Properties of Corrosion Layers Grown on Zr-based Alloys

Ms. Vera Vrtílková (main author)

ŠKODA-ÚJP, Praha, a.s., Nad Kamínkou 1345, 156 10 Praha-Zbraslav, Czech Republic

Jaroslav Jaroš
ŠKODA-ÚJP, Praha, a.s., Nad Kamínkou 1345, 156 10 Praha-Zbraslav, Czech Republic

Ms. Galina Gosmanová

Czech Technical University in Prague, V Holešovickách 2, 180 00 Praha-8, Czech Republic

Josef Krýsa
Institute of Chemical Technology, Technická 5, 166 28 Praha-6, Czech republic

Pavel Matejka
Institute of Chemical Technology, Technická 5, 166 28 Praha-6, Czech republic

Ladislav Belovsky (co-author for correspondence)

ALIAS CZ s.r.o., Bachova 1586/16, 149 00 Praha-415, Czech Republic

Abstract

A comparative out-of-pile experimental study on long-term corrosion behavior of four Zr-based alloys (Zr1Nb,
ZIRLO, low-tin and standard Zircaloy-4) is underway since 1996. These alloys were exposed in identical conditions
to different 360 °C water chemistries (VVER-1000 imitating chemistry, 70 and 210 ppm Li+) up to max. ~1100 days
and to 400 and 450 °C steam up to max. ~900 days. This paper is focused on the properties of corrosion layers
formed on these alloys with the aim to better understand the relations between the parameters of the corrosion layers
and both the duration & conditions of the corrosion tests (corrosion kinetics). The oxides grown on reactor-grade tubes
were investigated by X-ray diffraction, Raman spectroscopy and electrochemical impedance spectroscopy. The
results indicate that the characteristics of both the stresses and the tetragonal phase content in the oxide before
transition depend mainly on the alloy and its technology. We believe that the corrosion behavior cannot be
extrapolated from higher temperatures to reactor conditions. In contrast to both Zr1Nb and low-tin Zry-4, the
stresses in the oxide on ZIRLO are practically unaffected by the corrosion conditions. The thickness of the
impermeable layer within oxide provides information about the oxide quality only, but does not represent a measure
for the absolute comparison of the corrosion rates between the alloys.

Introduction

To achieve higher fuel burn-up and rating in Light Water Reactors reduction of corrosion rates of Zr-based fuel
rod claddings is required. This is a reason, why the existing alloys (Zircaloy-4, Zr1Nb) are being optimized and
new alloys (ZIRLO, M5, E635, …) are being developed. To predict the corrosion behavior of these alloys under
different conditions a deep understanding of the corrosion mechanisms is necessary.

The Czech Dukovany NPP (VVER-440) operates with Zr1Nb fuel claddings since 1985 with excellent results. The
Temelin NPP (VVER-1000) is in operation since 2001with low-tin Zircaloy-4. Both NPPs use the potassium-based
(KOH) water chemistry. In connection with the expected application of the low-tin Zircaloy-4 in the VVER-1000
KOH water chemistry a long-term experimental program with duration of min. 5 years was initiated in 1996. The
main aim of this extensive program (~5000 specimens) is to provide comparative out-of-pile data on corrosion
behavior of four Zr-based alloys (Zr1Nb, ZIRLO, low-tin and standard Zircaloy-4) in different corrosion
environments. The experimental conditions were selected to amplify both the positive and the negative corrosion
properties of each alloy. The ongoing mid-term results were presented in Vrtílková 1. The maximum exposure time
reached ~1100 days at the end of year 2000 and the project still continues. Although considerable amount of data
was obtained separately for each alloy in the past 2, the current corrosion program offers direct alloy-to-alloy
comparison in identical out-of-pile conditions, which allows assessing the differences between the alloys.

1
The present paper is focused on the relation between the corrosion kinetics and the microstructural and physical
features of the ZrO2 corrosion layer (amount of the tetragonal phase, stresses and oxide morphology). The corrosion
layers were investigated by X-ray diffraction, Raman spectroscopy and electrochemical impedance spectroscopy
after cooling to room temperature. The analysis was limited to specimens exposed to VVER-1000 simulating water
chemistry, water with 70 and 210 ppm Li+ (all 360 °C) and to 400 and 450 °C steam. The main issues were the
following: a) Is there a relation between the stresses in the oxide and the amount of the tetragonal phase, i.e. does the
tetragonal phase relax stresses ?, b) Is there a relation between the stresses in the oxide and the oxide thickness before
transition ?, c) Is there a relation between the impermeable oxide layer thickness and the observed corrosion stages ?

Experimental Procedure

Specimens and Conditions of the Isothermal Corrosion Tests

The corrosion tests were performed with 3 cm long specimens cut from reactor-grade tubing made of Zr1Nb (Russia),
low-tin Zircaloy-4 (Zry-4 W), ZIRLOTM (both Westinghouse) and standard Zircaloy-4 of Sandvik (Zry-4 S). The
chemical composition, geometry as well as the thermal and surface treatment of the specimens are shown in Table 1.
The degreased (but not pickled) specimens were exposed to the oxidizing environment on both surfaces. The tests
were performed in six static autoclaves (4 dm3 each containing max. 160-200 specimens) according to ASTM-G2M-
88 (re-approved in 1996) in the following corrosion environments:
a) demineralized and deionized water (≥ 1 MΩ⋅cm at room temperature with less than 45 ppb oxygen) at 360 °C at
pressure at saturation (~19 MPa) up to ~1100 days, containing the following additives:
• 15.9 ppm potassium as KOH + 1050 ppm boron as H3BO3 + 1 ppm lithium as LiOH, simulating the
Temelín NPP VVER-1000 water chemistry (further called VVER water)
• or 70 and 210 ppm lithium as LiOH
b) pressurized steam at temperatures 400 and 450 °C (~10.3 MPa) up to ~900 days.

Evaluation Methods

Besides the systematic measurements of weight gain (period of 21 days) and axial elongation on all specimens,
some specimens were investigated by the following methods applied to the external surface of the external oxide:

X-Ray diffraction tensometry (XRD). A θ/2θ-goniometer SIEMENS with Cr radiation was used to measure
lattice strains. The X-ray measurements were performed on 15 mm long specimens embedded in a special holder
with a 2 mm wide slit to keep optimal conditions the same for all the measurements performed. The measurements
were performed in oxide layers of samples on {10-4} planes with 2θ = 119.5° for the CrKα radiation (penetration
depth Te(10-4)Cr = 2.52 µm). The measurements in metal substrates were performed on {112} planes for which 2θ =
113.5° for the CrKα radiation (Te(112)Cr = 1.66 µm). The „sum of the surface principal stresses“ technique with a
reference substance was used with regard to the specific experimental conditions, especially to the marked texture of
the oxide layers and the shape of specimens. The same method was applied to determine the stresses in the substrate
near the oxide/metal interface. The method is based on the determination of the lattice strains εhkl perpendicular to
the surface of the sample, where (with regard to the origination) a centrally symmetrical state of stress is assumed (i.e.
σ1 = σ2 = σ). Thus, εhkl = (dS-dO)/dO = – (ν/E)⋅(σ1+σ2) = – (ν/E)⋅2σ, and σ = (E/2ν)⋅(δθ⋅ctg θo), because ε = –δθ⋅ctg
θo, where the σ, ν and E are the stress parallel to the sample surface, the Poisson’s ratio and the Young’s modulus
respectively; dS is stressed and dO unstressed spacing of the (hkl) planes parallel to the surface and θ is the Bragg´s
angle. It should be noticed that the measured values εhkl are supposed to represent the average within the effective
X-ray penetration depth TE, the values of which were calculated to produce 63% of the overall diffracted intensity.
The stress values were calculated using E = 20.7⋅104 MPa for zirconia and 9.4⋅104 MPa for α-Zr. The error of stress
determination was max. ~10% of the calculated stress values.

Raman spectroscopy (RAMAN). FT Raman spectra were collected using a Fourier transform near-infrared
spectrometer Equinox 55/S (BRUKER) equipped with a FT Raman module FRA 106/S (BRUKER). The samples
placed on a X-Y-Z motorized sample stage were irradiated by a focused laser beam (250 mW) of a Nd-YAG laser
(1064 nm, Coherent). The analyzed area was ≅ 1 mm2, the maximum penetration depth was ~10 µm. The scattered
light was collected in backscattering geometry. Quartz beam-splitter and Ge detector (liquid N2 cooled) were used to

2
obtain interferograms. 1024 interferograms were co-added and then processed by the Fourier transformation with
Blackman-Harris 4-term apodization a zerofilling factor 8 to obtain final FT Raman spectra in the range 4000 -
(-1000) cm-1 with 4 cm-1 resolution (using the OPUS 2.3 software). The tetragonal powder ZrO2 standard (stabilized
with yttria) exhibited a band at ~260 cm-1. To cover all alloys and conditions the method for calculation of the
relative amount of tetragonal ZrO2 in the oxide layer had to be several times modified 3. The finally applied equation
(yielding the lowest tetragonal phase fractions) uses the following peak intensities (integrals):
%(T-ZrO2) = IT(282) / (IT(282) + IM(190) + IM(179) + IM(480)) (1)
Raman spectra were also measured through the oxide thickness along an inclined cut (1°angle from longitudinal axis)
from ~1-2 µm depth, using a LabRam system (DILOR) equipped with an external Ar+-ion laser (MELLES GRIOT)
with an (×100) objective. The 488-nm line was used for excitation (power 25 mW). Raman spectra were also
measured from different depths of oxide layer (on one specimen only) using Ramascope (RENISHAW) focusing on
1 µm3 and using 10 mW power.

Electrochemical Impedance Spectrometry (EIS). After the corresponding corrosion exposure the samples were
immersed in 0.5 M K2SO4 and left at room temperature for different time (up to ~100 days). Before each impedance
measurement a sample was taken out of the container and placed into a electrochemical cell for impedance
measurements. The Ag/AgCl was used as a reference electrode and the Pt cylinder (φ 40 mm) as a counter electrode.
The open-circuit potential was continuously measured until achieving the steady state value. The impedance (plotted
in Bode diagrams) was then measured for various times the specimen spent in the electrolyte using a potentiostat (50
kΩ) in series with a frequency analyzer SOLATRON 1250 (10 mHz -65 kHz) using 10 mV amplitude. The stabilized
value of the measured impedance was then replaced by the calculated impedance of an equivalent seven-element
electrical circuit, composed of resistances and capacitances. Physical meaning was ascribed to each element. The
oxide was assumed to consist of a compact (B) and a porous layer. The compact layer was further divided into a part
near the metal/oxide interface impermeable for the electrolyte (A) and into a part permeable for the electrolyte. The
effective thicknesses dA and dB of layers A and B were estimated from the equation C = ε⋅εo /d [nF/cm2], where C
and d are the corresponding capacity and the layer thickness, εo is permitivity of vacuum 8.845⋅10-10 F/m and ε is the
dielectric constant of ZrO2 (selected value ~22). See Krýsa 4 for more details.

Results

The specimens used for XRD, RAMAN and EIS measurements of the corrosion layer were exposed in VVER water,
water containing 70 and 210 ppm Li+ (all at 360 °C) and in 400 and 450 °C steam. Their corrosion kinetics is shown
in Figure 1. With increasing of both the exposure time and temperature the originally black, bright and adherent
oxide became lighter. Nodular oxide appeared on Zry-4 S at 400 °C, on Zry-4 W at 450 °C, on Zr1Nb in water with 70
ppm Li+ (spalling oxide) and on ZIRLO in water with 210 ppm Li+. The corrosion resistance of the standard Zry-4 S
compared to the low-tin Zry-4 W is better in VVER water at 360 °C but worse in 400 °C steam (where the Zry-4 W
exhibited the lowest weight gain at all exposures). The weight gain curve of all alloys in both VVER water and 400
°C steam is characterized by a step-wise character differing only in the length and size of the steps. The
metallographic cuts have shown porosity parallel with the oxide/metal interface that divides the corrosion layer into
several sub-layers. The number of the sub-layers corresponds to the number of steps on the weight gain curve.

The compressive stresses in oxide versus oxide thickness (measured at room temperature) are shown in Figure 2 for
Zr1Nb, ZIRLO and Zry-4 W exposed in VVER water (360 °C), water with 70 ppm Li+ (360 °C) and in 400 and 450
°C steam. It can be seen that stresses in thin oxides before transition follow a different course, specific for each
alloy. The stresses also depend on the oxide thickness at transition. This is well visible especially for the Zr1Nb
alloy exposed in VVER water. The stresses grow with oxide thickness; reach a certain maximum at approximately
one half of the thickness at transition and then decrease. The stresses in the oxide on Zr1Nb and on Zry-4 W
decrease with increasing temperature of the corrosion test. ZIRLO seemed to be insensitive to both the temperature
and the corrosion environment. Zry-4 W specimens exhibited systematically lower stresses than Zr1Nb also in the
water with 70 ppm Li+. On the other hand, the highest compressive stresses in the oxide were found on ZIRLO. In
thick oxides (> 10 µm), i.e. after long exposures, the compressive stresses stabilized at approximately constant value
of 150 MPa for Zr1Nb, 400 MPa for ZIRLO and 200 MPa for Zry-4 W.

In Zr1Nb the tensile stresses in the underlying metal (at the metal/oxide interface) stabilized in dependence of the
oxide thickness (from weight gain) around 200 MPa regardless the corrosion conditions. In the 400 and 450 °C steam

3
was this value was reached already for 1 µm thick oxide. The stresses in the ZIRLO and Zry-4 W specimens reached
approximately 300 MPa.

The size of coherent regions (crystallites) in oxide was found to increase with exposure time (i.e. with oxide
thickness). The maximum size reached roughly 20 nm for Zr1Nb and ~23 nm for both ZIRLO and Zry-4 W. In Zry-
4 W specimens exposed in 400 °C steam the size of crystallites in oxide was ~30 nm for ~2 µm thick oxides, but
stabilized around 20 nm in thicker oxides (the crystallite size at 450 °C was smaller, max. 15 nm).

It was difficult to unify in the Raman spectra measurements the experimental method for all tested alloys and
conditions. Table 2 shows the most important monoclinic Raman band positions together with the deviations from
standards. Table 3 shows for specimens exposed in VVER water the positions of bands together with the band
shoulders that correspond to the tetragonal phase. We believe that the bands 282, 275 and 264 cm-1 (the last one
being close to standard) belong to a distorted tetragonal phase. The calculated tetragonal phase fraction was
especially in case of ZIRLO significantly influenced by the number of peaks included into equation (1).

The measured tetragonal phase fractions were expressed in form of equivalent thickness of tetragonal oxide. This
equivalent thickness was calculated as a product of the oxide thickness and the fraction of the corresponding
tetragonal phase in the oxide, and is plotted in Figure 3 in dependence on oxide thickness for different alloys and
conditions. The amount of the tetragonal phase depends on the corrosion environment, temperature and exposure
time (oxide thickness) and before transition increases with temperature. The highest fractional amount of the
tetragonal phase was generated in Zr1Nb specimens. The lowest fraction appeared on Zry-4 W specimens. The
amount of the tetragonal phase was also determined on few Zry-4 S specimens exposed in 400 °C, however was
systematically lower than that for Zry-4 W. In VVER water at 360 °C the amount of the tetragonal phase sharply
dropped at the transition point on the corrosion curve in case of all alloys. Such behavior was observed for Zr1Nb
alloy also at subsequent jumps on the corrosion curve (in VVER water at 360 °C), which is documented in Figure 4.

The standard Raman method allowed analyzing oxides up to ~ 10 µm only. The fraction of the tetragonal phase in
thicker oxides was, therefore, measured along an inclined cut (1 °) through the oxide on specimens exposed for 903
days in VVER water. This method confirmed the presence of the tetragonal phase in a Zr1Nb specimen (~13 µm
thick oxide) near the metal/oxide interface in a sub-layer of about 2.5 µm, Figure 5. On the other hand, the same
method did not detect the tetragonal phase on both the ZIRLO and Zry-4 W (both ~21 µm thick oxide). The
distribution of the tetragonal phase through the oxide thickness was determined for a Zr1Nb specimen with ~3.1 µm
thick oxide (before transition) exposed in VVER water. This method showed that the tetragonal phase was present
across the whole oxide thickness.

The growth of the non-porous (compact) layer in the oxide was measured using the EIS method. Based on the
seven-element equivalent circuit the thicknesses of the two following layers were quantified: compact layer (B) and
impermeable portion of this layer (A). The thicknesses of these layers A and B versus oxide thickness (determined
from weight gain) are plotted in Figure 6 for Zr1Nb, ZIRLO and Zry-4 W exposed at 360 °C in VVER water and
water with 70 and 210 ppm Li+. In VVER water both layers grow with exposure time on all alloys. For Zr1Nb and
Zry-4 W was the impermeable portion of the compact layer, however, thinner in Li+-containing water from the very
beginning. On the other hand, this layer was somewhat thicker on ZIRLO in water containing 70 ppm Li+ in
accordance with the corrosion kinetics. The growth of layers A and B for specimens exposed in 400 and 450 °C
steam is plotted in Figure 7 in dependence on the oxide thickness. The behavior of layers A and B in the 400 °C
steam is similar to that in VVER water at 360 °C. The Zry-4 S alloy exhibited significantly thinner layer A
compared with other alloys. In the 450 °C steam both layers A and B were much thinner on all alloys compared to
400 °C. Measurements on specimens with thick oxides (Zr1Nb ~100 µm and ZIRLO ~285 µm) exposed in 450 °C
steam have shown that both layers A and B are very thin (<< 3 µm for Zr1Nb and <<1 µm for ZIRLO).

Discussion

Earlier comparative studies of corrosion layer properties were focused especially on Zircaloys and concentrated e.g.
on the influence of different Sn content 5. Some studies 6, 7 were dealing also with Zr2.5Nb but very few studies
directly compared Zr1Nb with Zircaloys 8, 9. The current comparative experimental program provides some details on
corrosion layers properties measured on Zr1Nb, ZIRLO and low-tin Zircaloy-4 by XRD, Raman spectroscopy and

4
EIS. This study was focused on the characterization of the corrosion layer (near the metal/oxide interface), which is
believed to govern the corrosion kinetics, and on the transition between the parabolic (or cubic) to paralinear
kinetics. The major findings are discussed in the following paragraphs.

Both the stress in oxide in dependence on its thickness and the maximum stress depend on the type of the alloy. The
stress in the oxide on Zr1Nb and Zry4-W depend on the corrosion environment and is lower at higher temperatures.
On the other hand, the stress in the oxide on ZIRLO is independent on the corrosion environment (when compared
at the same oxide thickness).

Before the transition occurs on the corrosion curve the amount of the tetragonal phase in oxide (expressed as
equivalent thickness of tetragonal oxide layer) develops similarly as the stress in the oxide. In the vicinity of the
transition point the tetragonal phase fraction sharply drops approximately by a factor of two. This is noticeable
especially at 360 °C in VVER water, where the transition occurred after a relatively long period: Zr1Nb 260 days,
ZIRLO 80 d, Zry-4W 60 d (a relatively large set of specimens was available for these experimental conditions). It
was shown for the Zr1Nb alloy that the fraction of the tetragonal oxide increases after transition again up to the next
transition (jump on the corrosion curve), at which the tetragonal phase again partially transforms into monoclinic phase. It
is not excluded that this phenomenon occurs also in other alloys. It seems, however, that the tetragonal phase fraction
decreases during oxidation up to complete disappearance after sufficiently long exposure time. This was confirmed for
Zry-4W by measurements on the inclined cut through oxide layer. It was observed for each alloy that the tetragonal phase
fraction increases with temperature. The highest fraction was detected in the oxide of the Zr1Nb alloy. It seems that in the
case of Zr1Nb and Zry-4W alloys the presence of the tetragonal phase facilitates the stress relaxation at the metal/oxide
interface (lower stress in the oxide). Such a relaxation, however, did not become evident in ZIRLO.

It can be concluded from the above results that both the tetragonal phase fraction and the stress in the oxide are (in
dependence on the corrosion conditions) typical for each alloy characterized by chemical composition, content of
impurities and technology. It is, however, not possible, to predict the corrosion behavior (rate) only on basis of these data
(the corrosion rate cannot be related with the tetragonal phase fraction). But it is always true that the tetragonal phase
fraction reaches its highest value during the period before transition. After transition to paralinear kinetics this fraction
decreases (and possibly disappears ?). To answer this question specimens with long exposures will be analyzed in the next
stage of the project considering also oxidation of hydrides near the metal/oxide interface and their impact on the stress
relaxation and the tetragonal phase development.

Barberis 8 observed on Zry-4 and Zr1NbO at 470 °C in oxygen only continuous decrease of the tetragonal phase fraction
without any relation to the transition on the corrosion kinetics. The reason for this may be probably the relatively high
temperature, shorter time at transition and absence of the step-wise character of the corrosion curve. Barberis also
measured more tetragonal phase fraction in Zry-4 than in Zr1NbO and we agree with this finding. Our measurements of
stresses in oxide at 450 °C indicate lower stresses in Zry-4 than in Zr1Nb, which implies more tetragonal phase in Zry-4
than in Zr1Nb. Barberis, however, concludes that the relation concerning the tetragonal phase fraction between both alloys
can be applied also to reactor conditions. This conclusion is, however, in disagreement with our data at 360 °C in VVER
water because we observed much more tetragonal phase in Zr1Nb than in Zry-4W.

The good corrosion resistance of Zry-4 W in 400 °C steam compared to all other alloys may be connected with the large
size of oxide crystallites (30 nm) near the metal/oxide interface, because the oxygen ions diffuse in Zircaloys
preferentially along the surface of the crystallites in the oxide.

The EIS method confirmed the results of Barberis 10 that a portion of the oxide thickness before transition remains porous.
The thickness of the layers A and B (impermeable portion of compact layer and compact layer, respectively) in our
work are related with the corrosion kinetics only if the changes in the corrosion rate are significant. This is a case of
water with Li+ at 360 °C or steam 400 °C (see Zry-4W versus Zry-4S) and 450 °C. Application of the EIS method,
however, does not allow to distinguish the corrosion behavior of the alloys in VVER water or 400 °C steam (with
exception of Zry-4S – nodular corrosion), where the corrosion rates of the alloys are similar. The compact layer B
grows also after transition but we cannot say, whether this layer will reach a certain stabilized thickness as in the case of
Zry-4S. This will be answered after analysis of specimens with longer exposures.

5
 Conclusions

The results of this long-term out-of-pile comparative study obtained up-to-date provide a basis for systematic alloy-
to-alloy comparison aimed at better understanding of the corrosion mechanisms.

It seems impossible to explain differences in corrosion behavior of Zr-based alloys by the differences observed in
the stress and tetragonal phase fraction in oxide.

Both the evolution and the maximum value of stress in oxide as well as the similar behavior of the tetragonal phase
fraction in oxide before transition seem to be mainly influenced by the alloy and its technology. The evolution of
stresses in the Zr1Nb and Zry-4 W oxides depends on both the corrosion environment and temperature. In contrast to
this, the evolution of stresses in the oxide on ZIRLO is practically unaffected by the corrosion conditions.

The information drawn from the thickness of the impermeable layer in oxide speaks only about the oxide quality.
The behavior of this layer, therefore, cannot be used as a parameter for comparison of the corrosion rates between
alloys but can indicate for one alloy at least qualitatively its corrosion resistance in different corrosion environments.

Acknowledgment

This work was funded by CEZ (Czech Power Company), the Czech Ministry of Industry and Trade and partially
also by the Czech Ministry of Youth and Education (Project MSM No.210000021 on XRD). The authors wish to
thank Westinghouse for providing ZIRLO and Zry-4 W for the tests. We also thank M. Bartoš from ALEF for
development of the corrosion database. We especially thank the ŠKODA-ÚJP staff, namely L. Molin for the conduct of
experiments in autoclaves and J. Šustr for preparation of specimens. The authors appreciate the comments & assistance of
L. Novotný and J. Freimanová. We also thank Z. Bastl from Czech Academy of Sciences for Raman measurements.

References

1. V. Vrtílková, J. Jaroš, J. Cmakal, L. Belovsky, “Corrosion of Zr-Alloys”. In: Proceedings of the International
Topical Meeting on Light Water Reactor Fuel Performance, April 10-13, 2000, Park City, Utah, USA (2000).

2. B. Cox et al.: Waterside corrosion of zirconium alloys in nuclear power plants. IAEA-TECDOC-996 (1998).

3. J. Krýsa, J. Maixner, P. Matejka, V. Vrtílková: Structure and composition of zirconium oxide films formed in
high pressure water with different Li+ concentration at 360 °C. Materials Chemistry and Physics 63 (2000) 1-8.

4. J. Krýsa: EIS study of Zr-alloys exposed in high-pressure water with different concentration of Li+ ions at
360 °C. Acta Chimica Hungarica – Models in Chemistry 137 (2000) 249.

5. P. Barberis: Zirconia powders and Zircaloy oxide films tetragonal phase evolution during 400 °C autoclave
tests. Journal of Nuclear Materials 226 (1995) 34-43.

6. O. Gebhardt, A. Hermann, G. Bart et al.: Investigation of In-pile Grown Corrosion Films on Zirconium-Based
Alloys. 11th Int. Symposium on Zirconium in the Nuclear Industry, ASTM STP 1295 (1996) 218-241.

7. A. J. G. Maroto, R. Bordoni, M. Villegas et al.: Growth and characterization of layers on zirconium alloys.
Journal of Nuclear Materials 229 (1996) 79-92.

8. N. Pétigny, P. Barberis, C. Lemaignan, Ch. Valot, M. Lallemant: In situ XRD analysis of the oxide layers
formed by oxidation at 743 K on Zircaloy 4 and Zr-1NbO. Journal of Nuclear Materials 280 (2000) 318-330.

9. J. Godlewski et al.: Stress Distribution Measured by Raman Spectroscopy in Zirconia Films Formed by
Oxidation of Zr-Based Alloys. 12th Int. Symp. on Zr in the Nuclear Industry, ASTM STP 1354 (2000) 877-898.

10. P. Barberis, A. Frichet: Characterization of Zircaloy-4 oxide layers by impedance spectroscopy. Journal of
Nuclear Materials 273 (1999) 182-191.

6
Table 1 Chemical composition, thermal treatment and average dimensions of the cylindrical specimens.

Chemical composition Zr1Nb ZIRLO Zry-4 W Zry-4 S

Nb [wt %] 1.07 ± 0.1 0.98 - 1.03 - -
Sn [wt %] - 1.05 - 1.08 1.30 - 1.34 1.46
Fe [wt %] - 0.09 - 0.10 0.18 - 0.20 0.21
Cr [wt %] - - 0.10 - 0.11 0.09
Fe+Cr [wt %] - - 0.29 - 0.31 -
H [ppm] 10 ± 5 10 8 - 10 10
N [ppm] 25 ± 5 25 20 30
C [ppm] max. 100 74 - 101 130 - 150 max. 120
O [ppm] 400 ± 100 1100 - 1300 1140 - 1230 1.290
Si [ppm] - - 80 - 90 -
Thermal treatment recrystallized stress-relief annealed
Surface treatment ground finely ground ground
Outer diameter [mm] 9.175 9.137 9.145 10.742
Wall thickness [mm] 0.706 0.574 0.578 0.709
Length [mm] 30

Table 2 Monoclinic Raman band positions with deviation from the monoclinic ZrO2 powder standard in oxides
on different alloys after 465 days exposure in VVER water (360 °C).

Zr1Nb ZIRLO Zry-4 W

Band position Deviation Band position Deviation Band position Deviation
[cm-1] [cm-1] [cm-1] [cm-1] [cm-1] [cm-1]
179 0 179 0 179 0
190 +1 191 +2 190 +1
336 +4 336 +4 336 +4
382 +1 380 -1 385 +4
478 +2 477 +1 477 +1
638 0 638 0 641 +3

Table 3 Tetragonal Raman band positions in oxides on different alloys after different exposure times in VVER
water (360 °C). The first column shows the band position, which is shifted from that of tetragonal ZrO2
powder standard (~260 cm-1).The second column shows the band position close to the position of the
tetragonal ZrO2 powder standard.

Exposure time Zr1Nb ZIRLO Zry-4 W

[days] band positions [cm-1]
3 282, 276(sh) - 273 - 271 -
85 280 263 275, 283(sh) 264 281, 270(sh) -
273 283 261 280, 273(sh) 264 281, 270(sh) -
357 282, 272(sh) - 281,271(sh) - 275 264
462 282, 268(sh) - not detectable - 282, 276(sh) 264
819 280, 264(sh) - 280, 272(sh) - 280 267

7
 400 200 1000

VVER-1000 imitating 900

350 water+Li (ppm), 360°C steam, 400°C
water, 360°C
800
300 150

Weight gain [ mg/dm2 ]

700

Weight gain [ mg/dm2 ]

Weight gain [ mg/dm2 ]

250
600

200 100 500

400
150

300
100 50
Zr1Nb 70 200
ZIRLO 70
50 Zr1Nb ZIR LO Zry-4W 70 Zr1Nb ZIR LO
Zr1Nb 210 100
Zry -4 W Zry -4 S ZIRLO 210 Zry -4 W Zry -4 S
Zry-4W 210
0 0 0
0 200 400 600 800 1000 1200 0 50 100 150 200 0 200 400 600 800 1000

Exposure time [ days ] Exposure time [ days ] Exposure time [ days ]

Figure 1 Corrosion kinetics for Zr1Nb, ZIRLO, Zry-4 W and Zry-4 S in VVER-1000 imitating water (360 °C),
in water with 70 and 210 ppm Li+ (360 °C) and in 400 °C steam.

1400 1400 1400

Zr1Nb ZIRLO Zry-4 W

1200 1200 1200

Compressive stress in oxide [ MPa ]
Compressive stress in oxide [ MPa ]
Compressive stress in oxide [ MPa ]

1000 1000 1000

800 800 800

600 600 600

400 400 400

VVE R 360° C VVE R 360° C VVE R 360° C
70 ppm Li 70 ppm Li 70 ppm Li
400° C 400° C 400° C
200 450° C 200 450° C 200 450° C

0 0 0
0.1 1 10 100 0.1 1 10 100 0.1 1 10 100

Oxide thickness [ µm ] Oxide thickness [ µm ] Oxide thickness [ µm ]

Figure 2 Compressive stresses in oxide grown on Zr1Nb, ZIRLO and Zry-4 W in different environments. The
oxide thickness was calculated from weight gain. The arrow indicates the oxide thickness at transition.

8
 3.0 3.0 3.0

Zr1Nb ZIRLO Zry-4 W

Thickness of equiv. tetragonal oxide [µm]

Thickness of equiv. tetragonal oxide [µm]

Thickness of equiv. tetragonal oxide [µm]

2.5 2.5 2.5
VVE R VVE R VVE R
400° C 400° C
70 ppm Li 400° C 70 ppm Li
2.0 2.0 2.0

1.5 1.5 1.5

1.0 1.0 1.0

0.5 0.5 0.5

0.0 0.0 0.0

0 5 10 15 20 0 5 10 15 20 0 5 10 15 20

Oxide thickness [ µm ] Oxide thickness [ µm ] Oxide thickness [ µm ]

Figure 3 Calculated equivalent thickness of the tetragonal ZrO2 phase for Zr1Nb, ZIRLO and Zry-4 W that were
exposed in VVER water, in water with 70 ppm Li+ (all 360 °C) and in 400 °C steam. The arrow indicates
the oxide thickness at transition.

18 2.5
Oxide
16 Zr1Nb (VVER water, 360°C) thickness
8.99 µm
2
Thickness of eq. tetrag. phase [µm]
Oxide thickness from w. gain [µm]

14 6.15 µm
4.56 µm
Intensity [ a.u.]

12
1.5 3.54 µm
10
3.41 µm
8 2.77 µm
1 2.20 µm
6 1.79 µm
1.54 µm
4
0.5
Av . oxide thick. 0.82 µm
2 Oxide thickness 0.54 µm
Tetragonal phase
200 400 600
0 0
Wavenumber [ cm -1 ]
0 100 200 300 400 500 600

Exposure time [ days ]

Figure 4 Relation between the calculated equiva- Figure 5 Raman spectra measured along an inclined
lent thickness of the tetragonal ZrO2 phase in oxide cut (angle 1°) through Zr1Nb oxide (VVER, 360 °C). The
and the corrosion kinetics for Zr1Nb exposed in tetragonal phase was detected within a ~2.5 µm thick
VVER water at 360 °C. layer near the metal/oxide interface (see the peak ~280).

9
 5 5 5

Zr1Nb ZIRLO Zry-4 W

Thickness of layers A and B [ µm ]

Thickness of layers A and B [ µm ]

Thickness of layers A and B [ µm ]

4 4 4

3 3 3

2 2 2

1 1 1

0 0 0
0 5 10 15 20 0 5 10 15 20 0 5 10 15 20

Oxide thickness [ µm ] Oxide thickness [ µm ] Oxide thickness [ µm ]

A VVE R 360 C A 70 ppm Li A VVE R 360 C B VVE R 360 C A VVE R 360 C B VVE R 360 C
A 70 ppm Li B 70 ppm Li A 70 ppm Li B 70 ppm Li
B VVE R 360 C B 70 ppm Li A 210 ppm Li B 210 ppm Li A 210 ppm Li B 210 ppm Li

Figure 6 Thickness of the compact layer (B) and the impermeable portion of the compact layer (A) by the EIS
method on Zr1Nb, ZIRLO and Zry-4 W exposed at 360 °C in VVER water and in water containing 70 and
210 ppm Li+ versus the oxide thickness calculated from the weight gain.

12 12 12

Zr1Nb ZIRLO Zry-4 W, S

10 10 10
Thickness of layers A and B [ µm ]

Thickness of layers A and B [ µm ]

Thickness of layers A and B [ µm ]

8 8 8

6 6 6 A 400° C W
A 400° C A 400° C
A 450° C A 450° C A 400° C S
B 400° C W
B 400° C B 400° C B 400° C S
4 B 450° C 4 B 450° C 4 B 450° C W

2 2 2

0 0 0
0 20 40 60 80 100 0 20 40 60 80 100 0 20 40 60 80 100
Oxide thickness [ µm ] Oxide thickness [ µm ] Oxide thickness [ µm ]

Figure 7 Thickness of the compact layer (B) and the impermeable portion of the compact layer (A) by the EIS
method on Zr1Nb, ZIRLO, and Zry-4 W and Zry-4 S exposed in steam at 400 and 450 °C versus the oxide
thickness calculated from the weight gain.

10