Measurements of hydrogen permeation and absorption in zirconium oxide scales

The hydrogen absorption and the permeation behavior through the oxide layer formed on modified Zircaloy-4 (Zry-4) alloys were investigated. The modified Zry-4 was prepared by altering the chemical composition of standard Zry-4. The tin content of Zry-4 (1.5 wt%) was reduced to 0.5 wt%, and alloying elements Si, O and Nb were added from 0.01 to 0.2 wt%. The oxide layers were grown in a static autoclave at 360 °C under 18.3 MPa for 150 days. Fick’s law was used to calculate the diffusivity of hydrogen after the steady state of the permeation flux was reached. The diffusivity of hydrogen in the 0.5Sn–0.1Nb–0.1Fe–0.2Cr–0.2O–Zr specimen was lower than that in the 1.5Sn–0.2Fe–0.1Cr–0.1O–0.01Si–Zr and Zry-4 specimens. As the area fraction of precipitates increased, the hydrogen diffusivity increased whereas an inverse relationship between the diffusivity and the amount of the tetragonal phase was observed. In addition to the oxide structural study, the effects of the microstructure of the zirconium alloys such as precipitates and grain boundaries on the hydrogen absorption were studied.     

Characterization of Chemical Densified Coating as Tritium Permeation Barrier

In a fusion blanket design, ceramic coating on structural materials has been considered to be used as a tritium permeation barrier. The Chemical Densified Coating (CDC) method has some advantage compared with another coating method. This method is capable to form densified coating on either the outer or the inner surface of a tube or a container. This process temperature is low (450°C). The fabrication technique of Cr₂O₃-SiO₂ coating had been developed using CDC method. However, Cr₂O₃-SiO₂ coating had open pores in the coating. For filling open pores, the densification treatment by CrPO₄ was examined. In this study, the verification of open pores, the thermal shock resistivity, the adhesion strength and the deuterium permeability were evaluated and compared with Cr₂O₃-SiO₂ (Type 1) coating and Cr₂O₃-SiO₂ including CrPO₄ (Type 2) coating. From these results, it was confirmed that Type 2 coating had a good adhesion property, and permeation reduction factor of SS316 with Cr₂O₃-SiO₂ including CrPO₄ coating reached about 1,000 at 600°C.     

Compatibility between several heat resistant alloys and sintered Li2O in static helium gas environment

The reaction of sintered Li₂O discs with several commercial heat resistant alloys has been investigated under the conditions of 3.3 × 10⁴Pa ($\text{1}\text{3}\text{atm}$) static He gas atmosphere in the temperature range of 500 and 750° C. Reaction products were identified by X-ray diffraction analysis to be two phases of Li₅FeO₄ and LiCrO₂. The former was dominant below 650° C and the latter was dominant above 650° C. The activation energies of the reaction were determined by the Arrhenius plots for weight changes and sub-scale thickness measurements. The reactivity of the four Fe-Ni-Cr alloys decreased according to the order of Incoloy 800, 316 SS, Hastelloy X-R and Inconel 600. Grain boundary penetration was observed above 500° C for Incoloy 800, 550° C for 316 SS and 600° C for Inconel 600. There was no grain boundary penetration in Hastelloy X-R.     

Radial-hydride Embrittlement of High-burnup Zircaloy-4 Fuel Cladding

Prestorage drying operations of high-burnup fuel may make Zircaloy-4 (Zry-4) fuel cladding more susceptible to failure, especially during fuel handling, transport, and post-storage retrieval. In particular, hydride precipitates may reorient from the circumferential to the radial direction of the cladding during drying operations if a threshold level of hoop stress at or above a corresponding threshold temperature is exceeded. This study indicates that the threshold stress is approximately 75–80 MPa for both nonirradiated and high-burnup stress-relieved Zry-4 fuel cladding cooled from 400°C and, under ring compression at both room temperature and 150°C, that radial-hydride precipitation embrittles Zry-4. Specifically, the plastic tensile hoop strain needed to initiate unstable crack propagation along radial hydrides decreases dramatically from >8% to lt;1% as radial-hydride fraction increases. Lower hydrogen contents (lr;300wppm) appear to be more susceptible to radial-hydride embrittlement compared to higher contents (>600 wppm), like that found in high-burnup Zry-4.     

Mechanical characteristics of fuel rod claddings in transport conditions

Abstract

A synthesis on the mechanical characteristics of unirradiated and irradiated fuel rod claddings was performed by the French Institut de Radioprotection et de Sûreté Nucléaire (IRSN) in order to have reference data for the assessment of the safety demonstrations in normal and accident conditions of transport required by the procedure of package licensing. Indeed, the transport conditions correspond to a range of cladding temperatures (200–550°C) which is only partly covered by the data acquired within the framework of the safety demonstration relative to the reactor normal operating conditions, especially beyond 400°C. This work concerned Zircaloy-4 cladding material (Zry-4) and M5^TM. Data about mechanical properties (elastic and ductile properties, creep behaviour), oxidation (in reactor and under air during transport), hydrides and fracture toughness have been collected and synthesised. The laws presented in the document can be used to obtain orders of magnitude of oxide layer thickness, hydrogen content and creep deformation rate. The following phenomena which could influence the mechanical behaviour of the cladding were more particularly studied: oxidation which could become very important during transport in case of cladding temperatures of ～500°C; creep for which only a few data ～500°C are available and which depends in particular on the internal pressure of the rods, the cladding oxidation and the presence of the hydrides; and recrystallisation of Zry-4 at ～500°C, which could have consequences on the mechanical properties of the cladding after cooling during the storage. For other topics of interest for the study of the mechanical behaviour of the cladding, such as the fracture toughness for example, it was identified that the data available is scarce.     

Zircaloy-4 Cladding Embrittlement due to Inner Surface Oxidation under Simulated Loss-of-Coolant Condition

Embrittlement of Zircaloy-4 cladding by oxidation of the inner surface occurring in an LWR loss-of-coolant accident was studied using simulated fuel containing of A1₂O₃ pellets sheathed in Zircaloy-4 specimen cladding, filled with Ar gas, and sealed. This simulated fuel rod was heated from outside until the isothermal oxidation temperature between 880 and 1,167°C was obtained after the cladding burst. This exposed the inner surface of the cladding to the environmental atmosphere, provided by steam flowing at a constant rate in the range of 0.13–1.6 g/cm²-min.

The embrittlement of the specimen due to inner surface oxidation is influenced primarily by the amount of hydrogen absorbed by the Zircaloy-4. Ring compression tests conducted at 100°C on test pieces constituted of sliced sections of oxidized specimen showed that Zircaloy containing more than 200–300 wt.ppm of absorbed hydrogen became brittle when oxidized at temperatures above 1,000°C. In the range of oxidation temperature 932 to 972°C, brittleness did not appear below 500–750 wt.ppm absorbed hydrogen.

Hydrogen absorbed by the Zircaloy precipitated in the form of fine hydride crystals formed along previous β-phase grain boundaries. Peaks were found in the distribution of hydrogen absorbed on the inner surface, at a distance of 15–45 mm upward and downward of the rupture opening. Within this range, the distance was influenced by the oxidation temperature and steam flow rate.     

TRISO coated fuel particles with enhanced SiC properties

The silicon carbide (SiC) layer used for the formation of TRISO coated fuel particles is normally produced at 1500-1650 °C via fluidized bed chemical vapor deposition from methyltrichlorosilane in a hydrogen environment. In this work, we show the deposition of SiC coatings with uniform grain size throughout the coating thickness, as opposed to standard coatings which have larger grain sizes in the outer sections of the coating. Furthermore, the use of argon as the fluidizing gas and propylene as a carbon precursor, in addition to hydrogen and methyltrichlorosilane, allowed the deposition of stoichiometric SiC coatings with refined microstructure at 1400 and 1300 °C. The deposition of SiC at lower deposition temperatures was also advantageous since the reduced heat treatment was not detrimental to the properties of the inner pyrolytic carbon which generally occurs when SiC is deposited at 1500 °C. The use of a chemical vapor deposition coater with four spouts allowed the deposition of uniform and spherical coatings.     

Progress in compatibility experiments on lithium–lead with candidate structural materials for fusion in China

Liquid LiPb eutectic is one of the promising candidate tritium breeder materials for fusion reactors. This paper presents the progress in compatibility experiments with liquid LiPb achieved up to now in China for some candidate structural materials. The results showed that CLAM steel had good compatibility with flowing LiPb at 480 °C with the velocity of 0.08 m/s after 5000 h in DRAGON-I loop. On the other hand, after exposed in static LiPb at 700 °C for 500 h in a SiC crucible, the W and Mo specimens suffered much more weight loss compared with Nb specimen, and a thin reaction product layer was visible on the surface of all the three refractory metals. Preliminary analysis on SiC_f/SiC composite specimens indicated that there was no penetration of LiPb and no reaction products on the surface with CVD SiC coating, which showed SiCf/SiC composite were stable and compatible with static LiPb under 700 °C after 500 h exposure.     

Physical and chemical sputtering of graphite and SiC by hydrogen and helium in the energy range of 600 to 7500 eV

The erosion of pyrolytic graphite and silicon carbide due to the bombardment with monoenergetic hydrogen ions with energies of 600 to 7500 eV has been investigated in the temperature range of near room temperature to 750°C. The erosion yield of SiC is about 10^?2 and shows no pronounced temperature dependence. In contrast to SiC the erosion yield of pyrolytic graphite shows a maximum at a temperature of about 600°C. The ratio of the maximum erosion yield to that at room temperature depends on the energy of the hydrogen ions and increases from about 11 at 3000 eV to 32 at 670 eV. The production of CH₄ during the bombardment of the graphite has been found proportional to the erosion yield. When graphite was bombarded with He ions no hydrocarbon production and no temperature dependence of the erosion yield could be observed. The results are compared with values for the erosion yields of carbon by thermal atomic hydrogen taken from literature.     

Oxidation kinetics of Zry-4 fuel cladding in mixed steam–air atmospheres at temperatures of 1273–1473 K

This paper deals with the oxidation behavior of Zry-4 nuclear fuel cladding tubes in mixed steam–air atmospheres at temperatures of 1273 and 1473 K. The main goal is to study the oxidation kinetics of Zry-4 fuel cladding in dependence on the air fraction in steam in the range from 0% up to 100%. The purpose of this study is to provide experimental data suitable for an oxidation correlation, applicable for severe accident computer codes of nuclear power reactors. The influence of the air addition in steam on parameters of Zry-4 kinetic equation has been quantified using the results of weight gain measurements. At 1273 K, both pre-transition and post-transition regimes were treated. The results of weight gain measurements showed a strong dependence of the Zry-4 oxidation kinetics on the air fraction in steam, especially at 1473 and at 1273 K in the post-transition regime.     

Preparation and investigation of aluminized coating and subsequent heat treatment on 9Cr–1Mo Grade 91 steel

Iron aluminide inner coating with alumina top layer is being considered as a potential solution for tritium permeation barrier and mitigating MHD pressure drop for liquid metal blanket concepts in the fusion reactor systems. Hot-dip aluminizing with subsequent heat treatment seems to offer a good possibility to produce aluminized coating with alumina top layer. 9Cr–1Mo Grade 91 steel samples were hot dipped in Al melt containing 2.25 wt% of Si at 750 °C for 3 min. Heat treatment was performed at 650, 750 and 950 °C for 5 h; samples were either air cooled or furnace cooled. Coatings have been evaluated by SEM, EDX, X-ray diffraction, microhardness, scratch adhesion and Raman spectroscopy. The thickness of the layers and phases formed were influenced by the heat treatment adopted. Fe₂Al₅ was the major phase present in the samples heat treated at 650/750 °C, whereas FeAl and α-Fe(Al) primarily made up the outer and inner layers respectively in the samples heat treated at 950 °C. Cooling method deployed affected the hardness. Air cooled samples had comparatively higher hardness than furnace cooled samples. The scratch test showed the adhesion for the samples heat treated at 950 °C was much better as compared to the samples heat treated at 650/750 °C. Raman spectroscopy analysis showed the presence of both α-Al₂O₃ and γ-Al₂O₃ on the surface of the samples heat treated at 950 °C, while Fe₃O₄ was present in the furnace cooled sample only.     

Helium and hydrogen re-emission during implantation of molybdenum,vanadium and stainless steel

He re-emission has been measured during 300 keV He⁺ implantation from 400°C to 1200°C in V and Mo between ?170°C and 700°C in 316 SS. H re-emission has been measured during 150 keV H⁺ implantation of Mo, V, and 316 SS between ?90°C and 115 °C. In general the He re-emission is low until a critical dose is reached, at which time the re-emission abruptly rises to higher values. Both the critical dose and re-emission are strongly temperature dependent. The H re-emission generally rises smoothly to an equilibrium value which is both temperature and material dependent. Only at the lowest temperature does the H re-emission in Mo bear a qualitative resemblance to He re-emission.     

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.     

Characterization and storage of radioactive zeolite waste

For the safe storage of zeolite wastes generated by the treatment of radioactive saline water at the Fukushima Daiichi Nuclear Power Station, this study investigated the fundamental properties of herschelite adsorbent and evaluated its adsorption vessel for hydrogen production and corrosion. The hydrogen produced by the herschelite sample is oxidized by radicals as it diffuses to the water surface and thus depends on the sample's water level and dissolved species. The hydrogen production rate of herschelite submerged in seawater or pure water may be evaluated by accounting for the water depth. From the obtained fundamental properties, the hydrogen concentration of a reference vessel (decay heat = 504 W) with or without residual pure water was evaluated by thermal–hydraulic analysis. The maximum hydrogen concentration was below the lower explosive limit (4%). The steady-state corrosion potential of a stainless steel 316L increased with the absorbed dose rate, but the increase was repressed in the presence of herschelite. The temperature and absorbed dose at the bottom of the 504 W vessel were determined as 60 °C and 750 Gy/h, respectively. Under these conditions, localized corrosion of a herschelite-contacted 316L vessel would not immediately occur at Cl^? concentrations of 20,000 ppm.     

Uncertainty Analyses of Neutron Cross Sections for 235U in the Resonance Region

The helium embrittlement behavior of 316FR austenitic stainless steel was investigated by a tensile test at 750°C using miniature tensile specimens, which were helium-implanted below 100°C up to 5, 30, and 100 appm using a cyclotron accelerator, and were post-implantation-annealed at 750°C for 10 and 100 h. The helium-implanted specimens showed a fully intergranular fracture regardless of the helium concentration and annealing time. No microstructural changes in the as-implanted specimen up to 30 appm and formation of a small number of helium bubbles due to the post-implantation annealing were observed. The gradual release of the helium during the tensile test started after the yielding, and a sharp peak of the helium release was detected in the final fracture phase. The total number of helium atoms released was strongly dependent on the implanted helium concentration, rather than on the annealing time.     

Nitrogen and helium permeation tests of SiCf/SiC composites

The permeance of inert gases (N₂ and He) through coated SiC based ceramic composites both in form of tubes and discs has been measured, in particular SiC-SiC_f/SiC functionally graded material tubes made of SiC-SiC_f with a SiC polycrystalline sealing coating and chemically vapour infiltrated (CVI) SiC_f/SiC composite discs have been tested.The permeation tests have been aimed at verifying the effectiveness of coatings obtained by chemical vapour deposition (CVD) and used for closing the porosity of the composite materials and assuring their gas sealing. The measurements have been carried out at room temperature with operating pressure in the range 130-500 kPa. The SiC-SiC_f/SiC functionally graded material has shown very low permeability values. The CVI SiC_f/SiC composite tested has shown rather low permeance values, although the material is not gas tight: its reduced permeance was attributed to both the high fibre percentage and the dense SiC coating.     

Helium dilution effect on hydrogen permeation in 316L stainless steel and nickel-base heat-resistant alloys

Effects of inert-gas dilution on hydrogen permeation have been investigated in 316L stainless steel, Inconel 600, Inconel 750, Nimonic 80A and Hastelloy X at 1173 K and 1073 K, by employing a gas-flow system. We used gas mixtures of hydrogen and helium, whose hydrogen concentration ranged from 10^?5 to 10^?1. For the steady-state permeation, the dilution of hydrogen caused no anomalous effects and the permeation rate conformed to Sieverts' law. However, for the transient state, the hydrogen permeation was retarded by the dilution with helium. The retardation effect is discussed in terms of an adsorption model and explained by a decrease in sticking probability at the alloy surface with the dissociative adsorption of hydrogen.     

Compatibility of erbium oxide coating with liquid lithium–lead alloy and corrosion protection effect of iron layer

Li–Pb compatibility of Er₂O₃ and Er₂O₃-Fe two-layer coatings has been explored for an understanding of corrosion behaviors and effects of the protection layer. The coatings were peeled off after static Li–Pb immersion test at 600 °C due to the degradation of adhesion between the coating–substrate interface. A loss of Er and then subsequent corrosion of Er₂O₃ were shown after immersion at 500 °C for 500 and 1505 h. However, the outer Fe layer played a role to decrease corrosion rate of the coatings by comparing with the results of Er₂O₃ single layer coatings. Deuterium permeation measurements after corrosion tests at 500 °C showed that the Er₂O₃ coatings kept permeation reduction factors of 10²–10³ after 500 h immersion, but seriously degraded after 1505 h immersion. Corrosion mechanisms suggest that corrosion protection properties will be modified by an optimization of the outer Fe layer and a control of oxygen concentration in Li–Pb.     

Corrosion experiments and materials developed for the Japanese HLM systems

The static corrosion tests in lead-bismuth eutectic (LBE) were conducted from 450 °C to 600 °C to understand corrosion behavior and develop corrosion resistant materials for heavy liquid metal systems. While increase of Cr content in steels enhances corrosion resistance in LBE, the effect approaches a constant value above 12 wt% of Cr. Corrosion depth in LBE increases with increasing temperature and corrosion attack becomes severe above 550 °C even under the condition of high oxygen concentration. Nickel dissolution and Pb-Bi penetration occur in 316SS and JPCA above 550 °C under the condition of high oxygen concentration. When oxygen concentration decreases below the level of Fe oxide formation, corrosion attack on these steels also becomes violent due to dissolution of various elements and grain boundary corrosion. Whereas additions of 1.5 wt% Si to T91 and 2.5 wt% Si to 316SS improve corrosion resistance, the effect is insufficient taking fluctuation of oxygen concentration in LBE into consideration. Furthermore, addition of 1.5 wt% Si to T91 causes rise in DBTT. A new coating method using Al, Ti and Fe powders produces corrosion resistant coating layers on 316SS. The coating layers containing 6-8 wt% Al exhibit good corrosion resistance at 550 °C for 3000 h in LBE containing 10⁻⁶-10⁻⁴ wt% of oxygen.