Nb stabilization and high Cr content, have been used in several
reprocessing plants in the world for many critical applications. However, qualification of welding methods and
carrying out the boiling nitric acid (Huey test) on qualified specimens is essential to avoid failures.
The challenge in materials development with respect to the manufacturing of austenitic stainless steels lies in the
elimination of the corrosion problems discussed above and finding improved varieties with controlled alloying
elements and microstructure exhibiting higher corrosion resistance. The efforts are directed towards developing alloys
which would show corrosion rates less than 18 mpy (0.45 mm/year). The development is important as this would (i)
enhance the life of components and availability of plants for extended periods, (ii) avoid the use of other expensive
materials like titanium, zirconium and their alloys and associated problem of dissimilar metal joining, (iii) reduce the
thickness of the components where corrosion allowance is considered for desired life. It is essential that welding
technology appropriate to the alloy of service implemented with good quality management practices to avoid failures.
1.2. Evolution of nitric acid grade austenitic stainless steels
Nitric acid grade (NAG) austenitic stainless steels are the alloys inherently developed with (i) controlled chemical
composition of alloying elements, (ii) modified microstructures leading to elimination of weaker sites for passive film
break down and dissolution, and (iii) enhanced strength against transpassive dissolution leading to extended passive
state (Fig. 3). Several types of NAG alloys having compositions similar to AISI types 304L, 310L, and several new
proprietary alloys have been developed worldwide (Sedriks, 1979). Fig. 4 shows the corrosion rates for conventional
and nitric acid grade stainless steel alloys along with various other materials as determined by boiling nitric acid
(Huey) test (Kamachi Mudali et al., 1993). Significant decrease in the corrosion rates of NAG alloys can be noticed
with respect to conventional AISI type 304L SS. Table 1 shows typical chemical compositions of various materials.
Chromium imparts stability to the passive film of stainless steel and thus increasing chromium content increases
the stability and strength of passive film. However, in practice chromium levels below 30% are used as increases in
chromium contents beyond this level affects the stability of the austenite phase and enhances the formation of ferritic
phase during manufacturing of components. Nickel is another element which improves the strength and ductility of
passive films through stabilizing austenite, and normally this is kept within 15% as increases in nickel content
increases the cost of the alloy. Molybdenum is completely removed from the alloy due to two important reasons
namely, (i) increasing ferrite formation, and (ii) submicroscopic sigma precipitation during multipass welding of
components thicker than 6 mm (it is well known that sigma preferentially dissolves in hot oxidizing nitric acid leading
to excessive corrosion rates). Manganese, silicon, copper and aluminium are normally present as impurities in the
steel making. Controlling manganese is desirable as it reduces the presence of MnS inclusions which are deleterious
with respect to preferential corrosion in nitric acid service. Though 2% Mn is kept as upper level for AISI type 304L
SS in ASTM specifications, in order to achieve higher cleanliness and lesser inclusions content, Mn content less than
1% is recommended. Copper and aluminium are also reduced to low levels as they enhance selective corrosion attack
in nitric acid service. Silicon is a very important element with respect to developing special alloys for nitric acid
service. It is normally permitted up to 1% as per ASTM specifications for plates. However, silicon has dual role with
respect to corrosion of AISI type 304L SS in nitric acid. It has been reported (Sedriks, 1979) that when Si content is
less than 0.2%, excellent corrosion resistance is achieved while enhanced performance is also achieved with silicon
Fig. 3. Concept behind the development of nitric acid grade and other special alloys for nitric acid service in reprocessing plants (Kiuchi et al., 1994).
content beyond 1.6%. However, between 0.4 and 1% Si content, the performance deteriorates with excessive
intergranular attack. Hence, two grades of NAG alloys have evolved, one with Si less than 0.2%, and the other with
4% Si.
The impurity elements like S, P and B significantly affect the corrosion resistance (Fig. 5 (a) and (b)) of AISI type
304L SS in nitric acid (Uno Blom and Bengt Kvarnback, 1975; Beckitt et al., 1987). In association with manganese,
sulphur forms chemically soluble MnS inclusions which degrade the alloy with selective dissolution. One of the
major problems in using bars and cut sections including tapered machined parts of AISI type 304L SS is end grain
attack or tunnel corrosion (Steele, 1986). The longitudinally aligned MnS inclusions are vertically cut and such cut
faces expose MnS inclusions for selective attack leading to the formation of corrosion tunnels (Fig. 6) or a puff
candy appearance due to severe corrosion. The solubility of sulphur in the alloy is about 10 ppm and decreasing the
sulphur content below 50 ppm needs advanced steel making practices like electro slag remelting, electron beam
melting, and combined double arc melting followed by vacuum induction melting (VIM), or argon oxygen
decarburisation (AOD) or vacuum oxygen decarburisation (VOD) (Sedriks, 1979; Uno Blom and Bengt Kvarnback,
1975; Beckitt et al., 1987; Steele, 1986; Yanokura et al., 1994). Another method to eliminate the problem of inclusion
attack is shape controlling of inclusions by either adding rare earth elements (REMs) or Ca, or Ti or globularising
the inclusions in order to have low surface to volume ratio through special fabrication processes (Kiessling, 1989).
Fig. 4. Corrosion rate obtained for conventional and nitric acid grade SS alloys along with various other materials after boiling nitric acid (Huey)
test (Kamachi Mudali et al., 1993).
In comparison to longitudinal stringers of MnS, the globular MnS inclusions pose less severe problems. Unlike
sulphur, phosphorus does not form any compound, however segregates at the grain boundaries and interfaces to as
high as 105 times of original concentration (Sedriks, 1979; Uno Blom and Bengt Kvarnback, 1975; Beckitt et al.,
1987). For example, an initial concentration of 350 ppm of P in the alloy can segregate to about 3.5 wt% at the grain
boundaries due to non-equilibrium segregation phenomena during heat treatments. Passive films formed at such
boundaries are known to be weaker. Such a film undergoes selective corrosion attack along grain boundaries. An
example is intergranular corrosion in hot oxidizing nitric acid even in the absence of sensitization. Fig. 7(a)(c) show
the variations in the grain boundary attack of conventional and nitric acid grade special SS after the boiling nitric acid
test (Kamachi Mudali et al., 1993). The decrease in the grain boundary corrosion attack can be clearly seen as the
impurity elements in the alloy are decreased (Table 1). Phosphorous is controlled within 200 ppm in NAG grade
Table 1
Chemical composition of various materials used for application in reprocessing plants (wt%)
Elements CP Ti Ti5% Ta Zircaloy-2 Nuclear grade Uranus-16 NAG Uranus-65 NAG Commercial AISI
type 304L SS SS SS type 304L SS
Fe 0.041 0.028 0.230 Balance Balance Balance Balance
Cr 0.114 18.33 18.07 24.97 18.2
Ni 0.005 10.12 12.31 19.60 9.8
O 0.096 0.091 0.113
N 0.003 0.005 0.003 0.018 0.026
H 0.0025 0.0028 0.001
S 0.004 0.001 0.001 0.030
P 0.030 0.012 0.023 0.045
Sn 1.490
Ta 5.000
C 0.015 0.014 0.03 0.012 0.012 0.03
Si 0.008 0.064 0.09 0.190 1.0
Mn 1.640 0.69 0.562 2.0
Hf 0.003
Ti Balance Balance
Zr Balance
Fig. 5. (a) and (b) Corrosion rates obtained for various type 304 SS alloys with different contents of C, P and Si in nitric acid medium (Uno Blom and
Bengt Kvarnback, 1975).
alloys and both S and P together within 250 ppm to ensure good corrosion resistance. Boron is traditionally
maintained in austenitic stainless steels within 30 ppm to ensure adequate hot working and prevent cracking/fissuring
during hot working (Gladman, 1989). However, it forms dichromium boride (D-Cr2B) along grain boundaries even
during water quenching after solution annealing. This results in significant deterioration in corrosion resistance of the
conventional AISI type 304L and hence for NAG alloys, boron is kept within 10 ppm.
Carbon is an important element as far as application of austenitic stainless steels for corrosive environments is
concerned (USNRC Regulatory Guide 3.37, 1975; Cihal, 1994; Sedriks, 1979; Beckitt et al., 1987). In nitric acid
environment, carbon content significantly affects the corrosion rate depending on the heat treatment conditions
(Fig. 8). In a typical AISI type 304 SS, the carbon content is kept within a range of 0.060.08%. During welding, heat
treatment etc. whenever the alloy is slowly heated or cooled through the temperature regime 7231073 K, carbon
enhances the formation of chromium rich M23C6 carbide (MZCr, Ni, Fe; Cr-65, Ni-10 and Fe-5 wt%) at grain
boundaries. In this temperature range, carbide precipitation is thermodynamically possible, and kinetically the
diffusion of alloying elements like C, Cr, Ni etc. are favourable. Owing to the slower diffusion coefficient of Cr as
compared to C, chromium from the bulk of the alloy cannot diffuse to the regions adjacent to the carbides formed
along the grain boundaries. This leads to selective depletion of Cr (within 912 wt%) in a narrow region (as low as
200 nm) adjacent to the grain boundary M23C6 carbides, thus promoting excessive corrosion along the grain
boundaries due to the following reasons (IAEA-TECDOC-421, 1987): (i) galvanic cell formation between Cr23C6 and
Cr-depleted zone, (ii) less Cr at depleted zone favouring more corrosion, and (iii) strain build up at carbide/matrix
interface. Reduction of carbon below 0.03 wt% is an attractive proposal to overcome the selective intergranular
corrosion along the sensitized zones, and thus AISI type 304L SS alloys have been developed extensively for most of
the components in reprocessing plants. As we have discussed earlier, AISI type 304L SS has limitations when the
nitric acid concentration is 8 N and above, and the temperature is beyond 353 K. With the advancements taking place
in steel making, ultra low-carbon alloys with carbon levels less than 0.015% are being developed for nitric acid
Fig. 6. Selective corrosion attack leading to the formation of corrosion tunnels (Kamachi Mudali et al., 1993).
applications. Such an alloy has shown good corrosion resistance in several other environments also (Kikuchi et al.,
1991a,b, 1994). However, cost effectiveness is an important issue as these alloys are expensive (nearly, 1015 times
of conventional alloys). Comprehensive manufacturing technology must be suitably evolved to get full advantage of
NAG stainless steels.
1.3. Challenges in the application of NAG stainless steels
The choice of NAG SS for specific components in reprocessing plants demands attention to issues associated with
fabrication, welding and maintenance. Ultra low-carbon levels of 0.015% in the alloy reduces the mechanical strength
and poses fabrication related problem during hot working, forging and other metal forming operations. Contamination
of carbon at the surface due to diffusion of carbon from atmosphere, tools and other steel parts pose major problems
with respect to carbide precipitation on the surface and dissolution in nitric acid. Welding of NAG alloys needs
special welding consumables and requires the establishment of strict welding procedures. Low-carbon varieties of
stainless steels have a high propensity for sigma phase and other precipitation during multipass welding of thick
components (concentrators, evaporators), and it is well known that sigma phase preferentially dissolves in hot
oxidizing nitric acid (Sedriks, 1979). Heat inputs and consumables need to be clearly established for the success. One
way of reducing the cost of using NAG SS, and a most effective way of using these alloys for nitric acid service, is to
clad these special steels on conventional AISI type 304L. In Japan, special grade SAR SS was cladded to conventional
13Cr10NiNb stabilized stainless steel (Kikuchi et al., 1999). Caution should be exercised to avoid the diffusion of
carbon from conventional stainless steel to the special grade stainless steel during cladding, defects generated during
Fig. 7. (a)(c): Variations in the grain boundary attack of conventional and nitric acid grade special SS after boiling nitric acid test, (a) commercial
type 304L SS, (b) Uranus 16 SS, and (c) Uranus 65 SS (Kamachi Mudali et al., 1993).
cladding, and further fabrication and welding of cladded plates. In Japan, hot isostatic pressing, electron beam melting
and diffusion bonding techniques have been used for cladding of special grade modified electron beam melted-solution
annealed, aged, recrystallised (EB-SAR) and processed type 304ULC SS (ultra low carbon) on conventional type 304L
SS. Diffusion bonding by hot rolling at a suitable temperature above 1098 K, within 60% reduction ratio, exhibits
appropriate bonded area without any defects. Cladding of high CrWSi base RW (recrystallised, worked) alloy on
conventional AISI type 304L SS by diffusion bonding has been achieved at 1373 K, at a reduction ratio of 50%, by hot
rolling. The criterion for choosing the condition is based on austenite phase stability and grain growth control.
2. International experience in materials reliability vis-a-vis corrosion issues
International efforts over the last two decades for developing high performance austenitic stainless steels for
applications in nitric acid have resulted in better understanding and significant improvements in corrosion resistance.
Major materials of construction used in the Sellafield, Dounreay and Windscale reprocessing plants (UK) are
Fig. 8. Influence of carbon content on the corrosion rate in nitric acid environments (Beckitt et al., 1987).
18Cr/13Ni/Nb-stabilized AISI type 347 SS in the highly active primary plant, and 18Cr/8Ni/Ti-stabilized AISI type
321 for providing a maintainable secondary plant (Shaw, 1990). Corrosion problems have been experienced with the
dissolver due to knife line attack at weld regions, and end grain attack at pipe cut sections. Subsequently, the 18Cr/
13Ni/Nb-stabilized AISI type 347 was replaced with a specially manufactured nitric acid grade (NAG) type 304L.
25Cr/20Ni/low carbon AISI type 310L SS and 18Cr/15Ni/4Si alloys have been considered. In Japan, the materials
and corrosion investigations (Balakrishnan, 1992) carried out at Tokai reprocessing plant and Nuclear Fuel
Development Corporation facilities have revealed three leaking locations of welding lines of dissolvers made of
Uranus-65 (equivalent to 310L NAG SS) which led to the shut down of the plant for 2 years. Improved dissolvers
made of NAG 310L, Nb stabilized, and Ti5%Ta were subsequently commissioned for operation. Corrosion failure in
the welding lines of acid recovery distillator and evaporator have revealed vapour phase corrosion attack in the
titanium evaporator, and a leak in the AISI type 304L tower. For future applications, zirconium and its alloys, and Ti
5%Ta alloy have been recommended for overcoming the vapour phase corrosion attack. However, stainless steels
continue to be the major construction material for many applications. Similarly stainless steels are the major materials
of construction in the reprocessing plants in France (Decours et al., 1987). Materials development and corrosion
investigations at La Hague plants and Marcoule pilot plant have resulted in recommendation to use Z2CN18-10 (AISI
type 304L) alloy for use with up to 8 N boiling nitric acid, beyond which Z2CN25-20 Uranus 65 (AISI type 310L)
alloy is recommended. However, in the presence of oxidizing agents like Fe3C, Pu (VI), Cr (VI), Ce (IV) and various
fission products, Z1CNS17-15 Uranus S1N (Si added AISI type 304L SS) alloy has been recommended. The
satisfaction with austenitic stainless steels is not complete, hence, zirconium and its alloys have been recommended
for future applications. Indeed, a total of 80 ton of Zr and 5500 m of Zr piping have been employed for setting up a
pilot plant at Marcoule (IAEA-TECDOC-421, 1987).
In India, several corrosion-related failures have been experienced with stainless steels (Balakrishnan, 1992).
During the operation of the demonstration plant at Trombay, a number of leaks were detected near the weld joints of
dissolver made of AISI type 347 due to knife line attack. Nozzles made of AISI type 347 dipping into a process
solution containing ferrous sulphamate were found completely disintegrated, and the vessel walls suffered extensive
thinning and deformation. Pitting corrosion leading to perforation of AISI type 304L internal coils of some storage
vessels have been observed. Improper and extended storage in stagnant water conditions have resulted in pitting
attack and microbiologically influenced corrosion. AISI type 304 floorings of underground vaults developed hairline
cracks in the heat affected zones due to seeping in of sub-soil water. Several nozzles used for introducing
thermocouples were covered in the end with a machined cap manufactured from a bar stock. End grain and tunnel
corrosion attack of such caps led to formation of pinholes and subsequent leakage of nitric acid. Some of the
evaporators which had internal coils for heating developed leaks after a few years of operation. Incidents of failure of
heat exchangers/condensers in nitric acid medium, have been reported with corrosion at the tube/tube sheet fillet weld
joints at the entry point of the nitric acid vapour. At Kalpakkam Reprocessing plant (KARP), AISI type 304L SS
dished ends were stored in the coastal atmosphere. They contained heavy residual stresses and were not solution
annealed. The salt content in the coastal atmosphere resulted in condensation of chloride ions. The combination of
residual stresses and the condensation of chloride ions led to stress corrosion cracking failure of the dished ends
(Baldev and Kasiviswanathan, 1997). Pickling and passivation was recommended as one of the remedies to eliminate
the iron particles embedded on the surface of dished ends during manufacturing in the shop floor.
3. Promising metals and alloys for nitric acid service
The corrosion problems are more severe during dissolution of fast reactor fuel of high burn ups due to large yields of
FPs and TRUs in the spent fuel as well as complex organic species after dissolution (specific to carbide fuels). For the
dissolution of spent (U, Pu) C fuel from fast breeder test reactor (FBTR) at Kalpakkam, 11.5 N HNO3 with AgC/Ag2C
redox ion under electrolytic condition is employed (Palamalai, 1988). These conditions are found to dissolve the fuel
with the elimination of carbon complexes. Conventional AISI type 304L SS cannot be used for the fabrication of
electrolytic dissolvers due to the high corrosion rates in such corrosive conditions. High performance nitric acid grade
stainless steel would also undergo corrosion problems under these conditions (Kamachi Mudali et al., 1993). The
demand for a suitable material can be met from Ti, Ti5%Ta, Ti5%Ta1.8%Nb, zirconium and its alloys as materials
of construction for the electrolytic dissolver as these materials exhibit acceptable corrosion resistance in highly
corrosive nitric acid solution. The use of dissolvers made of these materials necessitated the development of dissimilar
joints through explosive joining, diffusion bonding, friction joining etc. to interconnect the dissolver equipment with
AISI type 304L SS. The use of the electrolytic process also necessitated the development of suitable and efficient anodes
with capability of requisite current densities in order to withstand the aggressive oxidizing conditions.
3.1. Development efforts in the application of titanium and its alloys
Extensive studies have been carried out at IGCAR to arrive at a suitable material of construction for the electrolytic
dissolver for the FBTR fuel demonstration facility (Baldev et al., 2000; Kamachi Mudali et al, 1993; Kamachi Mudali
et al., 1999; Kamachi Mudali et al., 1998; Ananda Rao et al., 1998). Titanium, Ti5% Ta, Ti0.25% Pd, surface
modified titanium (thermally oxidized and anodized), Zircaloy-2, weldments of Ti and Ti5% Ta, NAG grade special
SS etc. have been tested as per ASTM A 262 practice C (Huey test), simulated reprocessing boiling nitric acid test and
the 3-phase test (liquid, vapour and condensate). Figs. 4 and 9 and Tables 2 and 3 show the results obtained from these
Fig. 9. Corrosion rates obtained for weldments of various other materials after boiling nitric acid (Huey) test (Kamachi Mudali et al., 1995).
Table 2
Corrosion rate of materials in simulated radioactive solution
Materials Temperature Corrosion rate (mpy)

(K) Electrolytic dissolution (UC in 6 M HNO3) Refluxing condition (UC in 12 M HNO3)
Ti air-oxidised at 823 K 304 11
338 96, 21, 31
343 32
360 190, 109
Ti airoxidised at 873 K 304 2
338 31, 33 1.3
343 56
355 2, 7.5, 13
360 2.5
Tiair oxidised at 923 K 304 6
338 42.5
343 59
Anodised Ti 304 8.5
338 1
343 30
Ti (asreceived) 338 40, 5
358 28, 30
Ti5% Ta 338 4 17, 13
358 2, 1 13.5, 24
363 4
Ti0.25% Pd 338 4 50, 63, 20
358 41, 2 55, 143, 287
363 53, 119
Zircaloy-2 338 3 5, 2
358 6, 1 4
363 16, 18
investigations. Based on the results, titanium has been chosen as a material of construction for the fabrication of the
electrolytic dissolver (Fig. 10).
Unalloyed titanium exhibits good corrosion resistance in nitric acid medium even at concentrations and
temperatures where stainless steels undergo severe uniform corrosion and intergranular corrosion (IMI Handbook;
DECHEMA, 2001). Titanium corrodes at rates below 1 mpy (0.025 mm/year) for all concentrations between 308 and
433 K depending on the purity of nitric acid. Under the widely used conditions of reprocessing plants, i.e. within 35
65% of boiling nitric acid, titanium exhibits low corrosion rates. At temperatures beyond 353 K, the corrosion
resistance of titanium depends on the purity of the acid and the metal, and it varies between 10 to 100 mpy (0.25
2.5 mm/year) in red fuming acid conditions depending on the temperature. The inhibiting effect of Ti4C ions accounts
for the discrepancies in the corrosion rates measured for titanium in various applications depending on the titanium
surface area to acid volume ratio, the test duration and container, and the rate of solution replenishment. Unlike the
corrosion behavior shown by many metals and alloys in nitric acid environments, the corrosion resistance of Ti
improves dramatically as the impurity levels in hot nitric acid increases. Small amounts of dissolved species of Fe3C,
Table 3
Corrosion rates of various materials after 3-phase corrosion test in boiling nitric acid solution containing silver and chromium ions
Material condition Corrosion rate (in liquid), mpy Corrosion rate (in vapour), mpy Corrosion rate (in condensate), mpy
100 h 200 h 300 h 400 h 500 h 100 h 200 h 300 h 400 h 500 h 100 h 200 h 300 h 400 h 500 h
Titanium 1.1 0.3 0.9 0.0 0.9 4.8 3.3 2.7 5.4 6.0 3.3 1.2 0.3 0.0 0.9
Ti Weld 1.1 0.4 1.1 0.0 0.7 4.5 2.3 3.3 7.1 5.8 1.3 0.5 0.5 3.1 0.8
Ti5% Ta 0.2 0.6 0.4 0.8 0.0 0.2 0.6 0.6 0.8 0.8 0.4 0.4 0.6 2.5 0.6
Zircaloy2 0.2 0.2 0.4 0.2 0.2 1.1 0.6 0.0 0.4 1.5 0.2 0.0 0.4 0.6 0.6
Uranus 65 3.0 8.7 5.0 12.5 3.7 2.9 3.2 3.1 6.9 1.8 549.9 410.2 1684.7 1426.7 1134.9
Uranus SIN 3.2 1.1 1.1 5.3 3.2 2.9 2.0 1.4 3.7 2.5 CD
CDcompletely dissolved.
Fig. 10. Schematic diagram showing the all-titanium electrolytic dissolver.
Cr6C, Ti4C, Si4C and various fission product ions can effectively inhibit the corrosion of titanium in hot boiling nitric
acid solutions (Thomas, 1986; Bomberger, 1957). Thus, titanium exhibits excellent resistance to recirculating nitric
acid process streams, such as stripper reboiler loops, hold tanks and stripper sumps in which steady state levels of
dissolved Ti4C inhibitor is achieved. The corrosion rate of titanium decreases as the amount of Ti4C in the test
solution increases (Thomas, 1986). In this respect, titanium is also a good candidate material for evaporator reboilers
and other components in high temperature process streams used for U3O8 recovery.
In hot and pure, as well as in vapour condensates of nitric acid environments, titanium exhibits high corrosion rates
beyond 0.25 mm/year, with increase in temperature and within 2070% acid concentration. In such pure and
refreshed solutions, a semi protective oxide film is developed which undergoes continuous dissolution in service.
Fig. 11(a) and (b) show the micrographs of the surface of titanium after testing in the vapour and condensate zone of
the 3-phase test using 11.5 N boiling nitric acid. This situation is often experienced in evaporators where titanium
fails due to vapour phase attack. The semiprotective, loosely adherent, and hydrated TiO2 film gets detached from
Fig. 11. (a)(b) Corrosion attack on titanium after testing in the vapour and condensate zone of the three phase test using 11.5 N boiling nitric acid.
the surface, and causes blockages in disentrainment columns, lutes etc. (Steele, 1986; Bomberger, 1957). Some
oxides inevitably find their way into the concentrated product and need to be removed by methods like centrifuging.
The loose deposits of finely divided titanium also lead to ignition or pyrophoricity and explosion hazards. The
tendency increases as the NOx content of the fume is more than 20%, and the water content is less than 2%. To obtain
good corrosion resistance of titanium, formation of a completely protective thin titanium dioxide (TiO2) film
analogous to stainless steels is essential. However, titanium does not undergo transpassive dissolution with increase in
the oxidizing power as in the case of stainless steels. Hence, titanium vessels have been successfully used in
reprocessing plants under various plant operating conditions as its corrosion rate was less by a factor of at least ten to
that of competitive stainless steels (IMI Handbook).
On several occasions, titanium equipment handling nitric acid had failed in the acid concentration in range of 40
60% where it should exhibit low corrosion rate, and above 95% (IMI Handbook). These failures are attributed due to
preferential corrosion attack at weld regions. Detailed investigations have revealed that the corrosion attack occurs at
base and weld regions when the iron content in the titanium is high. Iron is soluble in titanium upto 0.04 wt%, beyond
which it precipitates out as an intermetallic with titanium. In addition iron also stabilizes beta phase when it is heat
treated above the beta transus. This is predominant when the iron content is above 0.05%. While the beta phase is
available as isolated fine particles in the base metal, due to slow cooling, iron appears as interconnected needles of
beta phase in weld and heat affected zones. Galvanic attack takes place between the alpha and beta phases when
titanium is exposed to nitric acid. In such a microstructure, corrosion attack penetrates along the needles in the weld
region (Kamachi Mudali et al., 1993; Kamachi Mudali et al., 1995; IMI Handbook). Fig. 12 (a) and (b) show corrosion
attack along the interconnected beta needles at the weld zone and the heat-affected zone, respectively. Preferential
attack does not take place when the iron content is maintained below 0.04% in the base metal.
Fig. 12. (a) and (b) Corrosion attack along the interconnected beta needles at the weld zone and the heat affected zone of Ti5% Ta weldment
(Kamachi Mudali et al., 1995).
Limited corrosion related information is available for alphabeta and beta phase titanium alloys in nitric acid
environments (DECHEMA, 2002; Kikuchi et al., 1999). It is reported that increasing aluminium and other beta
stabilizing elements normally decrease the corrosion resistance while the alpha alloys, in general, exhibit good
corrosion resistance in hot nitric acid environments. Indeed, high purity unalloyed titanium with low Fe, S etc. does
not accelerate the preferential corrosion at weld regions. Titanium stabilized with beta phase elements and
maintaining single phase near-alpha structure, and unalloyed titanium with low iron, enhance the corrosion resistance
in hot nitric acid environments. Ti5% Ta has been found to exhibit exceptional corrosion resistance (Figs. 4 and 13)
based on systematic investigations carried out towards application as electrolytic dissolver material (Kamachi Mudali
et al., 1993; Takamura, 1986; Fujii and Corr, 1990). It shows very low corrosion rates, particularly under condensate
and vapour phase regions of nitric acid. Alloying with Ta, which forms a more stable TiTaO2 and Ta2O5 film on the
surface, reduces the corrosion rate. Corrosion initially proceeds in Ti5% Ta alloy by the selective dissolution of Ti
into the solution and oxygen diffusion into the alloy. This leads to a strong enrichment of tantalum oxide in the scale
with about 40% Ta (Eickmans et al., 1990). It has been reported that addition of 5% Ta results in a five-fold decrease
in the corrosion rate while the cost is increased by three-fold (Furuya et al., 1984). In the Tokai reprocessing plant, an
evaporator made of Ti5% Ta alloy has been successfully used from 1985 onwards (Yamanouchi et al., 1987). In the
Huey test and as well as in tests in a simulated boiling reprocessing concentrated nitric acid solution containing Cr6C
and Ag2C ions, the alloy shows low corrosion rates that are acceptable (Tables 2 and 3). However, in welded
conditions, the alloy shows increasing corrosion rates (Fig. 9) of about 10 mpy (0.25 mm/year) in boiling nitric acid
medium (Kamachi Mudali et al., 1995). This corrosion behaviour has been attributed to the formation of Fe-based
intermetallics and the complex microstructure formed due to welding process. Weld regions show needle-shaped beta
phase secondary precipitates which could provide beta/alpha interfaces for galvanic attack (Fig. 12). Recent
investigations have indicated poor corrosion resistance of an evaporator made of this alloy with selective corrosion
attack at the liquidvapour interface due to the high dissolution rate in flowing condensed nitric acid solutions. A new
alloy with the addition of NbTi5% Ta has been developed to overcome such corrosion problems (Kikuchi et al.,
1991a,b; Kikuchi et al., 1999). Addition of 1.8% Nb has been found to significantly reduce the corrosion rate of Ti
5%Ta alloy in boiling nitric acid (Fig. 14). Among the various candidate metals, the bcc metals like Cr, W and Mo
Fig. 13. Corrosion rate of titanium in boiling nitric acid with the addition of tantalum (Furuya et al., 1984).
form MO3 type films, hcp metals like Ti and Zr form MO2 type films, and bcc metals like Nb and Ta form M2O5 type
films which exhibit superior corrosion resistance in nitric acid medium (Kiuchi et al., 2002). In general, the reasons
for adding Ta and Nb to titanium for improving the corrosion resistance includes: (i) similar atomic size of metallic
ions (corrosion resistance depends on differences in ionic radii between alloying elements and the matrix metal;
elements with different ion size tend to segregate along the crystal habit planes of hcp type, while lamellae type
structure favours selective dissolution of alloying elements), (ii) stable M2O5 type oxide film formation (within stable
alpha phase, corrosion resistance is increased), and (iii) tantalum is more effective because of less solubility of oxides
of Ta in HNO3 compared to those of niobium.
Fig. 14. Corrosion rate of titanium in boiling nitric acid with the addition of tantalum and niobium (Kiuchi et al., 1994).
Table 4
Chemical composition of Ti5%Ta2%Nb alloy
Element Ta Nb Fe O N C H Ti
Amount 4.39 1.94 0.026 502 ppm 47 ppm 125 ppm 9 ppm Balance
3.2. Ti5%Ta2%Nb alloy for electrolytic dissolver applications
Based on the extensive research and the international experience on the use of titanium and its alloys for
reprocessing plants Ti5%Ta1.8%Nb alloy has been developed in India for electrolytic dissolver applications in fast
reactor spent fuel reprocessing plants. The composition of such an alloy produced at Nuclear Fuel Complex,
Hyderabad is given in Table 4. Alloy melting and thermo-mechanical procedures have been evolved through
systematic investigations, and an optimized microstructural condition was evolved (Kapoor et al., 2003). The safe
operating window for hot working operations was determined based on determination of the temperature limits of the
two phases. The beta-to-alpha transition temperature and Ms have been determined for the first time by
metallography, DSC and computational methods. The beta transus of the alloy was found to lie between 1138 and
1143 K. The as-received material has been observed to have a transformed b structure with alternate lamellae of a and
b where the b phase is enriched with the b stabilizers Ta and Nb. In order to identify the optimum microstructure with
the best combination of corrosion resistance and mechanical properties, and for the refinement of the processing
route, a detailed experimental program on characterization of the alloy and structure-property correlations has been
undertaken (Baldev et al., 2003). The optimized microstructure showed beneficial equiaxed alpha with discrete
particles of retained beta with good corrosion resistance. Fig. 15(a) and (b) shows both deleterious and optimized
microstructure of the alloy. Specimens of the as received alloy were heat treated in a range of temperatures starting
from 1100 to 1273 K and both air-cooled and water quenched to understand their corrosion behaviour (Fig. 16). Three
phase corrosion studies on those specimens indicated that heat treatment at 1273 K followed by water quenching
resulted in the best corrosion resistance with very low corrosion rates (!1 mpy). Auger electron spectroscopic studies
Fig. 15. (a) and (b) Optical micrographs of (a) deleterious and (b) optimized microstructure of the TiTaNb alloy (Baldev et al., 2003).
Fig. 16. Corrosion rates of TiTaNb alloy specimens in heat treated as well as welded conditions after 3-phase corrosion test in 11.5 N HNO3.
of those tested specimens revealed that the protective film formed on the alloy heat treated at 1273 K showed higher
Ta and Nb contents compared to other specimens. Attempts were made to study the weldability of the alloy under
specified welding conditions, including for dissimilar joining of the alloy with type 304L. The welded specimen
exhibited good corrosion resistance with low corrosion rates (!1 mpy) for this alloy in liquid, vapour and condensate
conditions of boiling 11.5 N HNO3 (Kamachi Mudali et al., unpublished, 2005). Currently the industrial scale
production of this alloy is in progress.
3.3. Development of double oxide coating on titanium for reconditioning (DOCTOR)
The presence of iron greater than 0.05 wt% in titanium enhances corrosion rates in both base and the welded regions
due to segregation of iron and formation of iron-rich intermetallics. Detailed electrochemical investigations carried out
in our laboratory (Raju et al., communicated, 2005) indicated that the presence of iron in excess of 0.05% in solid
solution, irontitanium intermetallics at the surface, and iron embedment on titanium, significantly decreased the
passivation characteristics of titanium and enhanced active and transpassive dissolution. The crucial role played by iron
in deciding the corrosion resistance in concentrated nitric acid at high temperature motivated to develop a suitable
passivation technology for improving the corrosion resistance of titanium in both wrought and welded conditions.
Considering that the passivation technology needs to be implemented for fabricated components, treatments like
thermal oxidation, metal spraying, advanced coating technologies etc. are not considered for this purpose.
Chemical/electrochemical anodisation is a unique way of forming a surface oxide layer that can protect and distinctly
enhance the corrosion resistance of several metals and alloys. However, it has been reported in the literature that upon
anodisation in several chemical media, the corrosion resistance of titanium is not improved significantly in nitric acid
medium (DECHEMA, 2001). The salient features of the passivation technology development related to: (i) a method
to dissolve the iron particles segregated/enriched at the surface using chemical solutions by simple immersion
method; (ii) application of nitric acid based solution containing redox ions that can enhance anodic oxidation for
forming a stable oxide layer; (iii) further stabilisation and growth of oxide layer in an alternate chemical solution; and
finally, (iv) conditioning of the surface layer. Several electrochemical treatments have been attempted for improving
the corrosion resistance. After such treatments, the specimens were tested as per ASTM A262 practice C in boiling
11.5 N HNO3 solution for five successive periods of 48 h. Table 5 shows average corrosion rates obtained for the
specimens under different surface treatment conditions. Among all the treatments, anodising for 24 h in a solution of
nitric acid containing Ru, Cr and HF, and then subsequent anodic treatment in a solution of 10% ammonium
persulfate gave the best results. The corrosion rate reduced to about 4 and 6 mpy (0.10.15 mm/year) in the Huey test.
This passivation technology for developing a corrosion resistant layer on titanium has been named as double oxide
coating on titanium for reconditioning (DOCTOR), and can be used for surface modification of dissolver made of
titanium (Kamachi Mudali et al., unpublished, 2005). After the DOCTOR coating, the surface developed a smooth
appearance (Fig. 17(a) and (b)), and also exhibits higher polarization resistance confirming superior corrosion
resistance. Atomic force microscopic investigation of the DOCTOR coated surface revealed the presence of smoothly
distributed fine oxide particles of titanium (between 200 and 500 nm) over the surface (Fig. 18). Titanium forms
various types of oxide films on the surface depending on the conditions of preparation. The formation of films in a
fluorinated condition in nitric acid leads to dissolution controlled film formation mechanism (Zwilling et al., 1999).
Table 5
Corrosion rates in boiling 11.5 N nitric acid for titanium with various surface treatments
S. No Test condition Electrolysis parameters Average corrosion rate in huey test

(mpy)
Potential (V) Duration (h)
1 Conc. nitric Acid 10 0.5 19
2 10% sulfuric acid 12 100 18
3 10% ammonium persulfate 5 50 18
4 10% ammonium persulfate 12 50 16
5 10% ammonium sulfate 12 100 24
6 (i) nitric acid C1 ml HF C30 mg Ru C30 mg Cr6C, followed 5 24 8, 6
by
(ii) 10% ammonium persulfate 12 20
7 (i) nitric acid C1 ml HFC30 mg Ru C30 mg Cr6C, followed 5 24 4
by
(ii) 10% ammonium persulfate 12 50
The passivation layer developed on the surface establishes equilibrium with the highly corrosive environment in the
dissolver and ensures corrosion resistance for long life. This is similar to the passivation technology of stainless steels
or hot conditioning of carbon steels in water systems.
3.4. Development of dissimilar joints between titanium and AISI Type 304L SS
The fabrication and qualification of DMW joint between titanium and AISI type 304L SS is crucial in the reprocessing
plant especially because of zero failure requirements (Ananda Rao et al., 1999; Kamachi Mudali et al., 2003). Fusion
Fig. 17. (a) and (b) SEM micrographs of surface of titanium with DOCTOR coating.
Fig. 18. AFM image of the DOCTOR coated titanium showing the presence of fine oxide particles (between 200 and 500 nm) over the surface.
welding processes produce secondary precipitates which dissolve in nitric acid and hence, solid-state processes are
proposed for joining titanium and AISI type 304L. In Japanese reprocessing plants, both explosive bonded and
diffusion bonded sections are used (Irie, 1996). A satisfactory diffusion joint between zirconium and stainless steel at
a strength level of Zr could be achieved using annealed tantalum foils inserted into the joint interfaces. This avoids the
formation of the brittle and soluble intermetallic compound layer and favours the full contact of interfaces during
joining. A direct bonding between titanium and type 304L could be achieved by vacuum diffusion bonding with the
pre-cleaning of the surfaces using the ion sputtering.
High corrosion resistance in severely corrosive nitric acid with adequate mechanical strength and bent ductility are
the minimum requirements for this purpose. Solid-state welding processes, viz. explosive bonding, diffusion bonding
and friction welding were considered for fabricating this DMW joint to achieve adequate mechanical properties and
corrosion resistance. The friction-welded and explosive-bonded pipe joints were subjected to detailed investigations
including non-destructive examinations such as liquid penetrant, radiography and ultrasonic testing. The joints passed
all the NDT tests as per the acceptance standards.
Three-phase corrosion tests were conducted in 11.5 N boiling nitric acid for specimens obtained from both friction-
welded and explosive-bonded pipe joints. The test involved exposure of the specimens to the liquid, vapour and
condensate phases of the boiling nitric acid medium for five periods of 48 h each followed by measurement of the
corrosion rates in each of the three phases. It was observed that for both the joints, the corrosion rate in the condensate
phase is markedly higher than in the other two phases. Detailed optical and scanning electron microscopy examinations
of the specimens exposed to the condensate phase indicated severe corrosion attack of the friction-welded joints with
wide opening at the interface (Fig. 19(a) and (b)). In the case of the explosively welded joint, the interface was free from
corrosion, but corrosion attack at the vortex region of the AISI type 304 L SS was noticed. In general, the average
corrosion rate of the friction-welded joint in vapour and condensate phases was marginally lower than the explosively
welded joint. The corrosion rate of the friction-welded joint could be attributed to the selective loss of material at the
trench formed at the joint interface, an unacceptable situation for structural integrity considerations. Thus, explosively
welded joints showed better performance as compared to friction-welded joints with respect to corrosion point of view
(Kamachi Mudali et al., 2003). Micro hardness measurements were carried out across Ti/AISI Type 304L SS interface
of both the joints at an interval of 500 mm using a load of 200 g. It was observed that the hardness of AISI Type 304L SS
near the interface increased by only about 50 VPN for the friction-welded joint as compared to that of about 250 VPN for
the explosive-bonded joint. The high hardness of the AISI type 304L near the interface in the explosive-bonded joint
was attributed to the high degree of deformation/cold working of the SS surface during the explosive cladding
operation. On comparison of the results of the mechanical tests, it can be seen that the explosive-bonded joint has
significantly better bend and tensile ductility than the friction-welded joint. (Table 6). A comprehensive analysis
established superiority of the explosive welding process for the application. However, as the explosively welded joint
did not have enough ductility (only 801008 bend was obtained as against the desirability of 1808 bend), it was decided
to have an additional outer TiTiAISI 304L sleeve over the dissimilar joint in order to protect it from failure due
Fig. 19. Severe corrosion attack of the friction-welded joint (a) with wide opening at the interface compared to (b) smooth interface of explosive
joint (Kamachi Mudali et al., 2003).
to fracture. The final configuration of Ti-304L SS joint is shown in Fig. 20. In addition to catering to the needs of strength
requirements, the use of TiTiAISI type 304L SS sleeve provides extra corrosion allowances to the joint area. Since,
the TiTi welding is close to the bonded area, additional precautions were taken during the final preparation of such
dissimilar joints with sleeves. These additional precautions are: (1) providing a copper sink over the clad area for
absorbing the heat and thus, avoiding the opening up of the bonded area, (2) following the sequence of machining,
welding and boring to absorb the heat (Fig. 20), and (3) carrying out segment by segment welding, and after each pass
Table 6
Results of non-destructive, mechanical and corrosion tests
Tests Friction welded joint Explosive bonded joint

Non destructive tests
Liquid penetrant test Passed Passed
Radiography Passed Passed
Ultrasonic test Passed Passed
Mechanical tests Test 1 Test 2 Test 1 Test 2
Tensile tests
Ultimate tensile strength (MPa) 462 495 397 457
% Elongation Negligible Negligible 21.4 19.7
Bend tests
Root bend (bend angle at failure) !58 !58 608 768
Root bend (bend angle at failure) !58 !58 808 1068
Three-phase corrosion tests
Liquid phase (avg. corrosion rate) (mpy) 0.48 0.44
Vapour phase (avg. corrosion rate) (mpy) 0.72 1.5
Condensate phase (avg. corrosion rate) (mpy) 10.07 12.03
Fig. 20. Design sequence of the dissimilar joining of titanium and type 304L SS (Kamachi Mudali et al., 2003).
and completion of each segment of the welding, the temperature was brought down to room temperature as quickly as
possible by forced air circulation cooling. The final DMW joints, made on-site, were inspected for fit up, visual, liquid
penetrant and radiography examinations for the specifications.
A methodology was evolved for the erection of titanium dissolver equipment in containment box of the cell made
of AISI type 304L SS as titanium cannot be welded directly to AISI type 304L SS. The welding of titanium equipment
to stainless steel by appropriate design was a preferred one instead of mechanical fastening. A 6 mm Ti Grade 1 plate
was clad with 12 mm 304L SS plate, and then it was machined and welded to the top flanges of the dissolver. It was
essential that while welding the clad-ring to the dissolver flange at the bottom, it must be welded segment by segment.
In addition, cooling the welded segment to room temperature was practised, in order to avoid over heating of the clad
portion which other wise may lead to opening up of the bonded area.
3.5. Electrode development for electrochemical processes employed in reprocessing plants
Electrochemical processes are finding increasing applications in the reprocessing of spent nuclear fuels due to their
simplicity, high efficiency and easy control over the process including remote operation. Currently, electrolytic
dissolution and conditioning, electrolytic partitioning and purification, electrolytic production of uranous ions and
electrolytic destruction of nitric acid, organics, and radioactive wastes, all involving nitric acid as the process medium,
are either in use in reprocessing plants or in the way of process development at research laboratories (Baumgartner and
Schnieder, 1978). The success and current efficiency of the electrochemical processes mainly depends on the durability
or the corrosion resistance, electrocatalytic activity, and high conductivity of the electrodes. Longer life of the
electrodes is of paramount importance in order to avoid interruptions in the operations, and to eliminate the risk in
frequent replacement or addition of new electrodes in a radioactive environment. Currently, platinum is used as
electrode in the above applications. However, platinum undergoes corrosion during high current densities of operation
in nitric acid medium at high temperature (Baumgartner and Schnieder, 1978). Moreover, platinum is expensive
considering the overall cost involved in operating the plant with many unit operations, and the failed platinum
electrodes in a highly contaminated state cannot be refabricated for further use. These manifestations of platinum, in the
service environment, have necessitated development of high efficiency economical oxide coated electrodes with
corrosion resistant substrates. Attempts were made to use commercially available Titanium Substrate Insoluble Anodes
(TSIA) in 1984. These electrodes were similar to the dimensionally stable anodes (DSA) which are used in
electrochemical process industries such as the chlor-alkali industry. However, the electrodes could not perform beyond
338 K in 12 M nitric acid medium, and they failed showing insignificant current (Kamachi Mudali et.al., 1992).
For the reprocessing of the mixed (U, Pu) C fuel of FBTR, electrochemical methods have been developed
(Palamalai, 1988). Platinised tantalum and titanium electrodes were used for many electrochemical applications in the
reprocessing plants of other countries. Mixed oxide coated titanium anodes (MOCTA) were developed (Kamachi
Mudali et al., 1992) for application as electrodes in the electrochemical processes employed for the dissolution and
the purification of the spent (U, Pu)C fuel of FBTR, in India. MOCTA belongs to the category of DSA which are
basically a mixture of oxides of Ru, Ti, Pt, Rh, Ir and Pd coated over the surface of Ti, Ta, W, Cr, or Zr. The MOCTA
electrodes developed for current applications were Ti substrate coated with RuO2CTiO2, with or without an overlay
of PtO2. These electrodes were prepared by thermal decomposition method by which the salt solutions of Ru and Ti
were applied over a pretreated Ti surface and thermally oxidised at 773 K to get an adherent, conductive and
electrocatalytic coating. The MOCTA samples showed typical cracked-mud morphology while the application of
PtO2 layer resulted in the formation of smooth and fine-grained surface (Fig. 21). The presently used compositions of
MOCTA coating worked satisfactorily upto 215 h at an operating current density of 6.5 mA/cm2 in a simulated
uranium containing dissolver solution, beyond this, the cell current decreased to negligible values indicating the
electrode failure (Fig. 22). The platinised MOCTA developed subsequently worked satisfactorily upto 230 h at an
operating current density of 9 mA/cm2.
To increase the current density of operation and service life of the electrodes, a new approach (Kamachi Mudali
et al., 1999a,b) namely Thermochemical Glazing Process was evolved. This process consists of noble metal coating
over an intermittent MOCTA layer on Ti substrate. Metallic coatings of Pt and PtIr were prepared by
thermochemical glazing process on titanium substrates. Titanium substrates were applied first with a single layer of
RuO2TiO2. Followed by this, it was applied with Pt and PtIr chemical solutions. The electrodes were heat treated in
vacuum at different temperatures between 973 to 1473 K for developing the metallic Pt and PtCIr layers.
Electrochemical cathodic and anodic polarisation studies were carried out on these samples in 1 N HNO3 at room
temperature. Physical characterisation of these electrodes using SEM/EDAX indicated a smooth and compact coating
as compared to cracked-mud morphology of MOCTA (Fig. 21). XRD analysis indicated the presence of PtTi, PtIr
and other intermetallic compounds of Ti, Pt and Ir. SIMS analysis indicated the presence of Pt, Ru and Ir on the
surface. It was found that the specimens prepared at 1373 K showed better electrochemical performance in
comparison with Pt sheet electrodes. Significant changes in the open circuit potential (OCP) and the polarisation
behaviour of the electrodes were noticed. Life assessment of MOCTAG (MOCTA-glazed) electrodes in a simulated
reprocessing boiling nitric acid (10 N) test solution containing uranium and other redox ions showed good
performance of the PtIr layered electrode, prepared at 1373 K, in comparison with MOCTA electrodes. The
electrode prepared, by this process, continued to work up to 1840 h at an operating current density of 12.8 mA/cm2
(Fig. 22).
The limited life of MOCTA electrodes prepared by thermal decomposition method was due to the failure of the
coating with cracked-mud morphology and having cracks, pores and other defects. Hence, an attempt was made to
develop a compact, dense and crack-free mixed oxide coating of RuO2TiO2 on titanium using a plasma process to
enhance the life and stability of the electrodes for electrochemical applications (Kamachi Mudali et al., 1999a,b). The
preparation of the plasma-modified MOCTA (PMMOCTA) electrode involved (i) surface treatment of the titanium
substrate, (ii) preparation of RutileTiO2 thin film, (iii) application of coating solution, and (iv) final thermal
decomposition and consolidation by a plasma process. After the surface treatment as explained for MOCTA
preparation, the titanium substrate was pretreated in a DC reactive oxygen plasma to provide a RutileTiO2 coating of
thickness 20100 nm. In the next step, a solution containing salts of Ti and Ru are applied on the TiO2 formed
titanium. This coating was dried in the temperature range of 500600 K for 10 min. in a furnace of air atmosphere.
Multiple layers of solution were applied during this step to build up the thickness of the coating. Finally, the electrode
was subjected to a plasma consolidation step, in the temperature range 673973 K for 0.52 h duration to obtain a
coating of RuO2TiO2. The plasma assisted process (Kamachi Mudali et al., 1999a,b), involved the application of a
DC electrical potential to the electrode specimen which was kept as cathode in a reaction chamber maintained at
110 Torr oxygen pressure and in the temperature range from 573 to 973 K. The method is common for both the
formation of thin RutileTiO2 film on titanium and for the consolidation of the final coating.
The PMMOCTA specimen prepared as per the above methodology was examined for its coating morphology,
integrity and corrosion resistance. XRD study showed the formation of RutileTiO2 phase, which is crystalline,
Fig. 21. Surface appearance of various electrode coatings developed on titanium for electrochemical processes employed in reprocessing plants
(Baldev Raj et al., 2000).
Fig. 22. Life evaluation of various electrode coatings in boiling simulated reprocessing solution.
and the d-spacing matched well with the reported values. Compact and smooth oxide coating was noticed on the
surface while examining by SEM (Fig. 21). Impedance measurements in 1 N HNO3 for 24 h indicated a decrease in
the capacitance, and an increase in the impedance and/or polarisation resistance of the coating as the immersion
period in nitric acid was increased up to 72 h. The above measurements indicated that the coating was pore-free and of
high density. The coating life evaluation during the electrolysis of 10 M HNO3 solution containing 0.05 M AgNO3 at
371 K indicated a seven-fold increase in the life of the PMMOCTA electrode (Fig. 22). The conventional MOCTA
electrode worked up to 215 h, while the present PMMOCTA electrode worked up to 1460 h, at 6.5 mA/cm2 under
similar testing conditions. The presence of a thin film of RutileTiO2 structure at the interface enhanced the adherence
between the coating and Ti substrate. In addition, it effectively reduced the penetration of the electrolyte to the
substrate, and thus enhanced the useful life of the PMMOCTA.
4. Nitric acid loop for long term corrosion evaluation under simulated plant conditions
Materials selection for critical components in the nuclear programme has been given due considerations. The
selection of materials for pressurized heavy water reactors has been based on the results of materials tested under
simulated temperatures and pressures in autoclaves and loops. Similarly, for the evaluation of materials for fast
breeder reactors, sodium loops are established to study the materials behaviour under simulated operating conditions
of temperature and other parameters like, flow, impurities such as carbon content in sodium. The corrosion evaluation
of conventional AISI type 304L SS material for the reprocessing plants is presently evaluated as per ASTM A262
practice C (HUEY test) (American Society for Testing and Materials, A262-91, 1991). The test is also recommended
by the United States Nuclear Regulatory Commission (USNRC) for evaluating the materials intended for nitric acid
service in reprocessing plants (USNRC Regulatory Guide 3.37, 1975). It is an accelerated test involving boiling nitric
acid of 65% Nitric acid and the experiments are conducted by immersing the test coupon for five times of 48 h periods
in the solution. A small volume of the acid is used in a 1-L flask (350 ml) and every 48 h fresh solution is used. The
major drawbacks of this test procedure are that the specimens are tested in highly concentrated medium in static
condition, the total test period is shorter, and it is specific to evaluate intergranular corrosion only. The testing
procedure assesses resistance to intergranular corrosion, and does not simulate the plant conditions. It is well known
that AISI type 304L SS used in nitric acid medium undergoes several types of corrosion other than intergranular
corrosion, namely, end-grain attack, tunneling corrosion, transpassive dissolution, vapour phase attack etc. (Decours
et al., 1987; Steele, 1986). So, it is evident that comprehensive corrosion assessment of AISI type 304L SS by ASTM
A262 practice C test is impossible, taking into consideration the ranges of concentration of nitric acid used,
temperature of operation, impurities and redox chemicals present, and the metallurgical state of the materials used in
the reprocessing plants (Raju et al., 1997). The limitations of the current approach motivated us to design a dynamic
nitric acid loop made of AISI type 304L SS, with flowing nitric acid at different temperatures to evaluate the corrosion
performance of materials used in reprocessing plants (Fig. 23). A loop has been conceived and designed with a 350 L
capacity at IGCAR, Kalpakkam, for evaluating the corrosion performance over a long operating periods under plant
simulated conditions. Corrosion resistance of the materials in different metallurgical conditions, namely, cold
worked, solution annealed, sensitized, alloy composition etc. will be evaluated in this loop in flowing nitric acid at
different flow velocities (up to 1.55 m/s) and temperatures (313, 333, 353, 380 K and vapour phase). The data
generated over a long period of exposure (up to 10,000 h) would be used to arrive at an acceptable corrosion rate of
AISI type 304L SS used for applications in nitric acid service. The availability of such a reliable and useful data will
be helpful in predicting the remnant life of the components used in the reprocessing plants by developing suitable
analytical and modeling tools of the corrosion processes.
Currently, the loop is operating with AISI type 304L SS samples of solution annealed, sensitized (923 K/L h) and
welded conditions, used in demonstration fast reactor reprocessing plant. Results obtained after 100, 250, and 500 h
of operation indicated that the samples showed very insignificant corrosion rates (!1 mpy) at all temperatures of
testing as shown in Fig. 24. Nondestructive testing of the samples using eddy current and ultrasonic methods did not
reveal any significant defects on the surface of the samples investigated. Examination of the tested samples by
scanning electron microscopy (SEM) showed the grain boundary attack, and the samples tested in vapour phase
condition showed significant deposits on the surface (Fig. 25). Presently, the loop is operating with samples for 1000 h
campaign, and the testing will continue for more 1000 h operations in the future. The long-term operation of the loop,
and the resultant corrosion data of the materials, will provide valuable information on the life and performance of
Fig. 23. Flow sheet showing the various parts of the nitric acid loop.
Fig. 24. Corrosion rates of FRFRP solution annealed, sensitised and welded sample after 100, 250 and 500 h study in nitric acid loop.
Fig. 25. SEM micrograph of FRFRP solution annealed sample after, (a) 250 h, and (b) 500 h, exposure in boiling 6 N nitric acid.
the actual components in the operating plants, and in qualifying materials under realistic conditions for reprocessing
plant applications.
5. Choice of zirconium in reprocessing plants
Zirconium is highly resistant to corrosion attack in nitric acid environments (DECHEMA, 2001). With a proper
design, components made of zirconium can withstand highly concentrated nitric acid. The corrosion rate of Zr in 98%
HNO3 at boiling point and in 70% HNO3 at temperatures around 523 K is found to be less than 5 mpy (0.125 mm/
year). Even with 80 and 90% acid at 393423 K, the corrosion rates are found to be less than 1 mpy (0.025 mm/year).
The presence of several oxidizing agents like Fe3C and corroding agents like chloride ions has no or little effect on the
corrosion rate of zirconium. The corrosion resistance of zirconium is due to strongly adherent protective oxide
formation on the surface, and it does not form non-adherent oxide with poor corrosion resistance under condensing
conditions as in the case of titanium (Yau, 1992). However, zirconium is more expensive than titanium even though
the production and manufacturing technology has matured well. The main limitations in using zirconium and its
alloys for nitric acid service include: (i) it exhibits passive-transpassive transition unlike titanium, (ii) it exhibits high
corrosion potential; as concentration increases corrosion potential and transpassive potential move closer causing
higher corrosion, (iii) need for Zr sponge addition for inhibiting corrosion of Zr vessels in fluoride containing
environments, and (iv) the possibility of undergoing stress corrosion cracking (SCC), particularly in the heat affected
zones (HAZ) of welds.
The primary concern for the use of Zr and its alloys in nitric acid service is SCC in concentrated acidic conditions,
particularly above 30% at boiling point, thus limiting applications for dissolvers and evaporators (Kiuchi et al.,
1991a,b). Detailed investigations reveal that (i) SCC of Zr in HNO3 strongly depends on the crystallographic texture;
crack propagates along the close packed (0001) planes of hcp leading to transgranular SCC and the SCC susceptibility
is influenced by the presence of cleavage planes along the cracking path, and (ii) weldments show high susceptibility
to SCC, and the rate of SCC crack propagation is higher in HAZ away from weld as compared to HAZ near the weld.
However, sustained R&D efforts at French reprocessing plants enhanced the scope of using zirconium for making
several process equipments including dissolvers.
The La Hague plant of France has gathered major experience in the application of Zr for reprocessing plants
(Decours et al., 1987; Bernard et al., 1991). The first application was concerned with the concentration of oxalic
mother liquor containing plutonium by a factor of 50100 through evaporation, and to destroy the oxalic ions in
concentrated HNO3 of 1014 N. The use of stainless steels is not acceptable due to very high corrosion rates in the
presence of redox ions like Pu4C and Cr6C. Even a highly alloyed NAG grade Uranus 65 SS can operate for only 1
year in this environment. A thermo-siphon type evaporator made of Zr was first commissioned in 1971 and this
operated until 1983 without any failure and presently this has been replaced with a larger capacity unit. The other
units made of Zr are: (i) evaporator to concentrate Pu (1976), (ii) concentrator to process Pu effluents (1979), both for
UP1 plant at Marcoule, (iii) oxalic acid mother liquor evaporator (1982) for UP2 plant, and (iv) two Pu solution
concentrators (since, 1978), (v) a special dissolution unit (1985) and several dissolvers, condensers etc. for Marcoule
Pilot facility. All the above components were smaller in size and thin Zr sheets were used. However, for the UP3 and
UP2 plants, larger capacity vessels could be used in the future. In 1990, high quality Zr dissolvers made of material
with controlled chemical composition and fabricated with established welding procedures were erected at La Hague
for the continuous dissolution process. In total, more than 100 ton of Zr equipment and 5000 m of Zr piping have been
employed at UP3 and UP2 plants.
6. International developments related to new materials for reprocessing applications
To ensure a reliable, safe and economic operation of reprocessing plants, the development of high corrosion
resistant materials with high reliability is necessary. Materials development for reprocessing application is making
significant progress in many countries. Three criterion are considered for this purpose (Fig. 3): (i) stabilizing the
passive film and reducing dissolution, (ii) enhancing the passive range by shifting the transpassive conditions to
nobler potentials, and (iii) improved alloys with better corrosion properties. Alloys containing ultra-low carbon and
controlled amounts of impurities that segregate to grain boundaries have been developed (Yanokura et al., 1994;
Kikuchi et al., 1991a,b, 1999). These alloys also possess resistance against corrosion under diverse heat transfer
conditions encountered in reprocessing plants. Transpassive dissolution occurs due to the thermal decomposition of
HNO3 at the heat-conducting surface and by the formation of chemically unstable HNO2 due to low temperature
boiling. Typical composition of an alloy for such an application is (wt%): 0.007 C, 0.44 Si, 1.37 Mn, 0.021 P, 0.004 S,
10.3 Ni, 18.7 Cr, 0.0002 B and 0.019 N (solution annealed at 1323 K for 1 h). To inhibit the grain boundary attack and
eliminate the transpassive dissolution optimization of type 304ULC SS has been proposed (Kikuchi et al., 1991a,b,
1999). This means, (i) control on major elements (increase Cr and Ni, control Si between 0.1 and 0.2%), (ii) limit the
minor alloying elements (P, S, B, N etc. vacuum induction melting followed by electron beam melting), and (iii)
modify the microstructure (SAR thermomechanical treatment-full solution anneal, cold worked to w60%, aged at
848 K for 15 h and recrystallise at 1048 K for 5 h). Fig. 26 shows the corrosion rates obtained through the control of
carbon and other impurity elements through advanced melting procedures. Comparison of corrosion rates of
commercial type 304ULC SS with advanced materials developed through modification of microstructure and major
Fig. 26. Corrosion rates obtained through the control of carbon and other impurity elements through advanced melting procedures
(IAEA-TECDOC-421, 1987).
alloying elements are shown in Fig. 27 (Kiuchi et al., 1998). The modified alloy possesses fine grains with adequate
mechanical properties. It is inferred by theoretical analyses that a minimum quantity of less than 1 ppm of
supersaturated solute in austenite matrix can lead to grain boundary segregation. Recently, a new alloy with 2 ppm of
phosphorus has been developed at National Institute of Materials Science, Japan in contrast to 260 ppm in
conventional stainless steels [http://www.nrim.go.jp:8080/public/english/act/1996/ch193.html]. This alloy results in
a 100 times increase in the corrosion resistance in boiling 65% HNO3.
By considering the anodic and cathodic inhibition mechanisms, a new high Cr, Ni-base alloy with W and Si
addition (RW alloy) has also been designed (Kiuchi et al., 1998). Cr stabilizes the film, and Si polarizes the cathodic
reactions, that is, the reduction of HNO3 and Cr (VI). Tungsten stabilizes the film near transpassive zone because of its
low solubility in HNO3 medium. The alloy composition has been designed for inhibiting the transpassive corrosion by
enriching oxide former elements such as Cr, W and Si with different electrode potential for forming a stable film on
the surface (Fig. 28). For obtaining sufficient workability and high temperature cracking resistance, the alloy is
electron beam melted for purification. Typical composition of this alloy is (wt%): C!0.005, Si-2.72, Mn!0.1, P !
0.01, S!0.002, Cr-29.2, W-10.1, B!0.001, N!0.005, Ni-balance). The corrosion rates obtained for this alloy are
very low in comparison with other special grade alloys (Figs. 27 and 28).
Unknown corrosion problems existing with chemically active hcp type metals and alloys are an important issue for
the development of new alloys with high corrosion resistance. In this regard, though Ti-5% Ta alloy does not show
any corrosion attack in condensate vapour phase regions in comparison with pure Ti, incidences of corrosion attack at
condensate liquid-vapour interface and mass transfer of volatile corrosion products have been reported for Ti5%Ta
components in service (Kiuchi et al., 1998). Even though zirconium was considered as a potential material for
reprocessing applications one of the major problems associated with its application is its tendency to undergo stress
corrosion cracking. Recently, it has been reported (Motooka and Kiuchi, 2002) that the fatigue crack growth rate of
zirconium was remarkably accelerated in nitric acid while that of Ti5%Ta alloy was insignificant. So caution must
be employed while choosing zirconium for making a component that can undergo SCC and corrosion fatigue problem
in nitric acid. The enhancement in corrosion resistance of Ti5%Ta alloy under irradiation in nitric acid environment
has also been reported (Yamamoto et al., 1996). Niobium and NbW alloy have also been considered as potential
materials for critical applications involving highly oxidizing nitric acid under heat transfer conditions as they form
stable M2O5 protective film on the surface (Kiuchi et al., 2002). A new generation alloy has been developed by adding
varying amounts of Ta and Nb to titanium, and an alloy with an optimum composition was obtained as: Ti5% Ta
1.8% Nb (Kikuchi et al., 1991a,b). The alloy exhibits significant reduction in corrosion rate while testing in boiling
nitric acid medium (Fig. 14). The addition of Nb is also helpful during melting and making of the alloys as it acts as a
getter for many impurity elements in titanium. However, investigations on this alloy after welding and other
fabrication treatments need to be performed before using this material for plant applications. Materials,
manufacturing and inspection methods have to be investigated in a holistic perspective to ensure high reliability
in reprocessing plants. A life management plan taking into account the life cycle cost of fissile material produced in
reprocessing plant needs to be evolved.
7. Summary
An attempt has been made to focus on the materials challenges in the reprocessing plants. Newer materials like nitric
acid grade stainless steels, titanium, Ti5%TaNb alloy, Zircaloy etc. are some of the materials attempted at IGCAR,
Fig. 27. Corrosion rates of modified NAG 304 L SS (Kiuchi et al., 1998).
Fig. 28. Comparison of corrosion rates of type 304ULC SS with advanced materials (Kiuchi et al., 1998).
and several other materials attempted else where in the world are highlighted. The importance of dissimilar joining, in
the case of joining of exotic materials and conventional stainless steels is discussed with our own experience at IGCAR.
Electrode development, and the achievements in developing high performance oxide coated and metallic coated
titanium are brought out. Various issues related to current materials, development of newer alloys, challenges
associated with materials manufacturing and joining are brought out with examples from Indian experience and from
else where in the world. Success in materials development means continuous operation of the reprocessing plants with
zero failure over long periods (25 years). In this regard, the present paper guides in appropriate selection of materials and
associated joining processes for manufacturing of components with highest integrity and reliability combined with
adequate corrosion resistance in nitric acid environments for applications in spent nuclear fuel reprocessing plants.
Acknowledgements
Acknowledgements are due to many scientists and engineers of IGCAR, Kalpakkam who are associated with the
work reported in this article.
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Progress in Nuclear Energy 48 (2006) 283313

Materials development and corrosion problems in nuclear fuel

* Corressponding author. Tel.: C91 44 27480260; fax: C91 44 27480060.

1.1. Austenitic stainless steels for nitric acid service

1.2. Evolution of nitric acid grade austenitic stainless steels

1.3. Challenges in the application of NAG stainless steels

2. International experience in materials reliability vis-a-vis corrosion issues

3. Promising metals and alloys for nitric acid service

3.1. Development efforts in the application of titanium and its alloys

Materials Temperature Corrosion rate (mpy)

Fig. 10. Schematic diagram showing the all-titanium electrolytic dissolver.

3.2. Ti5%Ta2%Nb alloy for electrolytic dissolver applications

3.3. Development of double oxide coating on titanium for reconditioning (DOCTOR)

S. No Test condition Electrolysis parameters Average corrosion rate in huey test

Tests Friction welded joint Explosive bonded joint

3.5. Electrode development for electrochemical processes employed in reprocessing plants

5. Choice of zirconium in reprocessing plants

6. International developments related to new materials for reprocessing applications

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