Journal of ASTM International

PaperID#

Duriez C.1, Guilbert S.1, Stern A.2, , Grandjean C.1, Bělovský L.3, Desquines J. 1

Corresponding author:

CHARACTERISATION OF OXYGEN DISTRIBUTION IN LOCA SITUATIONS

ABSTRACT : The French « Institut de Radioprotection et de Sûreté Nucléaire » (IRSN) launched in

the recent years a research program named CYCLADES aiming at improving the knowledge on fuel
behaviour during Loss Of Coolant Accidents (LOCA). The CYLCADES program covers three main
topics of interest for LOCA issues: cladding mechanical behaviour and failure conditions, axial fuel
relocation, and coolability of fuel rods after flow blockage. The present study addresses part of the
research program on oxygen-induced cladding embrittlement which mainly depends on oxygen
distribution in the Zirconium β-phase. The influence of oxygen content on cladding embrittlement is
usually expressed using a single parameter: the Equivalent Cladding Reacted (ECR) directly related
to the mass gained during the LOCA transient. However the presence of the corrosion scale, grown
during normal operation, was not taken into account in the original ECR criteria. This pre-existing
oxide layer is potentially a source of oxygen for oxygen diffusion in the underlying metal. Actually,
at elevated temperature, partial or full dissolution of this pre-existing oxide layer is sometimes
observed and its oxygen content moves inwards by diffusion. As a consequence of this dissolution
process, significant oxygen embrittlement can be observed without any noticeable mass gain.
Furthermore, the hydrogen content as well as the cooling rate were recently demonstrated to play a
key role in the oxygen distribution and consequently in cladding embrittlement. It was thus decided
to reach better physical determination of the cladding embrittlement under LOCA conditions relying
on the oxygen distribution through the cladding wall rather than relying on the ECR parameter alone.
IRSN develops the DIFFOX diffusion code in order to achieve this objective.
The present paper focuses on the IRSN action plan, established to obtain an accurate simulation of
the oxygen profile within the cladding thickness using the DIFFOX code. This diffusion code will
later be applied to the many configurations of interest for PWR LOCA safety issues. Three main
subjects of interest are under investigation: the study of oxidation and oxide reduction kinetics at
high temperature, the study of the hydrogen influence on oxygen distribution after a LOCA transient,
and the study of the oxygen concentration at phase boundaries under non-stationary cooling
conditions. Only the two first topics are handled in this paper, since the last one started being
investigated too recently.
First, the paper describes the main assumptions for diffusion modeling in the DIFFOX code and
associated numerical methods. Next, the test devices and experimental protocols supporting this
study are presented. Then, experimental results relevant for oxidation and reduction kinetics are
discussed and compared to open literature data. Particular attention is paid to oxygen concentration
profiles, obtained by Electron Probe Micro-Analysis (EPMA), that are compared to DIFFOX
predicted distributions. Regarding investigation on the influence of hydrogen on oxygen distribution,
results obtained with 600 wppm hydrogen charged cladding samples have been obtained. The
influence of hydrogen is mainly focused on measurements at thermodynamic equilibrium, that lead
to new data on the Zr-O phase diagram for a hydrogen containing alloy.

KEYWORDS: LOCA, DIFFOX, oxygen diffusion, modeling, hydrogen.

Introduction
The French « Institut de Radioprotection et de Sûreté Nucléaire » (IRSN) launched in the recent years a
research program named CYCLADES aiming at improving the knowledge on fuel behaviour during Loss Of

1
IRSN/DPAM, BP3, 13115 Saint Paul-Lez-Durance, France.
2
Now at CEA/DEN-DANS/DMN/SEMI/LM2E, CEA/Saclay, 91191 Gif-Sur-Yvette, France.
3
ALIAS CZ s.r.o., Bachova 1586/16, 149 00, Praha, Czech republic.
Coolant Accidents (LOCA). The IRSN strategy is detailed in [1]. The CYLCADES program covers three
main topics of interest for LOCA issues: cladding mechanical behaviour and failure conditions, axial fuel
relocation, and coolability of fuel rods after flow blockage. The present study addresses part of the research
program on oxygen-induced cladding embrittlement which mainly depends on oxygen distribution in the
Zirconium β-phase [2-5]. The influence of oxygen content on cladding embrittlement is usually expressed
using a single parameter: the Equivalent Cladding Reacted (ECR), directly related to the mass gained during
the LOCA transient [3]. However the presence of the corrosion scale, grown during normal operation, was
not taken into account in the original ECR criteria. This pre-existing oxide layer is potentially a source of
oxygen for oxygen diffusion in the underlying metal. Actually, at elevated temperature, partial or full
dissolution of this pre-existing oxide layer is sometimes observed and its oxygen content moves inwards by
diffusion. As a consequence of this dissolution process, significant oxygen embrittlement can be observed
without any noticeable mass gain [6]. Furthermore, the hydrogen content as well as the cooling rate were
recently demonstrated to play a key role in the oxygen distribution and consequently in cladding
embrittlement [4, 5, 7]. It was thus decided to reach a better physical determination of the cladding
embrittlement under LOCA conditions by relying on the oxygen distribution through the cladding wall rather
than relying on the ECR parameter alone. IRSN develops the DIFFOX diffusion code in order to contribute
to achieve this objective.
The present paper focuses on the action plan, illustrated in FIG. 1, established to obtain in LOCA
situations an accurate simulation of the oxygen distribution within the cladding thickness using the DIFFOX
code. This diffusion code will later be applied to the many configurations of interest for PWR LOCA safety
issues. Three main subjects of interest are under investigation: the study of oxidation and oxide reduction
kinetics at high temperature, the study of the hydrogen influence on oxygen distribution, and the study of the
oxygen distribution under non-stationary cooling conditions. Only the two first topics are handled in this
paper, since the last one started being investigated too recently. The experimental program addressing these
oxygen distribution related problems has been called the MARGO-D program.
First, the paper describes the main assumptions for diffusion modeling in the DIFFOX code and
associated numerical methods. Next, the test devices and experimental protocols supporting this study are
presented. Then, experimental results relevant for oxidation and reduction kinetics are discussed and
compared to open literature data. Particular attention is paid to oxygen concentration profiles, obtained by
Electron Probe Micro-Analysis (EPMA), that are compared to DIFFOX predicted distributions. Regarding
investigation on the influence of hydrogen on oxygen distribution, results obtained with 600 wppm hydrogen
charged cladding samples are presented. The influence of hydrogen is mainly focused on measurements at
thermodynamic equilibrium, that lead to new data on the Zy-4-O pseudo binary phase diagram for a
hydrogen containing alloy.

The DIFFOX diffusion code

The development of the computer code DIFFOX was started in early 2006 at IRSN to calculate the Zircaloy
oxidation in steam under LOCA conditions with the aim to predict the Zircaloy cladding embrittlement as a
function of the oxygen & hydrogen content (& distribution) in the cladding wall.
In view of possible revision of the ECCS acceptance criteria towards the use of the oxygen content in
the prior beta phase as the leading parameter, it is important to be able to realistically calculate the transient
oxygen profile in the metal layers. For that purpose, an advanced tool is necessary for the calculation of the
oxygen diffusion in the different layers of an irradiated cladding under transient LOCA conditions. Such tool
should be able to reliably calculate:
o the partial dissolution of thick corrosion layer(s) in the initial stage of the temperature transient
(particularly below 1000 °C)
o the more or less protective effect of the corrosion layer with respect to oxygen diffusion
o the influence of hydrogen absorbed during in-service operation on the oxygen solubility in the beta
phase
The DIFFOX code issues partly from the PECLOX code by Neitzel [8], subsequently modified at IRSN
in a private version for the simulation of two-sided oxidation by steam. It has then been largely
reprogrammed and extended in the successive versions of the code under current development.
Main features

The DIFFOX code considers a 1-D system of reaction layers in finite cylindrical geometry, among the
numerous physically possible combinations of the following layers:
ZrO2 , α-Zr (low T or stabilized by O), (α+β)-Zr, β-Zr
The oxygen concentration profile is calculated in each reaction layer by solving the 1-D diffusion
equation (2nd Fick law) in cylindrical coordinates:

∂C (r , t ) 1 ∂
= ⋅ (r ⋅ Fr )
∂t r ∂r (1)
where the left side is the oxygen accumulation and the right side is the space change of the diffusion
flux Fr. The oxygen flux is assumed to be proportional to the oxygen gradient (first Fick law):

∂C (r , t )
Fr = − D(T ) ⋅
∂r (2)
where C(r,t) is oxygen concentration [kg/m3], D(T) oxygen diffusion coefficient as function of
temperature [m2/s], t is time [s], r is radius [m].
The movement of layer boundaries is derived from the mass balance of oxygen at the interface between
two layers (Stefan equation):
∂S F+ − F−
=
∂t 2π S (C + − C − ) (3)
where S is the interface position, F+ and F- are the oxygen fluxes, whereas C+ and C- are the oxygen
concentrations respectively on each side of the interface.
The oxygen diffusion coefficients D are taken from literature for the single phase layers. For the two-
phase layer (α+β)-Zr an “equivalent” weighted D is composed of values for the alpha and beta phases.
The oxygen boundary concentrations were initially taken from the equilibrium Zr-O & Zry-O phase
diagrams. However, instantaneous equilibrium at boundaries appeared to be not applicable to transient
conditions, particularly under cooling. A corrective approach has been introduced based on provisional
assumptions on the limited increase or decrease of the oxygen boundary concentration during the
temperature transient. This key question will be mainly addressed by specific experiments of the MARGO-R
series planned at IRSN in late 2010, with controlled cooling prior a final quench to freeze the oxygen
concentration profile which will be later determined by EPMA.
To predict oxidation of hydrided specimens, oxygen boundary concentrations must also be known as a
function of the hydrogen content. Only sparse data exist today for the oxygen solubility in β-Zr at 1200 °C.
Specific experiments have also been planned at IRSN within the MARGO-R program to provide the
necessary data required to allow a correct simulation of oxygen diffusion in hydrided material.
The above equations (1 to 3) are numerically solved using the implicit finite-difference method. A
reaction layer is divided into N meshes with a variable width increasing from the boundaries towards the
middle of the layer. The derivation of the finite-difference formulas leads to a system of linear equations
with a tri-diagonal matrix. The numerical solution of the system of equations is obtained by Gauss
elimination method.

Modelling of the oxide in DIFFOX

The existing models for Zircaloy oxidation in LOCA conditions approximate the oxide as a homogeneous
material, in which the diffusion coefficient of oxygen depends on temperature only. This is acceptable for
temperatures well above 1000 °C, where the oxide is in tetragonal phase and the oxidation kinetics is
parabolic. Such models, however, are no more sufficient in situations where the oxide has a more
complicated structure, i.e. at temperatures below ~1000 °C or in case of a pre-existing oxide scale, such as a
corrosion scale formed during reactor operation.
Although the monoclinic phase in ideal unstressed conditions is stable below 1200 °C, tetragonal phase
is stabilized in the growing high-temperature oxide through various mechanisms, especially near the
oxide/metal interface. During the oxidation, the oxide scale is in a continuous transformation including grain
growth, phase transformation, porosity development and thickening. All these parameters influence the
kinetics of the oxide growth.
There is a general agreement between experimentalists that during the oxidation below ~1000 °C the
oxide is a mixture of monoclinic and tetragonal phase. It is agreed that the low-temperature monoclinic phase
dominates at low temperatures. The meta-stable tetragonal phase preferentially forms near the oxide/metal
interface. The oxide layer, thus, can be virtually divided into several sub-layers.
In DIFFOX 1.2 the oxide model distinguishes up to three zones in the oxide layer, each with a distinct
oxygen diffusion coefficient: Tetragonal sub-layer, bulk oxide and pre-oxide (see FIG. 2). This allows to
better simulate the effect of the pre-oxide as well as the oxide dissolution process.
This approach requires the knowledge of the oxygen diffusion coefficient in the different phases of
oxide. The diffusion coefficients in the monoclinic (m-Dx) and tetragonal (t-Dx) phases were selected from
the literature as a best estimate of the experimental data for a thermally grown oxide. Also required are the
fractions of tetragonal phase in both the bulk oxide (FTA) and the pre-oxide (FTAP) sub-layers. The t-ZrO2
helps to simulate the cubic behavior of the kinetics below ~1000 °C, whereas the fractions FTA & FTAP
allows the transition from the monoclinic to the tetragonal structure in the oxide as the temperature increases.
As experimental values of these functions were not found in the literature, they had to be determined
empirically by fitting the package [m-Dx, t-Dx, t-ZrO2 and FTAs] with the aim to obtain a good code-to-data
agreement of the oxidation kinetics.

Management of the layer systems (sequences) and possible transitions between them

The earliest code version DIFFOX 1.0 (one-sided oxidation only) was able to manage the basic layer
sequences #1 to #4 only, including the transition between them:
#1: α-Zr + ZrO2
#2: (α+β)-Zr + α-Zr + ZrO2
#3: β-Zr + α-Zr + ZrO2
#4: β-Zr + (α+β)-Zr + α-Zr + ZrO2
The implementation of the two-sided oxidation into the latest DIFFOX 1.3 version increased the
complexity of the code. The maximum number of simulated reaction layers within the cladding wall has
increased up to 7:

[Inner ZrO2 + α-Zr + (α+β)-Zr + β-Zr + (α+β)-Zr + α-Zr + outer ZrO2]

The total number of simulated layer systems (sequences) exceeded 40 and the total number of the
programmed transitions between the layer systems climbed over 100, most of them were tested. There is a
considerable effort to cover all the possible layer sequences within DIFFOX that may physically form in a
Zircaloy cladding. At present, certain layer sequences still remain to be programmed.

Testing of the DIFFOX code capabilities

The early versions of the DIFFOX code were widely tested in the one-sided configuration in comparison
with various experimental data found in the literature.
Under isothermal oxidation of as-received cladding, a reasonable agreement was obtained against
Leistikow data (KfK) over the entire temperature range ~650-1400 °C for the growth of oxide and alpha
layers thickness and weight gain. A fair agreement of O profile prediction was obtained in comparison with
(few) available measurements.
Under transient oxidation a reasonable agreement was obtained for most simple transients with heating
& cooling through the α/β transus by modeling the (α+β)-Zr and β-Zr layers appearance & disappearance.
For a pre-oxidized cladding subsequently isothermally oxidized, or heat treated under inert gas
atmosphere, in the 800-950°C temperature range, code predictions of the oxide thickness variation and
oxygen concentration profile appeared in a fair agreement with partially available (proprietary) data. Oxygen
diffusion from an initial corrosion layer in the underlying metal appears well predicted by the code.
The aim of testing the current DIFFOX 1.3 version is to demonstrate the ability of the code to simulate
both the two-sided oxidation and the oxidation of the inner cladding surface only. The test matrix is
composed of a sub-set of all the possible layer sequences. It includes the ability of the code to treat both the
as-received and the pre-oxidized cladding. All the reaction layers in the programmed layer sequences can
appear or disappear according to the actual temperature, extent of the oxidation (consumption of the layer) or
the availability of the oxygen flux at the cladding surfaces.

Experimental
Materiel and equipments

The specimens used in this study were cut from low tin AFA-2G stress relieved annealed (SRA) Zircaloy-4
industrial cladding tubes, provided by AREVA-NP. Composition of the alloy is given in TABLE 1. Outer
diameter and wall thickness of the tubes are 9.5 mm and 570 µm respectively. Open samples were used
leading to two side oxidations.
For the low temperature pre-oxidation, 100 mm long cladding samples were pre-oxidised in a tubular
resistive furnace in a pure oxygen flow at 500°C. For the high temperature oxidations, samples were oxidised
in a vertical resistive furnace in a steam + argon flow and water-quenched by dropping into a water bath
(FIG. 3). The argon and steam flow rates were respectively 2 Nl.min-1 and 100 g.h-1 (50% vol. Ar and 50%
vol. steam).
To qualify the furnace and the oxidation protocol, results obtained in the laboratory at 900, 1000, 1100
and 1200°C on Zy-4 as-received cladding were compared to published data [9-13] (see FIG.4). In this figure,
the Cathcart-Pawel correlation is reported for 1000, 1100 and 1200°C. At 900°C, the parabolic CP
correlation is known to be no more valid. Thus, a cubic law is fitted to the 900°C literature data. Our results
appear to be in good agreement with the published data, which confirms the relevance of the experimental
protocol adopted for this study.
Weight and length of the samples were measured with an accuracy of 0.1 mg and 0.01 mm respectively,
before and after oxidation or annealing.
After each step of the preparation protocol, metallographic cuts were inspected by optical microscopy
(bright field and polarized light) and by scanning electron microscopy.
Radial oxygen concentration profiles and oxygen distribution maps were obtained by Electron Probe
MicroAnalysis (CAMECA SX-100). Prior the EPMA analysis, each sample was embedded in a conductive
resin with an as-received sample from the same Zy-4 batch. After mechanical polishing, a chemical etching
with a fluohydric acid colloidal silica suspension mixture was carried out and samples were immediately
introduced inside the microprobe vacuum chamber. Oxygen Kα line was measured with a W/Si multi-layer
synthetic crystal. Most of the profiles were performed along 200 µm long lines with 1 µm stage displacement
step. Maps were obtained from 100x200 µm² or 100x300 µm² surfaces with a stage displacement step of 1
µm.
Global hydrogen and oxygen contents were measured by the hot extraction technique (analyzer system
JUWE ON/H-mat 286): the samples are melted in a graphite crucible with a carrier gas passing through.
Hydrogen released from the sample is converted into H2O and measured using a catharometric cell, while
oxygen, converted to CO2 by reaction with the graphite crucible, is detected in an infrared absorption cell.
Measurements are repeated at least three times on small pieces of few tens of mg for each sample.

Steam oxidation of pre-oxidised versus bare samples

The DIFFOX code allows simulating the influence of a pre-existing oxide distinguishing up to three zones
within the oxide layer: a tetragonal sub-layer, the bulk high temperature oxide and if present, the pre-existing
low temperature oxide sub-layer. The oxygen diffusion coefficients of the different zones are different,
depending on their monoclinic and tetragonal fractions. To validate the DIFFOX pre-oxide model and its
ability to predict pre-oxide chemical reduction, two series of experiments were carried out on pre-oxidised
samples: for the first series, samples were vacuum annealed at elevated temperature to study the dissolution
of the pre-oxide layer alone, for the second series of tests, pre-oxidised samples were high temperature steam
oxidised. As-received samples were also steam oxidised in order to establish reference data on bare material.
The temperature and duration (900°C, 6000 s) were chosen to better observe the elementary phenomena
rather than to be representative of LOCA. The emphasis was placed on the reproducibility of the results, tests
being conducted using two to four different samples to repeat each experimental condition and analysis being
performed at least on two metallographic cuts for each sample. Special attention was paid to statistical
representativeness of measurements, specifically for oxide thickness determination. Mean values and
standard deviation were calculated from 32 measurements (thickness measurements of the oxide and αZr(O)
layers at eight different angular locations at both outer and inner surfaces on two different metallographic
cuts).

Pre-oxidisation - Specimens were pre-oxidised in pure oxygen at 500°C for 10, 20, 30, 40, 50 and 60 days,
leading to low temperature oxide layer mean thickness of 11.0 ± 1.7, 19.0 ± 1.3, 30.6 ± 2.8, 41.9 ± 2.4, 57.5
± 1.9 and 68.8 ± 3.5 µm respectively. Pre-oxidised samples have a brown color, more or less uniform, except
for the samples pre-oxidised 10 days which shows some regions having the black color characteristic of sub-
stoechiometric zirconia. High magnification examination of the oxide layer surface reveals, for pre-oxide
layer thickness of 30 µm and above, a network of regularly spaced cracks, giving to the surface a snake skin
aspect. On the metallographies, these cracks correspond to radially penetrating cracks nucleated at the outer
surface of the samples. Such cracks have also been observed on Zy-4 fuel cladding corroded in pressurized
water reactors, but for very thick corrosion layers (80-100 µm) [14]. Metallographies also reveal that the pre-
oxidation layers are interspersed with many circumferential cracks, periodically spaced in the radial
direction, giving rise to a stratified structure (FIG. 5). The existence of similar stratified microstructure has
often been reported for in-reactor corrosion oxide grown on Zy-4 [14-16]. A typical radial spacing of about 2
to 3 µm between two stratums is reported. Similarly to in-pile conditions, radially oriented veins are also
observed in the micrographs. The veins location usually corresponds to regions far from radially oriented
crack within the oxide. These features, circumferential and radial cracks, veins, have strong similarities with
PWR irradiated Zy-4 corrosion layers [14-16]. From this point of view, the pre-oxide layers of the present
study are representative of in-reactor corrosion. However cicumferentially oriented cracks are probably
longer and with larger crack opening close to the metal/oxide interface, specifically for high pre-oxide
thickness.
Examination of the metallographies in polarised light reveal equiaxed grain structure in the metal. For
all pre-oxidation durations, the metal is fully recrystallised, which is consistent with the recristallisation
kinetics provided by Bouffioux [17]. This is also confirmed by the Vickers micro-hardness values in the
metal which are lower than in the as-received cladding. At last, pre-oxide layer thicknesses increase linearly
with pre-oxidation duration and hydrogen content measurement show that the hydrogen pick-up increases
with the pre-oxidation duration, without exceeding 100 wppm for 60 day pre-oxidation duration.

High temperature steam oxidation of bare samples (900°C, 6000 s) - Post-test metallographies show a dense
and uniform oxide layer (FIG. 6). The morphology of this compact oxide is typical of a pre-breakaway
oxidation regime. The mean oxide layer thickness is 18.5 ± 0.7 µm, whereas the thickness of the αZr(O)
layer revealed by the polishing is 34.5 ± 1.0 µm. The hydrogen pick-up4 during the steam oxidation is
negligible (~5 wppm), which is also consistent with a pre-breakaway oxidation regime.

High temperature vacuum annealing of pre-oxidised samples (900°C, 6000 s) - The sample with an initial 10
µm pre-oxide layer has, after vacuum annealing, a metallic bronze colour with small black islets. On the
metallographic cut, the remaining zirconia layer can barely be observed. The pre-oxide has been fully
converted into metal, but memory of this formerly existing layer remains in the form of stratified zone in the
outer part of the αZr(O) region (FIG. 7). For 20 and 30 µm pre-oxide, part of the original zirconia layer
remains at the outer surface after annealing, but, similarly with the 10 µm pre-oxide, a stratified metallic
region appears beneath the oxide, showing that part of the oxide has been converted into metal.
Macroscopically, the samples are bi-coloured, black and bronze. For the 40 µm thick pre-oxide layer, the
sample colour is uniformly black after annealing, but the same features than for the samples with 20-30 µm
pre-oxide are observed on the metallographies. Finally, for the 60 and 70 µm pre-oxide, no conversion of the
oxide into metal is evidenced, only partial reduction (in the chemical sense) is revealed by the black, uniform
colour of the sample surface, typical of sub-stoichiometric zirconia. Thickness of the αZr oxygen rich region,
formed by dissolution of oxygen from the pre-oxide, is constant (~35 µm) whatever the pre-oxide initial
thickness, and equivalent to the αZr(O) thickness measured on bare samples directly subjected to high
temperature steam oxidation.

High temperature oxidation of pre-oxidised samples (900°C, 6000 s) - For comparison, samples having a
20 µm pre-oxide were oxidised in steam in the same experimental conditions. Samples are bi-coloured with

4
The hydrogen pick-up fractions is calculated as the ratio of the hydrogen incorporated in the metal to the hydrogen
released by the Zr + 2H2O Æ ZrO2 + 2H2 reaction.
coexistence of light brown and darker brown regions. Examination of their surface at high magnification
reveals that the light brown regions are interspersed with a network of radial cracks, whereas radial cracks
are not visible in the darker regions (FIG. 8). Metallographies show that HT oxide has formed only in the
regions where radial cracks are present. In the region with no HT oxide, thickness measurements indicate
that the thickness of the pre-oxide has not decreased. In the region where a HT oxide has grown beneath the
pre-oxide, the HT oxide thickness is about 20-25 µm, which is slightly thicker than the HT oxide thickness
formed by oxidation of bare samples in the same conditions. Where the HT oxide forms, the thickness of the
αZr(O) layer is approximately uniform and thinner compared to the regions without HT oxide. This is due to
inwards motion of the oxide-metal interface which reduces the extent of the αZr(O) diffusion layer.

DIFFOX validation - DIFFOX code was evaluated in three different configurations: HT steam oxidation of
as-received samples, vacuum annealing of 20 µm pre-oxidised samples and HT steam oxidation of 20 µm
pre-oxidised samples. Radial quantitative oxygen concentration profiles were measured by EPMA for each
of these configurations and compared to calculated diffusion profiles.
FIG. 9 (a) shows that the O-profile is well predicted for as-received samples after steam oxidation. EPMA
experimental profiles show that the αZr oxygen rich region is approximately 70 µm thick, in agreement with
DIFFOX calculations. It is worthwhile noticing that on optical metallographies, the bright region
corresponding to the oxygen enriched layer was only about 35 µm thick. It means that the polishing process
reveals only the part of the α layer where the oxygen concentration exceeds a given threshold, estimated to
be about 2wt%.
FIG. 9 (b) shows the result for 20µm pre-oxide sample after vacuum annealing. A good code-to-data
agreement is observed for the radial extension of the αZr(O) region and the oxide dissolution is well
predicted (DIFFOX remaining pre-oxide thickness 10 µm versus 11.3 ± 1.9 µm for experimental
measurement).
FIG. 9 (c) and (d) present the O-profile measured on pre-oxidised samples after steam oxidation in the region
where the HT oxide has grown and in the region where the HT oxide was not formed respectively. Where the
pre-oxide is not protective, the αZr(O) thickness is over-predicted and the growth of ZrO2 is not predicted by
DIFFOX. Experimental results on pre-oxidised then steam oxidised samples indicate that the strong
difference in thermal expansion between the oxide and the metal may induce crack spreading and opening
during the oxidation, particularly for thick pre-oxide layers. These phenomena would favour the percolation
of steam thus resulting in high weight gain and is not modelled in the actual version of DIFFOX.

Effect of hydrogen on the oxygen distribution after a LOCA

Hydrogen absorbed in Zr-based alloys during the in-reactor service can influence the oxygen distribution
in the cladding after a LOCA transient, because it shifts the β/α+β and the α+β/α phase limits of the Zr-O
phase diagram toward high oxygen concentration, or in other terms toward low temperature [4, 5, 18-20]
(see FIG. 10). It also means that it increases the oxygen solubility in the βZr phase. However, experiments
addressing this effect are scarce, specifically for temperatures above 1000°C. To take into account this
hydrogen influence on the Zr-O phase diagram in the DIFFOX code, it was judged necessary to obtain
complementary quantitative data relevant to this problem.
For that purpose, AFA-2G Zircaloy-4 fuel cladding tubes were pre-hydrided up to ~600 wt ppm, then
oxidised at high temperature for oxygen loading, then long term annealed under vacuum to achieve oxide
dissolution and oxygen concentration homogenisation, to reach thermodynamical equilibrium. Oxygen
uptake was adjusted to fall either in the α+β or in the α domains of the Zr-O phase diagram after
homogenisation. Oxygen distributions were investigated by Electron Probe Micro Analysis (EPMA),
before and after the long-term homogenisation. Before homogenisation, assuming local thermodynamical
equilibrium, oxygen profiles in the radial direction give access to the β/α+β and the α+β/α limits at the
considered oxidation temperature: these limits are derived by measuring on the profile the oxygen
concentrations at the interface between the α layer and the prior-β region, in the β side and in the α side
respectively (see FIG. 12). After homogenisation, for bi-phased samples, the oxygen concentration
measured in prior-β regions, saturated with oxygen, gives the oxygen solubility limit in the β-phase at the
annealing temperature, that is the β/α+β limit, while the oxygen concentration measured in α regions
gives the α+β/α limit. For mono-phased samples, an attempt to determine the α to β phase transformation
temperature by calorimetry has been made. These experiments, not fully completed, are not discussed
here.
The sample preparation protocol used is a 4 step process:
1 – Hydrogen loading is performed on 50 cm long cladding segments by the electrolytic route at
EDF-Les Renardières [21]. A 600 wppm concentration is targeted, corresponding to a typical Zircaloy-4
end-of-life hydrogen load. Total loading duration is 160 h (at room temperature), followed by 24 h
annealing at 430°C. Tubes are cut into ~16 cm long segments and samples for hydrogen content
measurements (by hot extraction) are taken at each end, thus at 4 different locations of the 50 cm tubes.
Values in the range 574-640 wppm are obtained.
2 – Pre-homogenisation in the β domain: tubes are cut into 2 cm long samples, sealed under vacuum
in quartz vials, heat-treated at 1050°C (thus in the βZr domain) for 5 min and cooled down in the furnace
by turning it off, for full homogenisation of the H concentration and texture elimination. For each 2 cm
segment, a small ring is cut after the β-treatment for H and O contents determination, both by hot
extraction. Hydrogen and oxygen contents are thus determined individually for each sample.
Metallographic examinations are also performed on few samples and a typical microstructure obtained
after the β heat treatment is shown in FIG. 11.
3 – High temperature oxidation in steam: for oxygen loading, double side oxidations are performed
in the vertical furnace in flowing steam, at 1000, 1100 and 1200°C. Oxidation duration are adjusted to
reach a given weight gain. 3 different values of the weight gain were initially targeted, corresponding to
1.3, 2 and 5 wt% mean oxygen content, chosen to fall, after long term annealing, either within the α+β
domain (1.3 and 2 wt%) or within the αdomain (5 wt%) (cf. FIG. 10). Here, the expected effect of
hydrogen on the position of the phase boundaries is taken into account. The Cathcart-Pawel correlation for
Zy-4 high temperature steam oxidation was used for calculation of the oxidation times, but it appeared
that faster kinetics were observed with pre-hydrided samples, maybe because the electrolytic hydrogen
loading induces a strong degradation of the surface state. Oxidation durations were thus adjusted to also
account for this phenomenon. Finally, O-contents between 1.1 and 8 wt% have been obtained (see
TABLE 2). Samples are water-quenched after oxidation. Post-quench hydrogen content is again
measured for each sample by hot extraction. Hot extraction is here not effective for oxygen because
temperature of the hot extraction apparatus is below the melting point of zirconia. Microstructure of the
samples is investigated by metallography.
4 – High temperature homogenisation: samples are individually sealed under vacuum in quartz vial
and heat treated in the same vertical furnace, at 1000, 1100 or 1200°C. Annealing durations are 10h at
1000°C and 3h at 1100 and 1200°C (see TABLE 2). They were determined from previous experiments at
CEA [21]. When a bi-phased sample is expected, the vial is drop into water and immediately broken to
achieve fast quenching of the sample. For α mono-phase samples, cooling is done by simply turning off
the furnace. Hydrogen content is also systematically measured after the annealing. When oxygen loaded
above ~1.5 wt%, samples are extremely brittle after annealing, and it is thus difficult to avoid loss of small
fragments, specifically for quenched samples. Weight gain measurements are then not consistent.
Fortunately, hot extraction is here applicable for oxygen mean content determination because the oxide is
fully reduced (in the chemical sense) after annealing. EPMA is used to check the homogeneity of the
oxygen distribution and for quantitative determination of its concentration within each phase.

Results
Main results regarding the H and O global content evolution through step 2 to 4 of the elaboration process
are summarised on TABLE 2. Hydrogen content after the pre-homogenisation at 1050°C annealing varies
from sample to sample, which may be explained by axial heterogeneity of the hydrogen distribution along
the initial 50 cm long segment. Values are in the 542 - 787 wt ppmn range, to be compared to the
measurements performed by EDF at each end of the 16 cm long segments, which were in the 574-645 wt
ppm range. The measurements on 2 cm segments thus show a higher scattering, however they indicate
that there is probably no significant variation of the hydrogen content during the 5 min vacuum annealing
at 1050°C. Regarding oxygen, hot extraction data are here in good agreement with the weight gain results,
showing that the uptake during this pre-homogenisation step is significant, generally on the order of 800-
1000 wt ppm and up to 1500 wt ppm.
After the HT steam oxidation, the hot extraction results show no significant H pick-up. Specifically,
it means that the oxidation conditions are well controlled, with a high enough steam flow rate to avoid
local H2O starvation, and that no breakaway oxidation regime is encountered. This is confirmed by
metallographies, where a columnar, compact and adherent oxide layer is always observed.
 After the long-term annealing, strong dispersion of the H content measurements for a given sample is
sometimes observed, as revealed by the rather high standard deviation values. Few samples seem to be
affected by significant hydrogen pick-up during annealing. There is no obvious reason for such pick-up,
and the explanation may be the following: because of strong embrittlement, α grains are lost during
sampling for hydrogen dosage, thus enhancing the β fraction, known to be strongly enriched with
hydrogen (hydrogen partitioning [5]). Concerning the oxygen load, the hot extraction technique gives
values rather coherent with the values determined by weight gain before the homogenisation process. It
means that there is no significant variation of the oxygen load during the long-term vacuum annealing. As
the uncertainties are sometimes rather high for oxygen with the hot extraction method, it is preferable to
retain the weight gain data as the reference value for the oxygen load.
EPMA results: an example of EPMA oxygen profile obtained after oxidation at 1200°C and
quenching is given on FIG. 12. The profile is superimposed to a back-scattered electron image of the
region where it has been acquired, and is compared to the oxygen diffusion profile calculated with the
DIFFOX code. Under-prediction of the αZr(O) layer thickness by the code may be explained by. Cette
tendance a été observée aussi aux autres températures (1000 et 1100°C) et à peu près pour tous les ech.
Est-ce que cela n’indique pas que le coeff de diffusion dans DIFFOX est trop faible, mais ce n’est pas en
accord avec ce que disait Claude, à savoir que le coef de diff depend peu de la teneur en H. Peut-on alors
expliquer cela par une sur-estimation dans DIFFOX de la limite de solubilité dans b ? Une autre
explication ? Dotted lines in FIG. 12 show how experimental oxygen concentration profiles can be used to
determine the β/α+β and the α+β/α limits, which are given by the oxygen concentrations close to the
α/β interface, in the β side and in the α side respectively. It has to be pointed out that uncertainty
associated to this method is rather large because the measurement has to be done close to the α/β
interface, thus it can be affected by the instrument lateral resolution, and averaging over a given area
cannot be used. TABLE 3 gives the values determined in this approach. Each value is an average of
values measured for all samples oxidised at a given temperature. Better accuracy is obtained when
analysing the homogenised bi-phased samples, measuring the oxygen concentration in O-saturated β
regions and in equilibrated α regions. Samples 15 and 19 could not be used for metallography after
homogenisation because they were too brittle. Finally, 6 homogenised samples were investigated by
EPMA, 2 for each annealing temperature. Oxygen, iron and chromium maps, as well as oxygen radial
profiles were acquired. An example of results is presented in FIG. 13. Maps and profiles are used to check
for the homogeneity of the α and prior-β regions identified on the back-scattered electron images. Then,
for each region, oxygen concentrations are accurately determined by point analysis. The electron beam is
defocused to be less sensitive to short range fluctuations and 5 to 10 measurement points per phase,
randomly distributed on the metallographic cut, are acquired and averaged. Edges, affected by polishing
problems, are avoided. Results are given in TABLE 4 for each bi-phased sample investigated.
The concentration limit data points obtained in this work before and after the long-term
homogenisation, for the β/α+β limit and for the α+β/α limit, are plotted on FIG. 14, which represents the
Zy-4-rich portion of the Zy-4-O pseudo-binary phase diagram. The data plotted for non-homogenised
cladding are average values over six samples oxidised at the same given temperature, while for
homogenised samples, each individual value is plotted. Comparison is made with the Chung & Kassner
limits for non-hydrided Zircaloy-4 [22]. Literature data obtained at low temperature for the α+β/α limit
with ~600 wt ppm hydrogen loaded Zircaloy-4 are also plotted. The present study confirms, in the
investigated temperature range, that the presence of hydrogen shifts the phase limits towards higher
oxygen concentrations (or lower temperatures). The dotted lines show the β/α+β and the α+β/α limits
proposed from this study. The β/α+β limit is obtained by linear regression on the values measured on
homogenised bi-phased samples. For the α+β/α limit, dispersion of the data points is high, thus empirical
fitting has been performed.

Conclusions

References
1. Barré, F., C. Grandjean, M. Petit, and F. Arreghini, Fuel Behavior under LOCA and
RIA and its implication on the current safety criteria, in Eurosafe Meeting. 2009:
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Cladding", Zirconium in the Nuclear Industry: 4th International Symposium, ASTM
STP 681, 1979, p. 479-496.
3. Chung, H.M., A.M. Garde, and T.F. Kassner, Mechanical Properties of Zircaloy
containing Oxygen, ANL-77-10, Argonne National Laboratory, 1976.
4. Brachet, J.C., L. Portier, T. Forgeron, J. Hivroz, D. Hamon, T. Guilbert, T. Bredel, P.
Yvon, J.P. Mardon, and P. Jacques, "Influence of Hydrogen content on the α/β phase
Transformation and on the Thermal-mechanical Behavior of Zy-4, M4 and M5 Alloys
During the First Phase of LOCA transient", Zirconium in the Nuclear Industry: 13th
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Waeckel, and J.-P. Mardon, "Hydrogen Content, Preoxidation, and Cooling Scenario
Effects on Post-Quench Microstructure and Mechanical Properties of Zircaloy-4 and
M5 Alloys in LOCA conditions", Zirconium in Nuclear Industry: 15th International
Symposium, ASTM STP 1505, Sunriver, Oregon, 2008, p. 91-118.
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7. Waeckel, N., "Fuel Safety Research at EDF ", FSRM Meeting, Tokai, 2005, p.
8. Hofmann, P., H.J. Neitzel, and E.A. Garcia, Chemical Interactions of Zircaloy-4
Tubing with UO2 Fuel and Oxygen at temperatures between 900 and 2000°C
(Experiments and PECLOX Code), 1988.
9. Brachet, J.C., J. Pelchat, D. Hamon, and R. Maury, "Mechanical Behaviour at Room
Temperature and Metallurgical Study of low-tin Zy-4 and M5TM (Zr-NbO) Alloys after
Oxidation at 1100°C and Quenching", Proceedings of the Technical Committee
meeting, Halden, Norway, 2001, p. 139-158.
10. Hózer, Z., C. Gyori, L. Matus, and M. Horváth, "Ductile-to-Brittle Transition of
Oxidised Zircaloy-4 and E110 Claddings", Journal of Nuclear Materials, Vol. 373(1-
3), 2008, p. 415-423.
11. Kawasaki, S., T. Furuta, and M. Suzuki, "Oxidation of Zircaloy-4 under High
Temperature Steam Atmosphere and its effect on Ductility of Cladding", Journal of
nuclear science and technology, Vol. 15(8), 1978, p. 589-596.
12. Ozawa, M., T. Takahashi, T. Homma, and K. Goto, "Behavior of Irradiated Zircaloy-
4 Fuel Cladding under simulated LOCA conditions", Zirconium in the Nuclear
Industry: 12th International Symposium, ASTM STP 1354, Toronto, Canada, 2000, p.
279-299.
13. Billone, M., Y. Yan, T. Burtseva, and R. Daum, Cladding Embrittlement During
Postulated Loss-of-Coolant Accidents, NUREG-CR-6967, US-NRC, 2008.
14. Bossis, P., D. Pêcheur, K. Hanifi, J. Thomazet, and M. Blat, "Comparison of the high
Burn-Up corrosion on M5 and low tin Zircaloy-4", Zirconium in the Nuclear Industry,
14th International Symposium, ASTM special technical publication, Vol. 1467, 2006,
p. 494-524.
15. Yilmazbayhan, A., E. Breval, A.T. Motta, and R.J. Comstock, "Transmission electron
microscopy examination of oxide layers formed on Zr alloys", Journal of Nuclear
Materials, Vol. 349(3), 2006, p. 265-281.
16. Busser, V., Mécanismes d'endommagement de la couche d'oxyde des gaines de
crayons combustible en situation accidentelle de type RIA. 2009, Institut National des
Sciences Appliquées: Lyon.
17. Bouffioux, P. and L. Legras, "Effect of Hydriding on the Residual cold Work Recovery
and Creep of Zircaloy-4 Cladding Tubes." Light Water reactor Fuel Performance,
Park City, USA, 2000, p.
18. Erickson, W.H. and D. Hardie, "The Influence of Alloying Elements on the Terminal
Solubility of Hydrogen in α-Zirconium", Journal of Nuclear Materials, Vol. 13(2),
1964, p. 254-262.
19. Yamanaka, S., T. Tanaka, and M. Miyake, "Effect of oxygen on hydrogen solubility in
zirconium", Journal of Nuclear Materials, Vol. 167, 1989, p. 231-237.
20. Moalem, M. and D.R. Olander, "The high-temperature solubility of hydrogen in pure
and oxygen-containing Zircaloy", Journal of Nuclear Materials, Vol. 178, 1991, p.
61-72.
21. Blat, M. and D. Noel, "Detrimental role of hydrogen on the corrosion rate of
zirconium alloys", 11th International Conference on Zirconium in the Nuclear Industry,
ASTM-STP 1295, Garmisch-Partenkirchen, Germany, 1995, p. 319-337.
22. Chung, H.M. and T.F. Kassner, "Pseudo-binary Zircaloy-Oxygen Phase Diagram",
Journal of Nuclear Materials, Vol. 84, 1979, p. 327-339.
TABLE 1: Chemical composition of the Zy-4 batch used in this study
Sn (wt%) Fe (wt%) Cr (wt%) O (wt%) H (wt ppm)
1.30 0.21 0.10 0.12 10
 TABLE 2: Oxygen and hydrogen global contents measured after pre-homogenisation in the β-domain, after steam oxidation and after homogenisation
sample After step 2 (annealing 5 min at 1050°C) After step 3 (HT steam oxidation) After step 4 (HT homogeneisation)
# O (wt%) O (wt%) H (wppm) Toxid. t (s) O (wt%) H (wppm) T (°C), t (h) O (wt%) H (wppm) Cooling Mono or
(1) (2) (2) (°C) (3) (2) (2) (2) (4) bi-phased
9 0.198 0.217 ± 0.031 772 ± 38.9 1000 104 3.32 746 ± 17.5 1200, 3h 3.92 ± 0.67 808 ± 12.7 Q αZr
11 0.207 0.236 ± 0.152 696 ± 15.7 1000 50 1.65 670 ± 7.8 1200, 3h 2.28 ± 0.29 703 ± 21.1 Q α+β
12 0.193 0.180 ± 0.022 626 ± 6.7 1000 50 3.10 649 ± 5.1 1200, 3h 3.82 ± 0.28 621 ± 14.8 Q αZr
13 0.203 0.205 ± 0.055 620 ± 7.2 1000 40 2.90 626 ± 15.9 1200, 3h 3.80 ± 0.01 607 ± 30.4 Q α+β
14 0.198 0.222 ± 0.041 631 ± 17.6 1000 30 1.62 637 ± 3.6 1100, 3h 1.79 ± 0.11 635 ± 4.0 Q α+β
15 0.174 0.316 ± 0.070 621 ± 12.0 1000 30 1.78 623 ± 2.6 1000, 10h 1.54 ± 0.29 720 ± 29,5 Q α+β
16 0.213 0.281 ± 0.002 609 ± 7.5 1000 30 1.13 621 ± 5.3 1000, 10h 1.03 ± 0.13 633 ± 15.6 Q α+β
17 0.270 0.286 ± 0.092 712 ± 19.9 1100 40 3.92 684 ± 3.5 1200, 3h 4.32 ± 0.34 683 ± 57.4 N αZr
18 0.274 0.233 ± 0.03 658 ± 16.3 1100 30 3.13 644 ± 3.5 1100, 3h 2.89 ± 0.23 685 ± 23.7 Q αZr
19 0.274 0.232 ± 0.034 641 ± 3.2 1100 30 2.81 611 ± 4.9 1200, 3h 2.35 ± 0.14 613 ± 20.5 Q α+β
20 0.234 0.223 ± 0.002 641 ± 12.8 1100 30 2.46 623 ± 4.5 1000, 10h - 903 ± 21.1 Q α+β
21 0.229 0.199 ± 0.037 639 ± 7.2 1100 30 2.51 517 ± 5.7 1000, 10h 2.18 ± 0.08 631 ± 17.2 N αZr
22 0.238 0.132 ± 0.051 654 ± 11.1 1100 30 2.52 631 ± 8.1 1100, 3h 2.39 ± 0.22 675 ± 10.7 Q α+β
23 0.218 0.240 ± 0.119 643 ± 15.2 1100 30 3.15 628 ± 8.2 1100, 3h 2.52 ± 0.08 651 ± 37.8 N αZr
24 0.228 0.186 ± 0.010 787 ± 14.8 1200 100 6.81 737 ± 17.2 1200, 3h 4.68 ± 0.30 717 ± 29.4 N αZr
25 0.229 0.172 ± 0.003 661 ± 15.9 1200 100 7.99 617 ± 8.0 1200, 3h 5.66 ± 0.66 729 ± 6.4 N αZr
26 0.120 0.242 ± 0.019 599 ± 0.6 1200 60 5.60 - 1100, 3h 3.26 ± 0.12 603 ± 21.1 N αZr
27 0.209 0.243 ± 0.088 570 ± 1.4 1200 50 6.22 620 ± 29.2 1100, 3h 4.79 ± 0.19 829 ± 57.2 N αZr
28 0.199 0.197 ± 0.012 573 ± 11.0 1200 40 6.24 645 ± 6.1 1000, 10h 4.45 ± 0.31 825 ± 113 N αZr
29 0.192 0.144 ± 0.001 562 ± 4.0 1200 40 5.65 549 ± 6.6 1000, 10h 3.96 ± 0.28 605 ± 13.0 N αZr
30 0.209 0.230 ± 0.083 542 ± 10.4 1200 40 5.89 523 ± 6.5 1000, 10h 4.19 ± 0.10 673 ± 48.3 N αZr

(1) from weight gain, including the initial 0.14 wt% of the Zy-4 batch.
(2) hot extraction. Uncertainties are standard deviation over the measurements.
(3) from weight gain, including the oxygen already present after the β-treatment.
(4) Q = quenched, N = cooled into the furnace, by turning it off.

.
TABLE 3: Mean values of oxygen concentrations measured at the α/β boundary on EPMA oxygen radial
profiles, on the α side and on the β side.

T (°C) O in α (wt %) O in β (wt %)

1000 2.16 0.44
1100 2.33 0.76
1200 3.27 1.02

TABLE 4: Oxygen concentrations measured by EPMA on bi-phased, homogenised samples. Each value is
an average of 5 to 10 measurements point. Standard deviations are given.

Sample Annealing O in α O in β
# temp. (K) (wt %) (wt %)
11 1200 2.41 ± 0.14 0.9 ± 0.24
13 1200 2.43 ± 0.18 0.81 ± 0.58
14 1100 2.11 ± 0.20 1.01 ± 0.10
16 1000 1.76 ± 0.09 0.4 ± 0.05
20 1000 2.46 ± 0.17 0.52 ± 0.08
22 1100 2.53 ± 0.14 0.6 ± 0.17

14
 CYCLADES: Oxygen distribution Sub-program

EPMA O profile
Steam oxidation kinetics
•Bare vs pre-oxidized
•Hydrided vs fresh Zr-O phase
•Loading sequence (T(t)) αZr(O)-βZr(O)
diagram of
transient cooling
•Zr alloys hydrided Zr alloys

Modeling
Reference experiments
for DIFFOX validation
DIFFOX:
O diffusion in:
ZrO2, αZr(O), βZr(O)
Validation

CYCLADES Key mechanisms controlling Oxygen profile

Residual ductility the residual ductility at room temperature
program

FIG. 1—Action plan for the modeling and validation of DIFFOX diffusion code.

high-temperature oxide low-temperature oxide

tetragonal sub-layer

outer oxide surface

monoclinic (<850 °C)

(<1200 °C)

or monoclinic (<1100 °C)

mon + tet (850-1200 °C)
Metal

or
or mon + tet (>1100 °C)
tetragonal (>1200 °C)

t-ZrO2 bulk oxide pre-oxide

oxide (total ZrO2 thickness)

FIG. 2—DIFFOX 1.2: Model of the oxide microstructure grown on Zircaloy cladding.

15
 steam generator
Ar

sample holder

furnace
with alumina

sample

cooling bath

FIG. 3—Vertical furnace used for the oxidation at high temperature under steam flow

1200°C 1100°C 900 °C Hozer 2008 (KFKI)

900°C Kawasaki 1978 (JAERI)
200
1000°C Ozawa 2000 (NDC)
1000°C
1000°C Hozer 2008 (KFKI)
1000°C Billone 2008 (US-NRC)
Weight gain (g/m²)

150 1100°C Brachet 2001 (CEA)

1100°C Ozawa 2000 (NDC)
1100°C Hozer 2008 (KFKI)
1100°C Billone 2008 (US-NRC)
100
1200°C Ozawa 2000 (NDC)
1200°C Hozer 2008 (KFKI)
1200°C Billone 2008 (US-NRC)
900°C
50 900°C present study
1000°C present study
1100°C present study
1200°C present study
0
0 1000 2000 3000 4000 5000 6000
Durations (s)

FIG.4—Weight gain as a function of heat treatment duration for steam oxidation of as-received samples from
[9-13] and present results. Solid lines correspond to the Cathcart-Pawel correlation. Dotted line corresponds to
a cubic law fitted to the experimental data.

16
 100 µm

FIG. 5—Metallographies of a 70 µm pre-oxide sample (right: in polarized light, left: in bright light)

100 µm 100 µm

FIG. 6—Metallographies of as-received samples subjected to steam oxidation at 900°C during 6000s

High temperature vacuum anneal (6000 s at 900°C)

Visual
examination
of the tubular
samples

ρ−θ
metallograph
at outer
diameter

Duration
10 20 30 40 50 60
(days)

FIG. 7—Photographs and metallographies of pre-oxidised samples after vacuum annealing at 900°C during
6000s

17
 0.5 mm

25 µm

FIG. 8— Surface photography and metallographies of 20 µm pre-oxidised

and HT steam oxidised sample showing two types of region: Left: region with
HT oxide. Right: region without HT oxide

18
FIG. 9—Code-to-data comparisons for (a) as-received sample after steam oxidation, (b) 20 µm pre-oxidised
sample after vacuum annealing, (c) and (d) 20 µm pre-oxidised sample after steam oxidation: (c) region without
HT oxide, (d) region with HT oxide.

Expected influence
1500
=0

of 600 wt ppm H
[H]

1400
α+β Zr
1300
βZr
Temperature (°C)

1200
1100
1000
900 αZr
800
α+β Zr expected
700 α Zr expected
600
500
1.3 2.0 5.0
0 1 2 3 4 5
O (wt%)
FIG. 10—Expected influence of hydrogen on the
β/(α+β) and α
 +β)/α phase limits of the Zr-O phase
diagram.

19
 FIG. 11—Polarized light
metallography of a pre-hydrided (600
wt ppm) Zy-4 sample after the pre-
homogenisation step in the β domain (5
min at 1050°C).

25
Measured O profile
DIFFOX simulation
Oxygen concentration (wt%)

20

Oxide αZr Prior-βZr

15

10

α/(α+β)

(α+β)/β 0
-50 0 50 100
Distance to metal/oxide interface (µm)

FIG. 12—Zy-4 cladding pre-hydrided at 600 wt ppm and

oxidised 60s at 1200°C. BSE image, oxygen profile measured
by EPMA and calculated diffusion profile. Dotted lines
indicate where the α/(α+β) and the (α+β)/β oxygen
concentration limits are measured on the experimental
profile.

20
 Oxygen concentration (wt %)
3

prior-βZr
200 µm
2

αZr(O)
1

0
0 50 100 150 200 250 300
Distance to the external surface (µm)

Fe

Cr

FIG. 13—Sample #20, loaded with 2.46 wt% oxygen and

homogenised at 1000°C. Back-scattered electron image, and
oxygen, iron and chromium EPMA maps. The line scanned
for the oxygen concentration profile superimposed on the
high magnification BSE image is indicated by the dotted line
on the oxygen map. Locations of EPMA point analysis for
quantitative determination of the oxygen content of the α
and prior-β regions are indicated by triangles and circles
respectively.

1400

1300

1200

1100

1000
T (°C)

900
This work, on oxydised
800
This work, on homogenised (Provisoi)
This work, on homogenised
700
Erickson ~600 ppmH (1964)
600 Brachet 600 ppm (2001)
Chung & Kassner, 0 ppm H (1979)
500
0 1 2 3 4
O concentration (wt%)

FIG. 14—Zy-4-rich portion of the Zy-4-O pseudo

binary phase diagram. Dotted lines are the
β/α+β and the α+β/α limits proposed from this
work for 600 wt ppm hydrogen loaded zircaloy-4.

21