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Journal of Nuclear Materials 202 (1993) 239-244

North-Holland

Improvement in oxidation resistance of Zircaloy-4
by surface alloying with a thin layer of palladium
G.A. Eloff a, C.J. Greyling a and P.E.Viljoen b
aAtomic Energy Corporation of South Africa Ltd., P.O. Box 582, Pretoria 0001, South Africa
b University of the Orange Free State, P.O. Box 339, Bloemfontein 9300, South Africa

Received 13 October 1992; accepted 18 December 1992

Economic considerations and environmental pressures have forced reactor operators world-wide to consider higher
burnup, to the extent that standard Zircaloy-4 fuel cladding is now approaching its design limitations. One of the main
factors limiting the safe in-reactor lifetime of PWR fuel is the waterside corrosion of the fuel cladding. In this investigation
the oxidation resistance of Zircaloy-4, surface alloyed with a thin layer of palladium by annealing in vacuum at 95O”C,was
studied. Short term oxidation in air shows a retardation of the transition to linear oxidation kinetics. It is argued that this
retardation is caused by the incorporation of intermetallic particles into the oxide layer which increases the ductility of the
oxide, thereby retarding the onset of cracking from the outside surface of the oxide layer.

1. Introduction
The performance of Zircaloy4 fuel cladding tubes
in pressurized water reactors (PWRs) all over the world
has been extremely satisfactory over the past two
decades. In the past decade, however, economic considerations have been forcing reactor operators to consider higher bumup levels of their fuel in order to
contain reload cost and to minimize reactor downtime.
An added attraction of higher burnup is that the
amount of spent fuel is accordingly reduced. The latest
PWRs are designed to operate at higher coolant temperatures than the previous generations of PWRs with
longer fuel cycles than before, which means that the
fuel is now required to withstand a much more hostile
environment for considerably longer periods [l].
It is generally accepted that waterside corrosion
(oxidation and hydriding) of fuel cladding represents
the single mosti important limitation on the safe in-reactor lifetime of fuel [2-41. The developments referred
to in the previous paragraph have spurred various
programs to develop alternative zirconium base alloys
capable of meeting the demands of reactor operators
through the next decade. Considerable improvements
in corrosion resistance have already been achieved
with new alloys such as ZirloTM (Zr-l%Nb-l%Sn0022-3115/93/$06.00

O.l%Fe) [5,6]. The search for better materials, meanwhile, continues unabated as economics and environmental concerns about nuclear safety keep the pressure up. This investigation was carried out with the
purpose of determining whether the oxidation resistance of Zircaloy-4 can be improved by surface alloying
with palladium.

2. Background
The effect of a small addition of one of the PGMs
to some alloys can be quite dramatic, as evidenced by
the significant improvement in corrosion resistance obtained by alloying pure titanium with a small amount of
palladium [7]. This effect, generally referred to as
cathodic modification or cathodic alloying, is normally
brought about by either adding a small amount of the
PGM to the alloy, or by ion implantation of the desired
PGM into the surface where the cathodic protection is
required [8,9].
The comparable chemical and metallurgical behaviour of titanium and zirconium suggests that addition of palladium to Zircaloy-4 may have a similarly
beneficial effect. Very little reference to any such work
can, however, be found in the literature. This is proba-

0 1993 - Elsevier Science Publishers B.V. All rights reserved

there is no more evidence of a separate surface layer after 4 h of annealing. It was essential to perform the annealing in vacua to contain the high affinity of zirconium for oxygen at elevated temperatures. Another sample of each group (A2-E2) was mounted end-on in resin. / improvement in oxidation resistance of Zircaloy-4 240 bly due to the results published by Dixon [lo] who found no improvement in the corrosion resistance of Zircaloy-2 enriched with small amounts of palladium. 3. 4 it appears that there is still a 3.2. were then separately vacuum-annealed at 950°C for 30 min. During oxidation the samples were periodically removed from the furnace and weighed to determine the oxide weight gain as a function of time. Auger electron spectroscopy line profiles The other two samples of each group (A3. The average cooling rate through the (a + p&phase was approximately 18 K/s. Sample preparation A number of 10 mm pieces were cut from a standard Zircaloy-4 fuel cladding tube in the cold-worked. Some grains in the inner band. stress-relieved condition. Fig. according to Schleicher [ll]. There is a clear distinction between the two types of microstructure. In fig. 2. surface alloyed with a 2 km thick palladium layer. 1.3. up to several microns into the bulk of the sample. Two AES line profiles. after vacuum annealing at 950°C for an hour (sample B2) (200 x 1. 1 to 3. 4.O.2.rn thick palladium layer was electroplated onto the surfaces of these samples. the zirconium/palladium interface is difficult to distinguish. After annealing the samples were quenched. 1. while the inner band consists mostly of equiaxed a-zirconium grains. They were divided into five groups of four each. In both cases.A. abraded down to 4000 grit finish. have also transformed to the WidmannstPtten structure. Microstructure One sample of each group (Al-El) was subjected to Auger line scan analysis over a cross section of the tube. As may be seen in fig. In fig. are shown in figs.A4E3. and these groups.G. inside a quartz tube which was evacuated to a vacuum of better than 10m4 Pa. 1. The microstructures of samples B2. 2. Eloff et al. respectively.1. From fig. 4 and 8 h. D2 and E2 are shown in figs./50% H. 1. Oxidation 4. Sample characterization . and the band of the Widmannstgtten structure is considerably wider than is the case of fig. to determine the depth distribution of palladium in the samples. The microstructures of these samples were then studied under a metallographical microscope. Cross section of a Zircaloy-4 tube. respectively. The outer bands of the zirconium matrix consists of a fine a-Widmannstltten structure with a high concentration of intermetallic precipitates on the sub-grain boundaries of the WidmannstHtten structure. A 2-p. designated Al-A4 through El-E4.E4) were oxidized at 450°C in a quartz tube furnace open to the atmosphere. respectively. Results 4. 3 it is shown that the bands of the WidmannstHtten structure are even wider and that several of the equiaxed grains throughout the inner band have also transformed. closer to the boundary between the two types of microstructure. 4 and 5. to room temperature by withdrawing the evacuated tube from the furnace. still in vacuum. both the zirconium and the palladium profiles are shown for scans from outside of the outer surfaces of the samples. Alloying pure zirconium with varying small amounts of palladium.Pd intermetallic precipitates. obtained on samples Al and Dl. Experimental procedure 3. I. and given a 15-s etch using a solution of 5% HF/45% HN0. brought about an improvement in corrosion resistance through anodic protection by galvanic corrosion of Zr. 3.

For Fig. clarity. Auger line scan of a cross section of sample Al. Oxidation The average weight gains of the five pairs of samples. after vacuum annealing at 950°C for 4 h (sample D2) (200 x 1. 1 ‘. occurs at a much higher weight gain for the palladium-treated samples. 4. Eloff et al. that group B has broken away to linear kinetics considerably earlier than group C. expressed as a function of the oxidation time at 450°C in air. which normally takes place at a weight gain in the vicinity of 30 mg/dm*. 2%. Cross section of a Zircaloy-4 tube. the palladium-treated samples oxidize more rapidly to a weight gain of approximately 15 mg/dm’. however. Cross section of a Zircaloy-4 tube. This transition. however. after which the oxidation rates slow down considerably up to the transition to linear oxidation kinetics. surface alloyed with a 2 km thick palladium layer. In fig. 7. The lowest overall weight gain was achieved by group B. which was annealed for 1 h.G. 2.. 6. showing a distinct palladium layer on the sample surface after 30 min of annealing at 950°C in vacuum. 5. which started breaking away to linear kinetics after about 180 . The highest average weight gain among the palladium-treated samples was achieved by group E. together with the weight gain curve (F) of two Zircaloy-4 samples in the as-received (cold-worked. Fig. stress-relieved) state. 4- 3.3. 4.. are compared to that of the as-received samples in fig.A. 5. distinct palladium min of annealing layer on the sample surface after 30 at 950°C. after vacuum annealing at 950°C for 8 h (sample E2) (200 x ). 6. the initial oxidation kinetics of two of the palladium-treated groups representing the highest and lowest average weight gains during the first 100 h. It is fairly evident. 3. are shown in fig. and started breaking away after approximately 350 h of oxidation at a weight gain of about 45 mg/dm*. surface alloyed with a 2 km thick palladium layer. which only started deviating after about 500 h of oxidation at a weight gain of approximately 53 mg/dm*. / Improvement in oxidation resistance of Zircaloy-4 241 7. These figures show that when compared to the as-received-group. it is obvious that the palladium layer has completely dissolved into the zirconium matrix during annealing. O0 i 20 40 60 60 POSKION 100 120 140 1’ (pm) Fig.

Average weight gain curves showing the initial oxidation kinetics for two sets of palladium-treated samples (curves A and B) and the as-received samples (curve F). however. 2 and 3 is a .5 at% at 1030°C [12]. Auger line scan of a cross section of sample Dl.A. The (a + P)/p-phase boundary temperature is lowered with increasing palladium content to a minimum of 755°C at 7 at% palladium. Error bars have not been included as they are smaller than the symbols in the graph. 5. showing complete dissolving of the initial palladium surface layer into the zirconium matrix after 4 h of annealing at 950°C in vacuum. This is confirmed by the dense agglomeration of intermetallic precipitates observed on the sub-grain boundaries of the a-Widmannstltten structure. Curve F represents the average weight gain of two “as-received” samples. It is therefore expected that the palladium which had gone into solution in p-zirconium during annealing. 6. Discussion The solid solubility of palladium in a-zirconium is virtually zero at room temperature and is still lower than 0. Eloff et al. 5. the solid solubility of palladium is almost two orders of magnitude higher and reaches a maximum of 11. which started 100 I I DI OXIDATION TlME (h) Fig. / Improvement in oxidation resistance of Zircaloy-4 242 0 50 100 150 POSITION 200 250 300 350 (pm) 0 I I I I I I I I 1 10 20 30 40 50 60 70 60 90 Fig. 1.2 at% at 800°C. In the P-phase. This is still considerably better than the performance of the as-received samples. The distinct boundary between the two observed types of microstructure observed in figs. h of oxidation at a weight gain of approximately 40 mg/dm*. OXIDATION TIME I 100 (h) Fig. would virtually completely precipitate in the form of one or more of the known Zr-Pd intermetallic compounds. 7.G. breaking away at the expected weight gain of 30 mg/dm’ which was reached after about 80 h. Average weight gain curves as indicated for groups A to E respectively.

From fig. The results obtained in this way correspond more closely to a fourth power rate law (n = 4) as can be seen in table 1.8 (I) the diffusion coefficient of palladium in B-zirconium was calculated to be 1. 5 one may assume a significant diffusion distance of approximately 200 pm after 4 h at 950°C. at least partially. and that the melting point of zirconium decreases almost linearly from 1852°C for pure zirconium to 1030°C at the eutectic point. Table 1 Kinetic parameters n. For the purpose of comparison. published results fit a cubic (n = 3) rate law which. [17] suggested that a homogenous distribution of fine precipitates. 6 was fitted to eq. k obtained by fitting data to eq. though many possible explanations have been offered.94 3.92 3. still remains without a solid theoretical base [14]. More often than not. such as is obtained by P-quenching.6 9. only the data points up to weight gains of 30 mg/dm* were used. Although the transition to linear oxide kinetics is still not fully understood. The formation of new oxide at this interface creates a radially outward pressure on the oxide layer. According to Nowok [19]. which is an order of magnitude higher than the self-diffusion coefficient of 95Zr in pure p-zirconium at this temperature [12]. (1) is the well-known parabolic rate law of Tammann. Using the well-known solution for Fick’s second law x=J2Dt.85 10. [18]. Douglass [16] has shown that the presence of impurity atoms increases oxide plasticity. The experimental data represented in fig. (1) Sample group A B C D E As received Annealing time (h) n k 0. and o-zirconium (the so-called Pilling-Bedworth ratio) is 1.86 3.6 9. Pilling and Bedworth [13] which indicates that oxide growth takes place by a simple diffusion mechanism. This is not surprising when considering that there is a eutectic point at 24. by cracks or pores in the oxide which develop as a result of the tensile stress in the outer part of the oxide layer [15]. This boundary represents the distance from the surface at which the palladium concentration falls below the value needed to cause complete transformation to the P-phase. In addition.4 x 10m8 cm’/s. The improvement in the oxidation resistance brought about by surface alloying Zircaloy4 with palladium is quite substantial.2 9.2 6. gives rise to the formation and maintenance of a fine-grained structure for the oxide layer. which means that the growing oxide is under a compressive stress at the metal-oxide interface. Eloff et al. The ratio between the molar volumes of ZrO. which depends on the atomic structure and the nature of the atomic bonding forces. Bangaru et al. however. this would benefit the formation of new oxide at the metal-oxide interface at the expense of internal oxidation of intermetallic precipitates within . An increase in oxide plasticity or ductility implies that the oxide should accommodate higher stress conditions by plastic deformation before cracking commences. presumably by enhancing dislocation mobility in the oxide matrix. a fine oxide grain structure implies a high diffusion rate for oxygen ions through the oxide layer. 243 (2) where n is the exponent which is characteristic of the rate law being followed.5 1 2 4 8 _ 3. and which is comparable to the self-diffusion coefficients of many metals close to their melting points.56. / Improvement in oxidation resistance of Zircaloy-4 manifestation of the concentration gradient created by the inward diffusion of palladium from the sample surfaces. This enhancement in dislocation mobility could be due to a lowering of the Peierls-Nabarro stress. A possible explanation for the delay of the transition to linear oxidation may be found by considering the role of intermetallic precipitates in preventing cracks in the oxide layer. as further annealing resulted in an earlier transition to linear oxidation kinetics. (2) by linearizing the model and applying a “least squares” fitting technique. The oxidation kinetics of zirconium-based alloys are usually described by a rate law equation of the general form (AW)” = kt.70 3. If n = 2 then eq. and can be associated with an extension of the protective nature of the oxide layer to a substantially thicker oxide. a view shared by Glazkov et al. as oxygen transport occurs mainly through grain boundary diffusion. it is generally accepted that this is caused.51 2.8 9. which results in a tougher oxide with improved crack resistance under tensile stress conditions.G. which eventually causes a tensile stress on the oxide-atmosphere interface.A.5 at% palladium on the zirconium-palladium phase diagram. The results suggest that the most favourable palladium surface concentration was obtained after 2 h of annealing.

Ottawa. J. Thornburg and R. eds. This retardation is ascribed to increased ductility of the oxide which allows a higher deformation tolerance before cracking.M. Staehle (Plenum Press. Ohio. Schemel. Wissenberg.R.S. Garzarolli. Report AECL 5548 (Atomic Energy of Canada Ltd. Mines Branch. Japan. Cox. 1976). Miller.W. V. Philadelphia. Wagner. Goldbeck. 325. 44 (1991) 47. . Senevat and P. EPRI J.G. Schleicher. Vienna. Dixon. F. Schlemmer. 158 [I91 J. Kilp. 1990) p. Symp. the 6. Ozer. Chem. Potgieter and M.H. A. Atomic Energy Review Special Issue no. Nowok. Picraux and H. Conclusion This investigation has demonstrated that the oxidation rate of Zircaloy-4 in air can be significantly reduced by surface alloying with a thin layer of palladium. Busch and J. Fontana and R. Electron. M. IAEA Report IWGFPT/34 (IAEA.vol. Nikulina and V. L. AEC-EURATOM Conf.F. S. Sidorenko. Kon’kov. Metals 5 (1965) 1. August 1976).P.V. A.G. Clayton. October 1959.U. van Reenen for their contributions to this study. Charquet. Vienna. in Surface Alloying by Ion. E.T. [61 G. Sot.V. [31 J.E. Canada (April 1962). when incorporated in the oxide layer during oxidation. IAEA Report IWGFPT/34 (IAEA. act to retard the transition to linear oxidation kinetics. Comstock. 341. Energy 31 (1992) 47. IAEA Report IWGFPT/34 (IAEA. D. New York. S.M. Symp.G. [lOI C.R. 5.J. Report TID-7587.244 G. References [l] 0. J. [I81 A. Proc. on illI H. Eur. D. Kobe. R. thereby leading to a reduction in the internal stresses in the oxide layer.R. Thomazet. to be published. 108. which act to prevent cracking of the oxide layer by increasing oxide plasticity and reducing stresses in the oxide layer.T. 106 171 M. during B-quenching. J. in: Advances in Corrosion Science and Technology .G. Kubachewski-von chemical Properties of its Compounds and Alloys. Mardon. eds. Eloff et al. 1990) p. J. 0 Kubachewski. Acknowledgements The authors are indebted to Dr. 255. Mr. 1985) p. Kincer. in Zirconium: Physico[l-a 0. Glazkov. Douglass. All the above-mentioned arguments support the idea that the improvement in oxidation resistance achieved by surface alloying with a thin layer of palladium is brought about by postponing the transition to linear oxidation kinetics through the formation. Oxidation of Metals 18 (1982) 1. Proc.F. [2] R. [I41 B. on Zirconium in the Nuclear Industry.S. Bangaru.J.I. Traccucci.F. p. [I31 C.L.W. Aqueous Corrosion of Reactor Materials. 1987) p. [I61 D. Marin. Rehn. J.H. The microstructural effect of this treatment is the formation of a region of a-Widmannstatten structure near the surface with an abundance of intermetallit precipitates on the subgrain boundaries which. of a high concentration of intermetallic particles near the surface. Wiedersich (American Society for Metals. Grigor’ev. 1990) p. Stern and H. Less-Common [171 N.A. V. Moinov. van der Kouwe. 1151 B. (1959) 755.. Weidinger. E. RI J. Vienna. W. 13 (1973) 3. 145.A. / Improvement in oxidation resistance of Zircaloy-4 oxide layer. J. [51 R. ed. Electrochem. Vienna. Nucl. Nucl. on Zirconium in the Nuclear Industry. Berthet and Worldscan 3-4 (1990) 14. [41 F. [91 C. Seventh Int. Afr. Report PM-I-62-5. 1976). November 1990. 9th Int. Billet. Metals Park. (1990) 47. Steinberg and H. Bresser and Miss M. A. and Laserbeams. 6 (International Atomic Energy Agency. Department of Mines and Technical Surveys. de Wet. Corrosion Sci. J. Cox. Dr. ASTM STP 939 (American Society for Testing and Materials.