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Corrosion of Zircaloy-4 and its welds

in nitric acid medium
A. Ravi Shankar a, V.R. Raju a, M. Narayana Rao a,b,
U. Kamachi Mudali a,*, H.S. Khatak a, Baldev Raj a
a

Corrosion Science and Technology Division, Indira Gandhi Centre for Atomic Research,
Kalpakkam 603 102, India
b
Nuclear Fuel Complex, Hyderabad, India
Received 5 June 2006; accepted 27 March 2007

Abstract
Zirconium and its alloys are considered as candidate materials for various applications in spent
nuclear fuel reprocessing plants involving nitric acid of various concentrations at dierent temperatures. In the present work an attempt was made to study the corrosion behaviour of Zircaloy-4 (Zrwith Sn-1.5%, Fe-0.22%, Cr-0.1%) in wrought and welded forms in comparison with other candidate
materials like commercially pure Titanium (CP-Ti), Ti5%Ta and Ti5%Ta2%Nb. Manual TIG
welding and electron beam welding was carried out with Zircaloy-4 pipes of 5 mm thick and
120 mm diameter, and radiography was made for choosing defect-free regions for making samples
for corrosion investigations. Three phase corrosion testing in liquid, vapour and condensate regions
was conducted in boiling 11.5 M nitric acid medium using a specially designed experimental set up.
The results indicated that Zircaloy-4 exhibit superior corrosion resistance in both wrought and
welded conditions in comparison with other materials. The electron beam welded samples did not
show any deterioration and performed similar to wrought alloy. The detailed results of microstructure, microhardness, corrosion rate, morphology of attack and nature of surface lm formed are presented in this paper. The results of the present investigation indicated that Zircaloy-4 could be a
candidate material for nitric acid medium of high concentration and temperature in reprocessing
plants and other industries.
 2007 Elsevier Ltd. All rights reserved.
Keywords: A. Zirconium; B. Weight loss; SEM; XPS; C. Welding; Acid corrosion

Corresponding author. Tel.: +91 44 27480121; fax: +91 44 27480301.

E-mail address: kamachi@igcar.gov.in (U. Kamachi Mudali).

0010-938X/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2007.03.029

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1. Introduction
Reprocessing of spent nuclear fuel used in fast breeder reactors (FBRs) involves use of
nitric acid of high concentrations and temperatures for dissolvers and evaporators which
are highly corrosive. The materials chosen for the fabrication of such reprocessing plant
equipment should possess excellent corrosion resistance, ease of fabricability and reliability [1,2]. Conventional austenitic stainless steels are not preferable in such highly oxidizing
conditions as they undergo severe intergranular corrosion [3]. Extensive studies have been
carried out world wide for selecting suitable materials for fabrication of equipments for
highly oxidizing nitric acid applications in spent nuclear fuel reprocessing plants [1,4,5].
Studies carried out earlier on American Iron and Steel Institute (AISI) type 304L SS, nitric
acid grade SS, CP-Ti, Ti5%Ta indicated good corrosion resistance of CP-Ti and Ti
5%Ta compared to AISI type 304L SS in highly oxidizing nitric acid [3,6]. Titanium
was chosen for fabricating electrolytic dissolver with a dissimilar joint by explosive joining
process for linking to type 304L SS equipments in the reprocessing of spent fuel from Fast
Breeder Test reactor (FBTR) at Kalpakkam [7]. For future reprocessing plants, based on
research and international experiences, developmental eorts have been made for the fabrication of dissolvers by using Ti5%Ta1.8%Nb alloy [1,810].
The excellent corrosion resistance of Zirconium in nitric acid has been known for
over 50 years [11]. Zirconium is highly resistant to nitric acid environments [11,12] and
is considered as candidate material for various applications in spent nuclear fuel reprocessing plants involving highly concentrated nitric acid medium. In France, 80 tons of
zirconium and 5500 m of piping were employed in La Hague reprocessing plant for the
manufacturing of various components like dissolvers, oxalic mother liquor evaporator
and heat exchangers, vitrication dust scrubber, and liquid waste treatment reactors
[5,13].
The corrosion resistance of unalloyed titanium improves dramatically as the impurity
levels in hot nitric acid solutions increases. Titanium exhibits excellent resistance to recirculating nitric acid process streams [12]. However, in hot and pure nitric acid solutions and
vapour condensates of nitric acid, signicant corrosion was observed for titanium [12,13].
Unlike titanium [13,14], Zirconium is unaected by vapour condensates in boiling nitric
acid [13]. Zirconium is much more corrosion resistant to nitric acid than titanium, but
the only concern with the use of Zirconium is its susceptibility to corrosion fatigue and
stress corrosion cracking (SCC) in highly concentrated nitric acid [1,15,16]. Particularly,
the heat aected zone of Zirconium weldments was considered to be more sensitive to
SCC. However, Chauve et al. [13] concluded that the tests carried out in nitric acid up
to 65 wt% proved that the risk of stress corrosion cracking was extremely low and does
not have to be taken into account for industrial application.
Zirconium and its alloys are extensively used as fuel cladding and for coolant channels
in water cooled power reactors due to the unique combination of properties like low neutron absorption, good ductility, strength and corrosion resistance in high temperature
water. Controlled additions of Fe, Cr and Sn to Zircaloy-2 lead to a new alloy Zircaloy-4, which has good corrosion resistance in water/steam, and low hydrogen absorption
rates [17]. Zircaloy-4 has been proposed in the present work as a candidate material for the
fabrication of dissolver and evaporator in future fast breeder reactor reprocessing plants.
The present paper deals with corrosion behaviour of Zircaloy-4 in wrought and welded
forms (Manual TIG welding and Electron Beam welding) in boiling 11.5 M nitric acid
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solution. The results are compared with other candidate materials like CP-Ti, Ti5%Ta
and Ti5%Ta1.8%Nb.
2. Materials and experimental methods
2.1. Specimen preparation and characterisation
Ti5%Ta1.8%Nb alloy of 25 mm diameter rod and Zircaloy-4 (Zr-4) plate was
received from the Nuclear Fuel Complex (NFC), Hyderabad. Ti5%Ta1.8%Nb alloy
rod was rolled into plate and stress relieved at 923 K for 1 h. The nominal composition
of the materials used in the present study is given in Table 1. Manual TIG welding
(TIG) and Electron Beam welding (EB) was carried out at NFC, Hyderabad on Zircaloy-4 pipes of 5 mm thick and 120 mm diameter. The welding parameters for the TIG weld
and EB Weld pipes are given in Table 2. The Manual TIG welded and EB welded Zircaloy-4 pipes were subjected to radiography as per ASME Section 3 acceptance criterion for
reprocessing plant equipment. The samples for corrosion testing were chosen from the
defect-free regions of the welded pipe.
2.2. Three phase corrosion testing
The corrosion of titanium has been reported to be inuenced by its own corrosion product (Ti4+), the titanium surface area to acid volume ratio, and test duration. The rate of
solution replenishment was also critical to the corrosion rate of titanium [12]. In view
of this a new type of three phase corrosion testing apparatus was designed and used by
Furuya et al. [18] for testing corrosion of titanium under liquid, vapour and condensate
conditions to estimate the corrosion rate. A similar designed three phase corrosion testing
apparatus was employed in the present study to estimate the corrosion rate of materials.
Fig. 1. shows the schematic of the three phase corrosion testing apparatus used.
The samples for three phase corrosion test were polished up to 600 grit emery paper.
The samples were suspended in the liquid, vapour and condensate phases using Teon
(PTFE) thread and exposed for a total period of 240 h. After every 48 h, the samples were
removed and the changes in the weights were recorded, and fresh test solution was used for
each period. After completion of the test, the average corrosion rate for ve individual
periods was calculated. The ratio of volume of solution to the total specimen surface area
in liquid, vapour and condensate phases together was about 35 ml/cm2. The equilibrium
concentration of nitric acid in condensate phase was 6 M [18]. In this corrosion testing
apparatus, the corrosion rate of sample in the condensate phase is not inuenced by dissolved ions, as the solution condensed in the inner vessel automatically drained o the
Table 1
Nominal chemical composition in wt%
Material

Zr

Ti

Ta

Nb

Sn

Fe

Cr

Zr-4
CP-Ti
Ti5Ta
Ti5Ta1.8Nb

Balance

Balance
Balance
Balance

5.00
4.39

1.84

1.4

0.2
0.041
0.028
0.03

0.1

0.12
0.096
0.091
0.050

0.003
0.005
0.004

0.015

0.012

0.0025
0.0028
0. 0009

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Table 2
Welding parameters for the TIG weld and EB weld pipes
Welding Parameter

TIG Welding

EB Welding

Speed
Current
Voltage
Gas ow
Vacuum

300 mm per min

60 A

Torch 8 IGPM (50% Argon and 50% Helium)

1000 mm per min

24 mA
45 kV

5 104 torr

Fig. 1. Three phase corrosion testing apparatus.

ask through siphon pipe and fresh solution was renewed at regular intervals. In the liquid
phase, corrosion rate was inuenced as the concentration of ions in the solution increased.
SEM examination was carried out using ESEM Philips XL-30 on tested samples to
observe the morphology of corrosion attack.
2.3. Surface analysis using XPS and SIMS
In order to study the nature of surface lms formed X-ray photoelectron spectroscopy
(XPS) and Secondary ion mass spectroscopy (SIMS) have been carried out on Zircaloy-4
sample exposed to liquid phase of nitric acid. The condensate exposed sample of Zircaloy4 was also further studied by using XPS. X-ray photoelectron survey and high resolution
spectra for selected elements were obtained using VG ESCALAB MX II spectrometer
using Al Ka radiation (1486.6 eV), pass energy of 20 eV, base pressure = 2.1 109 mbar
and binding energy reference to C1s is 285.1 eV. SIMS analysis was carried out with
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CAMECA ims 4f using 4 KeV Ce ions as primary ions of energy +1.75 KeV (120 nA).
Specimen was scanned over 200 200 microns, from which ions were collected from
60 lm diameter.
3. Results and discussion
3.1. Microstructure and microhardness
Zirconium and its alloys in nitric acid display excellent corrosion resistance and are
insensitive to intergranular corrosion unlike stainless steels. Zirconium is usually welded
in a glove box by the TIG weld process, or under vaccum by Electron beam process
[13]. Zirconium welds often display brilliant tints ranging from pale yellow to intense blue
[19]. The EB welding of Zircaloy-4 pipe displayed an intense blue coloured weld region.
These stains are caused due to interference tints caused by thin oxide layers. Literature
suggested that such stains on Zr-welds did not eect the mechanical and corrosion properties and they can be eliminated by using very pure inert gas and avoiding turbulence [19].
The weld region of the TIG welded Zircaloy-4 exhibited a hardness value of 387 VHN,
while the hardness in the base metal was only 183 VHN. The weld region of the EB welded
Zircaloy-4 showed a hardness value of 197 VHN in the weld region. The increase in the
hardness in the TIG weld region might be due to increase in oxygen or nitrogen content
in the weld region. It has been reported [13] that hardness is raised 10 points by a
140 ppm increase in nitrogen content (for an initial content ranging between 20 and
1000 ppm) or by a 200 ppm increase in oxygen content (for an initial content ranging
between 500 and 4000 ppm).
The radiographic examination of Zircaloy-4 pipes, as per ASME Section 3 revealed that
the Manual TIG welded pipe did not meet the acceptance criterion while EB welded pipe
was acceptable. The radiography results of manual TIG welded pipe revealed the presence
of various weld defects like lack of penetration, excess penetration, mismatch and tungsten
inclusions etc. However, the regions free from such defects have been chosen for making
samples for corrosion testing.
The microstructure from the weld region of TIG and EB welded Zircaloy-4 samples are
shown in Fig. 2. The welds exhibited a transformed grain structure or acicular a grains

Fig. 2. Microstructure from the weld region of TIG weld and EB weld Zircaloy-4 sample.

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surrounded by prior b grain boundaries (Widmanstatten or basketweave structure). The

weld region of TIG welded Zircaloy-4 sample exhibited coarse acicular a structure in comparison to ne acicular structure of EB welded sample. This would be attributed to the
slower cooling and solidication of TIG welds in comparison with EB welds.
3.2. Corrosion rate and morphology of attack
The average corrosion rate for ve individual periods in liquid, vapour and condensate
phases of boiling 11.5 M nitric acid for CP-Ti, Ti5%Ta, Ti5%Ta1.8%Nb, Zircaloy-4,
Zircaloy-4 TIG weld and EB weld samples are shown in Fig. 3. As the corrosion rates
are in close ranges the values are also provided in Table 3. The corrosion rates clearly indicated superior corrosion resistance of Zircaloy-4 in both wrought and welded conditions
in comparison to CP-Ti, Ti5%Ta, and, Ti5%Ta1.8%Nb. The high corrosion resistance
of Zirconium and its alloys in highly oxidizing nitric acid conditions is due to stable and
adherent ZrO2 lm formed on their surface [1].
The corrosion rates for CP-Ti, Ti5%Ta, and, Ti5%Ta1.8%Nb in condensate phase
was higher than those in vapour and liquid phase conditions. In general, titanium exhibits
good corrosion resistance in boiling concentrated nitric acid medium due to the formation
of strong and stable TiO2 lm developed on their surface. Titanium dissolved as Ti4+ ions
and the excessive Ti4+ ions formed in the liquid facilitated the formation of such protective
TiO2 layer on the surface. However, in condensate/vapour phase the formation and accumulation of Ti4+ ions is prohibited due to replenishment of the fresh condensed acid
formed at frequent intervals. Thus the corrosion rates for Ti and its alloys are higher in
condensate/vapour phase of nitric acid. White and non-adherent oxide layer is formed
above the liquid level in the condensation zone of titanium vessels due to the constant
trickling of acid condensate which prevents the formation of stable and strong oxide lm.
This is due to lack of Ti4+ ion build up in the condensate phase, as reported in the literature [18,20].
Liquid
Vapour
Condensate

Corrosion Rate, mm/y

0.1

0.01

1E-3

CP-Ti

Ti-5Ta Ti-5Ta-1.8Nb Zr-4

Zr-4TIG

Zr-4 EB

Material / Condition
Fig. 3. The average corrosion rate in liquid, vapour and condensate phases of boiling 11.5 M boiling nitric acid
for 240 h.

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Table 3
The average corrosion rate values in liquid, vapour and condensate phases of boiling 11.5 M nitric acid for 240 h
(Corrosion rate in mm/y)
Material/Condition

Liquid

Vapour

Condensate

CP-Ti plate
Ti5Ta plate
Ti5Ta1.8Nb plate
Zr-4 Plate
Zr-4 TIG weld
Zr-4 EB weld

0.1592
0
0.0033
0
0.0005
0

0.0132
0.0142
0.0063
0.0007
0.0012
0.0015

0.2799
0.0637
0.0119
0.0017
0.0010
0.0010

The corrosion rate of Zircaloy-4 in wrought and weld forms are nearly same in all three
phases (<0.0017 mm/y). Unlike Ti and its alloys, the corrosion rate of Zircaloy-4 and its
weldments were similar in all three phases and are not aected by the condensate phase.
This is because unlike Ti, the corrosion resistance of Zircaloy-4 is not inuenced by its
own ion, i.e, Zircaloy-4 is unaected by trickling condensates above boiling nitric acid.
The corrosion resistance of Zirconium is due to the formation of strong and adherent protective ZrO2 oxide formation on the surface, in both liquid phase and condensate/vapour
conditions [1]. It is also not sensitive to changes in concentration of nitric acid, concentration of its own ion in solution, small amounts of heavy metal ions, and the crystal structure of Zirconium [11]. In the present work a thin and black protective oxide was noticed
on the surface of Zircaloy-4 and its welds after the corrosion testing. The corrosion rates
of weldments of Zircaloy-4 samples are nearly same, indicating that the corrosion of
Zircaloy-4 is not sensitive to microstructure as reported in literature [13].
The SEM micrographs of CP-Ti, Ti5Ta, and Ti5Ta1.8Nb exposed to liquid, vapour
and condensate phases are shown in Fig. 4. The surfaces of CP-Ti, Ti5Ta and Ti5Ta
1.8Nb showed signicant corrosion attack in condensate phase. The SEM micrographs of
Zircaloy-4, Zircaloy-4 TIG weld and Zircaloy-4 EB weld samples exposed to liquid,
vapour and condensate phases are shown in Fig. 5. The smooth and compact lm present
over the surface resulted in superior corrosion resistance of Zircaloy-4 and their weldments
in all three phases in comparison to CP-Ti, Ti5Ta, and Ti5Ta1.8Nb.
3.3. Nature of the surface layers
XPS survey spectra of Zircaloy-4 sample exposed to the liquid phase and condensate
phase is shown in Fig. 6. The XPS spectra indicated major Si and O peak for the sample
exposed to liquid phase while for the sample exposed to the condensate phase major peaks
for O, Zr and N are seen. The contamination of the surface lm by silicon is due to leaching of silicon from glass vessel [12]. In order to avoid the inuence of silicon and determine
the true corrosion rate of titanium, zirconium and their alloys in highly concentrated nitric
acid at high temperatures, all titanium and all zirconium test facilities has to be made.
Eorts are being done in our laboratory in this direction. The high resolution spectra of
Zircaloy-4 sample exposed to the liquid phase and condensate phase shown in Fig. 7 indicated the presence of Zr in +4 valency state, while in liquid phase no such Zr peak was
x
found since the surface is totally covered with thick SiO2 layer. The binding energy of
Zr3d5/2 from high resolution spectra is 182.6 eV. The standard value for ZrO2 is
182.9 eV. From this we can conclude that zirconium is present as ZrO2 on the surface.
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Fig. 4. SEM micrographs of CP-Ti, Ti5Ta, and Ti5Ta1.8Nb exposed to liquid, vapour and condensate phases
of boiling 11.5 M nitric acid for 240 h.

Nitrogen on the other hand is present in elemental state (seen in both the samples) as
shown in Fig. 7.
SIMS depth prole of the sample exposed to liquid nitric acid for 240 h is shown in
Fig. 8. The prole also indicated contamination of silicon in the surface lm. There is
increase of silicon and oxygen and decrease of zirconium content in the lm. This suggests
that zirconium ions are replaced by silicon ions in the oxide lattice as the test duration is
increased. Silcon ion being smaller than zirconium ion distorts the oxide lattice and higher
the relative stability of the distorted lattice, higher the protective properties of the oxide
lm. The replacement of oxygen by nitrogen in the oxide lattice has a negative eect on
the corrosion resistance. The nitrogen in the oxide lm dilates the oxide lattice and matching between oxide and metal lattice decreases, thus reducing the corrosion resistance. The
nitrogen content in the lm is decreased from the base metal to the surface lm, thus
increasing the protective properties of the lm [21].
3.4. On the corrosion resistance of Zircaloy-4 and its welds
Zirconium is resistant to many powerful acids particularly sulphuric acid, hydrochloric
acid, phosphoric acid and nitric acid at various concentrations. While reacting with acids
Zirconium has a great tendency to decompose water with the evolution of hydrogen, and
dissolves as zirconic ions Zr4+, and as zirconyl ions ZrO2+ in very acid solutions [22].
Zr ! Zr4 4e
Zr

2H2 O ! ZrO2 4H

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Fig. 5. SEM micrographs of Zircaloy-4, Zircaloy-4 TIG weld, and Zircaloy-4 EB weld exposed to liquid, vapour
and condensate phases of boiling 11.5 M nitric acid for 240 h.

O1s
Zr3p
N1s

Zr3p
C1s

Condensed Nitric acid

Zr3d

KCPS

Si2s Si2p

O1s

C1s
Si2s

Si2p

Liquid Nitric Acid

1000

800

600

400

200

B.E (eV)
Fig. 6. XPS spectra of Zircaloy-4 sample surface exposed to liquid, and condensate phases of boiling 11.5 M
nitric acid for 240 h.

These zirconic ions form stable ZrO2 lm on the surface according to reaction (2). Even
a marginal positive shift in the equilibrium potential could lead to the formation of a
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Zr3d

N1s

5/2

KCPS

Zr3d 3/2

Condensed Nitricacid

N1s

Liquid Nitric acid

170 175 180 185 190 195 385

390

395

400

405

410

B.E (eV)
Fig. 7. XPS high resolution spectra of Zircaloy-4 sample surface exposed to liquid, and condensate phases of
boiling 11.5 M nitric acid for 240 h.

10000

Normalised KCPS

Zr

1000

N
Cr
Fe

100

O
Si
Ni

10
0.2

Sn
0.4

0.6

0.8

1.0

1.2

Fig. 8. SIMS depth prole of Zircaloy-4 sample surface exposed to liquid phase of boiling 11.5 M nitric acid for
240 h.

thick oxide lm on the surface of zirconium. It has been reported that in elec40200 A
thick oxide lm which
trolytes containing oxidizing agents zirconium forms nearly 1000 A
behaves like an inert surface with high ohmic resistance [21]. It is generally acknowledged
that the excellent corrosion resistance of zirconium to acids has been related to the crystal
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11

structure and stability of the ZrO2 lm formed. During anodic polarization of zirconium,
oxide lms of various varieties like monoclinic, amorphous and cubic are formed
depending on the operating conditions. Anodic polarisation in 0.1 N HNO3 has been
reported to produce passive lm of cubic ZrO2 [22]. The initial stage in the electrochemical oxidation during anodic polarization should be the adsorption of hydroxyl ions, as a
result of the positive shift in the potential. The lm formed, as the potential has been
continuously shifted in the positive direction, withstands further dissolution of zirconium
from the surface. The addition of alloying elements to zirconium, and their introduction into the zirconium oxide, can basically change the properties of the metal and oxide,
this leading to a change in the interaction between metal and oxide [21]. The replacement
of oxygen by nitrogen in the oxide lattice leads to dilation of the oxide lattice and thus has
a negative eect on the matching with the lattice of the metal. While the replacement of
zirconium ion in the oxide lattice by a tin ion leads to the contraction of the lattice and
nullies the negative eect of nitrogen in zirconium alloys [21]. The elements Fe, Ni and
Cr form insoluble intermetallic compounds that can act as microcathodic zones for
imparting anodic polarization to the matrix zirconium leading to the development of
stronger thin oxide layers of ZrO2 [21]. It has also been reported that the corrosion rates
of zirconium and its alloys were extremely low, less than 0.5 mdd for most metallurgical
conditions with dierent microstructural features [21]. In accordance with all the
above, the results of the present investigation conrmed the excellent corrosion resistance
of Zircaloy-4 and its electron beam and tungsten inert gas welds in 11.5 M nitric acid
medium.
4. Conclusions
1. Zircaloy-4 exhibited superior corrosion resistance in both wrought and welded condition in comparison to CP-Ti, Ti5%Ta, and Ti5%Ta1.8%Nb in 11.5 M HNO3.
2. The corrosion rates of CP-Ti, Ti5%Ta, and, Ti5%Ta1.8%Nb in condensate phase
are more than those in vapour and liquid phases, while for Zircaloy-4 in wrought
and weld forms such behaviour was not noticed.
3. SEM examination revealed insignicant corrosion attack of Zircaloy-4 and its welds in
all three phases in comparison to CP-Ti, Ti5Ta, and Ti5Ta1.8Nb after testing in
liquid, vapour and condensate phases. Accelerated corrosion attack was noticed for
Ti and its alloys after testing in condensate phase.
4. XPS and SIMS analysis of tested Zircaloy-4 samples indicated signicant Zr content in
the lm with contamination by Silicon in liquid and condensate phases. Nitrogen was
also noticed in the lm.
5. Zircaloy-4 could be a candidate material for handling nitric acid of high concentrations
and temperature in reprocessing plants, with the support of the results of the present
investigation.
Acknowledgements
The authors would like to acknowledge Smt. M. Radhika and Shri A.K. Balamurugan
of Indira Gandhi Centre for Atomic Research, Kalpakkam, and Dr. Santanu Bera of
BARC Facilities, Kalpakkam, for SEM, SIMS and XPS analyses, respectively.
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Please cite this article in press as: A. Ravi Shankar et al., Corrosion of Zircaloy-4 and its welds
..., Corros. Sci. (2007), doi:10.1016/j.corsci.2007.03.029