Yoshiaki Ishii

Role of Iron for Hydrogen Absorption Mechanism in Zirconium Alloys

The latest PIE results of Zry-2 and HiFi alloy (0.4 %Fe-Zry2) showed that iron addition reduces the hydrogen pick-up ratio. In order to clarify this lower hydrogen absorption mechanism, three types of experiments were carried out for both alloys: (1) Measurements of the hydrogen pick-up ratio in the pre-transition region using an autoclave. (2) CPD ( C ontact P otential D ifference) and FBP ( F lat- b and P otential) measurements of oxide film using a High Temperature Kelvin system and Photocurrent system. (3) Investigation of hydrogen absorption properties by Sieverts system and corrosion properties by autoclave for intermetallic compounds simulating SPPs Fe/Cr and Fe/Ni ratio in Zry-2 and HiFi. Autoclave tests showed that the corrosion behaviors of both alloys were similar. However, the hydrogen pick-up ratio depended on not only iron addition but also surface treatment (with and without pickling). Iron addition and non-pickling (as-received) reduced the hydrogen pick-up ratio. ΔCPD and FBP shifted to the positive side as the result of iron addition, and FBP changed with and without pickling. This difference in surface potential might be caused by the existence of anion vacancy concentration in the oxide film and furthermore may affect the electrochemical potential gradient over the oxide film. This potential gradient might control the proton diffusion in the oxide film. In the results of the hydrogen absorption tests on intermetallic compounds, Zr(Fe,Cr)2 with a higher Fe/Cr ratio showed lower hydrogen absorption, and Zr2(Fe,Ni) showed higher hydrogen absorption than Zr(Fe,Cr)2. In the results of corrosion tests on intermetallic compounds, Zr2(Fe,Ni) showed a much larger corrosion rate than Zr(Fe,Cr)2. It is considered that Zr2(Fe,Ni)-type precipitate might be oxidized easily in the oxide film, thus it might not contribute to the window for hydrogen absorption, and Zr(Fe,Cr)2 with a higher Fe/Cr ratio would reduce the amount of hydrogen penetrating through SPP at the oxide/metal interface. Based on these results, a tentative hydrogen absorption mechanism is proposed, explaining both roles of the electrochemical potential gradient over oxide film and the SPP window for the hydrogen absorption.

Irradiated behavior at high burnup for HiFi alloy

Irradiation tests of a BWR advanced Zr alloy (HiFi alloy) and Zircaloy-2 (Zry-2) were carried out in a Japanese commercial reactor and the irradiation performances of the materials were investigated. HiFi alloy and Zry-2 showed excellent resistance to corrosion up to 70 GWd/t, and furthermore, HiFi kept lower hydrogen pickup compared with Zry-2. TEM observation showed that the Fe/(Fe+Cr) ratio of Zr(Fe,Cr)2 type second phase particles (SPPs) for HiFi alloy and Zry-2 tended to decrease as fast neutron fluence increased and to saturate at high fluence. Zr-Fe-Cr SPPs did not completely disappear even for 6 cycles for the irradiated HiFi alloy and Zry-2. In order to clarify the mechanism of hydrogen absorption, an electrochemical technique was used for the oxide film of both materials as part of the out-of-pile test. The relation between the oxide surface potential and the hydrogen pickup fraction was estimated suggesting that the potential difference over the oxide film suppressed hydrogen (proton) diffusion in the oxide film.

Development of new zirconium alloys for a BWR

Specimens for irradiation testing in a commercial BWR were prepared from 24 kinds of Zr alloys. The corrosion performance of these specimens was investigated after irradiation for up to four cycles. Two cycles of irradiation were not always sufficient to identify the lowest corrosion alloys. Marked acceleration of corrosion occurred for many alloys between one and four cycles. The onset of mildly accelerated oxidation was observed for standard Zircaloy-2 at four cycles of irradiation. On the other hand, for Zircaloy-like alloys, increasing Fe and Ni contents or decreasing the Sn content promoted a saturation oxidation between two and four cycles of irradiation. The effects of alloying elements on corrosion behavior were evaluated by both in-pile and out-of-pile corrosion tests. The alloying elements Fe, Cr, and Ni, which have smaller valences than Zr, improved the in-pile corrosion resistance of Zr alloys, while the alloying elements Nb, Mo, and Te, which have larger valences than Zr, were responsible for increased weight gain during the irradiation test in the BWR.

Effect of Metallographic Factor on Hydrogen Pick-up Properties of Zircaloy-2

Zirconium alloy sheets were prepared with varying Fe, Cr and Ni systematically. The corrosion and hydrogen pickup property were estimated in steam at 673 K, in water at 633 K and in super critical water at 673 K. The effect of the SPP and the oxide film on the hydrogen pick-up was studied from the hydrogen pick-up route using D2O and the microstructure of the oxide film and secondary phase particle (SPP) in the oxide film. The hydrogen pick-up ratio decreased with increase of Fe and decrease of Ni. It was affected by Fe/Ni ratio of the matrix. The hydrogen pickup was not related to SPP but was related to the oxide film when the oxide film was relatively thick. The tetragonal ZrO2 is considered to act as a barrier for hydrogen pick-up.

A New Non-destructive Technique for Hydrogen Level Assessment in Zirconium Alloys using EMAR Method

In order to study the applicability of EMAR (electromagnetic acoustic resonance) method to non-destructive hydrogen level assessment in fuel spacer bands at pool side, an ultrasonic transmitter and receiver together with an EMAT (electromagnetic transducer) were used. Unirradiated Zircaloy-2 thin plates were hydrogen charged for the measurements. An irradiated fuel cladding tube was also used to examine the detection sensitivity of the resonance spectrum of the irradiated material. The following results were obtained. Acoustic anisotropy Δf, defined by using two resonance frequencies for shear waves with different polarization, was adopted as a parameter to express the ultrasonic resonance property. A hydrogen concentration dependence of Δf was observed in the range up to 1,200 ppm. Specimen thickness and oxide thickness were found to have negligible effect, on Δf, and liftoff of the sensor up to 1mm did not affect the Δf value. The acoustic anisotropy proposed in this paper was not sensitive to any of specimen dimension, surface condition, or sensor liftoff.

Interpretation of Acoustic Parameters Obtained by EMAR Measurement for Non-destructive Hydrogen Concentration Measurement in Zr Alloy

An obvious quantitative relation between hydrogen concentrations in zirconium alloy and acoustic anisotropy parameters obtained by the electromagnetic acoustic resonance (EMAR) method was reported. To elucidate the mechanism, the acoustic parameters were calculated based on the elastic theory and the equation of motion. The acoustic parameters obtained by the EMAR method were interpreted quantitatively using the anisotropic elastic constants of the specimen, and values calculated from texture data for non-hydrogen charged specimens showed good agreement with those obtained by the EMAR method. Calculated temperature dependence of the acoustic anisotropy for the non-hydrogen charged specimen also agreed well with that by the EMAR method. The consistencies demonstrated that the absolute values of the acoustic parameters for non-hydrogen charged specimens can be calculated from both the texture data of (0002) pole figure and the elastic constants of the specimen. Hydrogen addition up to approximately 650 ppm was found not to change the original (0002) pole figure and, correspondingly, no hydrogen concentration dependence of the acoustic parameters was obtained from the calculation. These results implied that the zirconium hydride itself played an important role for the change in the acoustic parameters of the hydrogen charged specimens, and the importance of obtaining the information on the elastic constants of the zirconium hydride was pointed out.

Effect of Hydrogen Water Chemistry on Zircaloy-2 Fuel Cladding and Structure Material Performance

The effects of hydrogen addition to the feedwater on the corrosion and hydrogen uptake performance of Zircaloy-2 fuel cladding tubes, a water rod tube and spacer materials irradiated for four cycles in a BWR were evaluated. The uniform oxide behaviors of the cladding tubes, water rod and spacer materials were not affected by hydrogen water chemistry (HWC) condition. The hydrogen uptake and pickup fractions of the water rod and spacer materials were similar to those of water rods and spacer materials under normal water chemistry (NWC) conditions. As for the fuel rods, in spite of comparably heavy crud deposition, their hydrogen uptake and pickup fractions were clearly lower than the values under NWC conditions. Overall, the results indicated that HWC had no adverse effects on fuel performance.

Annealing Study on Neutron Irradiation Effects in Resonance Frequencies of Zircaloy Plates by EMAR Method

To develop the nondestructive hydrogen concentration measurement method for the irradiated zirconium alloy, the effect of neutron irradiation damage on acoustic properties obtained by the electromagnetic acoustic resonance (EMAR) method was investigated through annealing tests. It is confirmed that the recovery of irradiation damage begins at a lower annealing temperature than that in unirradiated coldworked materials. Unirradiated recrystallization-annealed materials did not show any change in acoustic properties or hardness during the additional RX annealing at 580°C, whereas the acoustic anisotropy (Δf) of the as-cold-worked unirradiated specimen was significantly increased. Four-cycle irradiation clearly decreased the shear wave velocity of the specimen by 1% compared to the RX-annealed specimen. In comparison with the wave velocity change, the acoustic parameters defined in this study are found to be less sensitive to irradiation damage. From the annealing study of the as-irradiated specimens to the RX condition, it is concluded that the absolute value of (Δf) increases by 0.1% and the frequency ratio (fl/fr) by about 0.006 as a result of the damage induced by the four-cycle irradiation in BWRs. These values are applicable to the relationships between the acoustic parameters and hydrogen concentrations of unirradiated materials as the correction factors to compensate the effects of irradiation damage.

Reducing Hydrogen Penetration through Corrosion Layer Formed on Zirconium Alloys by Iron Addition

Latest post-irradiation experiment results of Zry-2 and HiFi alloy (0.4%Fe-Zry2) showed that iron addition reduces the hydrogen pickup by these alloys compared to oxidation amount. In order to clarify the mechanism of reduced hydrogen absorption rate, (1) autoclave test, (2) surface potential measurement and (3) hydrogen absorption test of the intermetallic compound were carried out. Based on these results, a tentative mechanism for hydrogen absorption by zirconium alloys is proposed, taking into account of both the electrical potential gradient over the oxide film as well as the SPP window for hydrogen absorption.