Journal of Nuclear Materials 95 (1980) 303-306
0 North-Holland Publishing Company
LETTER TO THE EDITORS - LETTRE AUX REDACTEURS
PRODUCTS AT THE SURFACE OF ZIRCALOY CLADDING UNDER LOCA CONDITIONS
Zircaloy cladding might experience a burst during
a loss-ofcoolant accident (LOCA) in light water reac-
tors. If so, the inner surface as well as the outer sur-
face of the cladding would be oxidized by steam
invading from the rupture during the subsequent
heat-up stage of the LOCA transient. The oxidation
at the inner surface of the burst cladding will likely
occur in a mixed gas environment of steam and hy-
drogen, for hydrogen generated by the Zircaloy-
steam reaction would hardly have time to flow out to
the outside of the burst cladding. It is, therefore,
questionable whether the oxidation behaviors at the
inner surface of the burst cladding will be the same as
that at the outer surface.
We have conducted rod-burst/oxidation tests to
determine the oxidation behavior at the inner surface
of the burst cladding. The Zircaloy claddings used in
this experiment are the same size and chemical com-
position as those in commercial pressurized water
reactors. The cladding material has the following
chemical composition: 1.46% Sn by weight, 0.22%
Fe, 0.10% Cr, 80 ppm by weight of C, 20 ppm H,
18 ppm N, 1400 ppm 0 and balance Zr. A Zircaloy-
clad fuel rod filled with alumina pellets to simulate
fuel was pressurized by argon gas, and then plunged
into an electric furnace in a steam with flow rate of
18.4 g/m’s. The specimen was burst at around 1150
K, and subsequently exposed to steam for 420 s at
1273 K.
Fig. 1 shows a typical example of oxide layers at
both outer and inner surface of the burst cladding.
The dense oxide layer is seen at the outer surface,
while the porous and thicker one is seen at a location
away from a rupture opening on the inner surface.
The porous layer can also be found at a location away
from a rupture opening in the axial direction. The
microstructures of Zircaloy oxidized at the inner sur-
face are, moreover, characterized by the wavy and
laminated oxygen-stabilized (Yphase, when the porous
oxide layer makes its appearance.
We have conducted the identification of products
303
in the oxide layers by means of an X-ray diffrac-
tometer using crystal-monochromated CuI&r radia-
tion. The scintillation counter was step-scanned at the
rate of O.O2’/min in the range of scattering angles
from 15 to 120’ at room temperature. Fig. 2 shows
the X-ray intensity profiles of oxide layers at both
outer and inner surface of the burst cladding. The dif-
ference in intensity profiles between outer and inner
surface can be observed in this figure. For the pro-
ducts in oxidized Zircaloy, the lattice spacing data
observed and calculated from the literature [l-3] are
listed in table 1. The dense product at the oufer sur-
face, which is harder than that at the inner surface,
consists mostly of monoclinic ZrOa form; the X-ray
pattern agrees very well with that reported by Mccul-
lough [l]. The porous product at the inner surface
consists mainly of a mixture of zirconium oxides,
namely, the monoclinic form and the tetragonal form
which has been reported by Teufer [2]. The diffrac-
tion lines of the face-centered cubic form can also be
found in the oxide at the inner surface of the burst
cladding, as shown in fig. 2. This form, which also has
a 462.0 pm lattice spacing, agrees with that of ZrO
reported by Wyckoff [4]. The ZrC and ZrN as com-
pared to ZrO are similar in lattice spacing. Nickel et
al. have reported that the ZrC form has a 469 pm lat-
tice spacing [S]. Baker has reported that the ZrN
form has a 457 pm lattice spacing [6]. We then
undertook Auger electron spectroscopy, which has
the advantage of analysis for light elements, to
determine the crystal form precisely, though these
elements cannot by any possibility contaminate the
specimen. Fig. 3 shows Auger electron spectra from
the metal-oxide interface cleaned by argon-ion bom-
bardment in the segment, which was sectioned from
the bulged section of the burst cladding, showing the
intensity profiles of the face-centered cubic form.
The major peak of nitrogen at 380 eV cannot be
observed in any of the spectra in this figure. That of
carbon at 273 eV decreases with increasing cleaning
time, while that of oxygen at 503 eV as compared to
Fig. 1. Cross-section of a simulated fuel rod burst, oxidized in flowing steam (burst at 1150 K and held at 1273 K for 420 s; steam
flow rate: 18.4 g/m2s),
carbon increases with the cleaning time. From the
facts described above, we have identi~ed the product
at the metal-oxide interface as a ZrO. Therefore, the
products at the inner surface of the burst cladding are
a mixture of monoclinic and tetragonal ZrOz and
zro.
The stabilization ~ie~hanism of the metastable
tetrag~n~ form has been studied by many investiga-
tors [7-9). The stab~~ation of high tem~rature
structures has actively been studied as a development
of refractory materials [IO-121. In oxidized zirco-
nium”base alloys, the presence of the metastabie
tetragomd form has been established under high com-
pressive stresses at the metal-oxide interface [ 13J, ox
under the presence of hydrogen in an oxidizing
atmosphere [ 14f. Therefore, we performed chemical
analysis for hydrogen content in segments sectioned
from the burst cladding. The result indicted that
large contents of hydrogen absorbed by Zircaloy can
be analyzed in those segments which show a strong
intensity probe of the tetragonal form in the mixture
of oxides. It can, therefore, be concluded that the
presence of hydrogen generated by the Zircaloy-
steam reaction at the inner surface of the burst clad-
ding considerably influences the formation of the
mixture of oxides, for hydrogen at the inner surface
can hardly have time to flow out to the outside of the
burst cladding.
The oxidation behavior at the inner surface of the
burst cladding differs from that at the outer surface
in that hydrogen absorption by Zircaloy can occur
and a mixture of oxides can be formed at the surface.
If hydrogen should be absorbed by the Zircaloy clad-
ding, then degradation of mechanical properties of
 T. Furuta, H. Motohashi /Products at the surface of Zircaloy cladding 305

ZrO* ZlOS. Oxide layer at the outer surface

20 - 2lOD (TI (MI
(MI
2rOz

30 -
.s-1
. 2rO.
(MI Oxide layer at the inner surface
3 .. 2rOn
;, (Ml
u: . . DATA OF X-RAY DIFFRACTION
c
. .
2rO. Cu Km, 35kV 30mA
20- (T)
. .
. . :* 2rOz
" *, (MB
..
., . . 2rOp 2rO. Zr
2rO
2rOa IM) (M)
. IT)
10 -
l
: II

I I I I 1 I I 1 I I I
0-l
27 26 29 30 31 32 33 34 35 36 tf 39 40

Diffraction angle 20 deg

Fig. 2. X-ray diffraction intensity profiles of oxide layers at outer and inner surface of the burst cladding (burst at 1140 K and
subsequently exposed to steam for 420 s at 1273 K).

Table 1
Lattice spacing data observed and calculated from the literature (scattering angle, 20 : (27 -40”)

Observed Calculated

Various parts Matrix ZrOz (monoclinic) [l] ZrOs (tetragonal [2] ZrO (cubic) [ 31 Zr (hexagonal) [ 31
of surface

d(pm) 1 d(pm) I d(pm) I hkl d&W 1 hkl d(v) I hkl d(v) I hkl

318.9 VS 316.0 vs 111

297.7 S 299.5 S 101
286.0 S 284.0 vs Iii
280.4 M 279.8 S 100
264.0 M 263.5 W 002 264.7 M 111
262.0 W 262.0 M 002
260.0 M 002
258.0 W 258.3 VS 257.4 W 110 257.3 S 002
256.0 254.0 W 220
251.0 W 250.0 W 102
246.8 W 247.3 S 245.9 VS 101
233 VW 233.0 W 021
229 VW 229.2 W 220
221 W 221.0 W 221
213 VW 112
162.1 VW 220 189.4 VS 102
306 T. Furuta, H. Motohashi /Products at the surfhce of Zircalqy cladding

tion of the mixture of oxides associated with hydro-

gen absorption.
The authors wish to thank Drs. Y. Hamaguchi and
S. Kawasaki, Japan Atomic Energy Research Insti-
tute, for their helpful suggestions.

References

[l] J.D. McCullough and J.D. Trueblood, Acta Cryst. 12

E(eV)
Electron enerw
Fig. 3. Auger electron spectra from the metal-oxide
face in Zircaloy exposed to steam for 420 s at 1273 K.
the cladding will likely occur during a LOCA tran-
sient. Accordingly, it wi!l become a matter of great
concern to determine the mechanism of the forma-
(1959) 507.
[2] G.Teufer, Acta Cryst. 15 (1962) 1187.
[3] W.B. Peason, Handbook of Lattice Spacings and Struc-
ture of Metals (Pergamon, London, 1958) p. 1037.
[4] R.W.G. Wyckoff, Crystal Structures, Vol. 1 (lnter-
science, New York, 1963) p. 91.
[5] H. Nickel, 0. Inane and K. Luecha, 2. Metallk. 59
(1968) 935.
[6] T.W. Baker, Acta Cryst. 11 (1958) 300.
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Sci. 11 (1959) 31.
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-_j (91 T. Mitsuhashi, M. Ichihara and U. Tasuke, J. Am.
Ceram. Sot. 57 (1974) 97.
inter- [lo] H.G. Scott, J. Mater. Sci. 10 (1975) 1527.
[ 1 l] T.K. Gupta, J.H. Bechtold and R.C. Kuznicki, J. Mater.
Sci. 12 (1977) 2421.
[12] T.K. Gupta, F.F. Longe and J.H. Bechtold, J. Mater.
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[13] J.P. Pemsler, J. Electrochem. Sot. 112 (1965) 477.
[14] T. Nakayama and T. Koizumi, Trans. J. Japan Inst. Met.
31 (1967) 839.

Received 14 August 1980 Teruo Furuta * and Haruhiko Motohashi **

Japan Atomic Energy Research Institute, Tokai-mura,
Ibaraki-ken, Japan

* Division of Reactor Safety, JAERl.

** Division of Physics, JAERI.