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.     

Hydrogen isotope permeation from cooling water through various metal piping

In order to investigate the behavior of hydrogen isotope on the water–metal boundary, deuterium permeation experiments from heavy water vessel through various metal piping, such as pure iron (Fe), nickel (Ni), stainless steel (SS304), and pure iron with 10 μm gold plating, were performed at 573 K and at 15 MPa. During the experiment, surfaces of metal piping except gold plating one were oxidized at the heavy water boundary and then deuterium would generate by the oxidation reactions. This deuterium could be detected by mass spectrometer, which monitored the inside gases of the piping under continuous evacuation. The result showed clearly that the deuterium permeated through Fe, Ni, and SS304 piping was detected as mainly deuterium gas (D₂) under continuous evacuation, though that through gold plating one could not be detected effectively. The D₂ permeation rate through Fe, Ni, and SS304 piping reached equilibrium conditions with oxide generation at D₂O–metal boundary, although concluding the transfer mechanism will require further testing and modeling activities.     

The oxidation behaviour of the ferritic alloy DT02 in carbon dioxide and in argon containing 0.7 Pa water vapour and 37.5 Pa hydrogen at 823—1123 K

The oxidation behaviour of the ferritic alloy DT02, dispersion-strengthened with titania (Fe + 13 wt% Cr + 2.5 wt% Ti + 2 wt% TiO₂) has been compared in two environments, carbon dioxide and argon containing 0.7 Pa water vapour and 37.5 Pa hydrogen. The temperature range covered was 823–1123 K. Over 4827 h the kinetics of oxidation in argon + water vapour + hydrogen were paralinear at 923 K and linear at ? 1023 K. Oxidation resulted in the formation of a chromium rich oxide scale with titanium rich bands at the oxide-steel interface and also at ? 1023 K at the gas interface. In carbon dioxide, due to its higher oxygen potential and the thermodynamic possibility for iron to be involved in scale formation, the alloy was attacked more severely with successively paralinear, linear and breakaway kinetics at increasing temperature. Duplex oxide scales were produced with outer Fe₃O₄ and inner Fe, Cr and Ti-bearing oxide layers. Carbon was picked up within the oxide scale, particularly in the inner layer, while any unoxidised alloy was extensively carburised.     

Angular Distributions of Resonance Neutron Scattering from Fe-56

Chromium depletion near grain boundaries of austenitic stainless steel during irradiation was investigated. Specimens were kept at 1,473 K for 30 min, and were quenched into the water. Irradiations were done using 400 keV He⁺ ions at 573, 673 and 773 K up to 10dpa with a dose rate of 2.4×10^?4 dpa/s. After irradiation, the Cr concentration profile near the grain boundary was measured using an analytical electron microscope with a 1 nm beam diameter. At 573 K, Cr depletion is small, and its concentration at the grain boundary decreases to 15.5 mass% at 3 dpa from the initial concentration of 18.5 mass%. At 673 and 773 K, Cr concentration at the grain boundary rapidly decreases between 0 and 0.2dpa, and then gradually approaches a constant value, 7.0 mass% at 673 K and 5.0 mass% at 773 K. Two stages are found in radiation induced segregation (RIS) behavior, one stage in which Cr depletion and Ni enrichment balance and another in which Fe depletion and Ni enrichment balance.

These experimental results were compared with the calculations based on the vacancy-induced inverse Kirkendall effect. Predicted Cr segregation at 673 and 773 K above 3dpa agrees with the experimental results. But Cr depletions at low doses which were obtained in the experiments are much faster than calculated. At 573 K in the experiments, depletion is smaller than calculated up to 10dpa.     

The general corrosion behavior of ENiCrFe-7 weld overlay cladding material in deoxygenated high-temperature and high-pressure water

The general corrosion behavior of Alloy ENiCrFe-7 in deoxygenated high-temperature and high-pressure water was investigated. The results showed that the precipitates of Alloy ENiCrFe-7 included niobium carbide and Al-Ti-O compounds, and the weight gain increased fast firstly before 2250 h, then the weight gain slowed down. There were obvious large particles spread on denser oxide film after 3000 h exposure. Ni was present at a single chemical metallic Ni state, Feⁿ⁺ content of the outer layer was close to 60%, which was much higher than that of the matrix. The oxide film consisted of an inner layer and an outer layer, the inner layer was mainly composed of Cr₂O₃ and the outer layer was mainly composed of Fe₃O₄ and FeCr₂O₄. Finally, it is found that the preferential corrosion location of pitting was niobium carbide precipitates by in same site observation, while Al-Ti-O compounds was not dissolved in deoxygenated high-temperature and high-pressure water for 1500 h exposure. The size and number of the pitting was not significantly changed with increasing exposure time.     

Characterization of oxide films formed on alloy 182 in simulated PWR primary water

The oxide film, formed on the alloy 182 due to the exposure to simulated Pressurized Water Reactor primary water conditions, is characterized using X-ray Photoelectron Spectroscopy, Scanning Electron Microscopy and Raman spectroscopy. As a consequence of the low redox potential for nickel, loosely bound oxide film consisting mainly of chromium oxide, is formed on the surface of the alloy. The oxide film is found to have a double-layer structure, with an inner layer rich in Cr₂O₃, outer layer rich in FeCr₂O₄. Thin Ni(OH)₂ and Fe₃O₄ clusters were observed on top of the oxide film. The morphology and thickness of the layers critically depend on the exposure times and surface treatments prior to the exposure.     

Characterization of solidified melt among materials of UO2 fuel and B4C control blade

To predict the fundamental phase relationships in the solidified core melt of the Fukushima Daiichi Nuclear Power Plant, solidified melt samples of the various core materials [B₄C, stainless steel, Zr, ZrO₂, (U,Zr)O₂] were prepared by arc melting. Phases and compositions in the samples were determined by means of X-ray diffraction, microscopy, and elemental analysis. With various compositions, the only oxide phase formed was (U,Zr)O₂. After annealing, the stable metallic phases were an Fe-Cr-Ni alloy and an Fe₂Zr-type (Fe,Cr,Ni)₂(Zr,U) intermetallic compound. The borides, ZrB₂ and Fe₂B-type (Fe,Cr,Ni)₂B, were solidified in the metallic part. Annealing at 1773 K under an oxidizing atmosphere (Ar-0.1%O₂) resulted in the oxidation of U and Zr in the alloy and in ZrB₂, and consequently the (Fe,Cr,Ni)₂B and Fe-Cr-Ni alloy became dominant in the metallic part. The experimental phase relationships in the metallic part agreed reasonably with the thermodynamic evaluation of equilibrium phases in a simplified B₄C–Fe–Zr system. The metallic Zr content in the melt was found to be a key factor in determining the phase relationships. As a basic mechanical property, the microhardness of each phase was measured. The borides, especially ZrB₂, showed notably higher hardness than any other oxide or metallic phases.     

Hydrogen and Deuterium Transport through Type 304 Stainless Steel at Elevated Temperatures

The permeation time-lag method have been used to determine the permeabilities, diffusion coefficients and solubilities of hydrogen and deuterium in type 304 stainless steel of three kinds of surface treated specimens; with oxide film, reduced by H₂ gas and Pd coated. For the specimen with a thin oxide film the permeability increased abruptly at the temperature higher than 1,050 K owing to reduction of the oxide film by H₂ gas introduced. The permeability and diffusion coefficient for hydrogen-reduced specimens agreed with those for Pd-coated specimens showing the data of bulk diffusion limited. The isotope effects for permeability Φ_H/Φ_D, diffusion coefficient D _H/D _D and solubility were about 1.4, 1.2 and 1.1, respectively. From these values θ(=hν/k)=1,530±50K and θ′(=hν/k)=2,740±20K were obtained by the quantum effect of a harmonic approximation.     

Depth profile of chemical states of alloying elements in oxide layer of Zr-based alloys

To understand the basic oxidation kinetics of alloying elements which is considered to be strongly related with the corrosion and hydrogen pickup, the depth profiles of chemical states of alloying elements (Cr and Fe) were measured in the oxide layer of Zr-0.5Sn-1.0Cr-0.5Fe alloys. The depth profiles were obtained by combinations of a surface-sensitive XANES and an extremely low energy Ar ion sputtering. The XANES measurements revealed that the chemical states of alloying elements (Fe and Cr) varied with the depth in the oxide layer. Especially in the oxide layer formed in steam, a decrease of the fractions of oxidation states was significant rather than that in LiOH solution. In the oxide layer formed in steam, the oxidation rate of chromium was faster than iron by a factor of approximately 2.     

Prediction of corrosion product stability in high-temperature aqueous systems

Calculated thermodynamic data for metal oxidation/oxide reduction reactions of Fe, Ni, Co and Cu, and for formation, oxidation and reduction of NiFe₂O₄, CoFe₂O₄, CuFeO₂ and CuFe₂O₄, are examined for aqueous systems containing dissolved hydrogen and oxygen at temperatures up to 300°C. The data are presented as equilibrium partial pressures of oxygen and hydrogen for specific reactions. This information is used to predict which solids are stable in an equilibrium system containing known concentrations of oxygen and hydrogen, and in a non-equilibrium system in which γ and neutron radiation fields cause the concentrations of oxygen and hydrogen to be much greater than the equilibrium values. Results of X-ray diffraction studies of corrosion products filtered from the heat-transport system of the Douglas Point Generating Station are compared with phase stability predictions.     

Deposition of Nickel and Cobalt Ions with Iron Crud on Heated Stainless Steel Surface under Nucleate Boiling Conditions

Deposition behaviors of Ni (II) and Co (II) ions on a heated surface using simulated Fe crud which was mainly composed of amorphous Fe(III) hydroxide have been studied under nucleate boiling conditions at 553 K and 70 atm. The deposition process of Ni (II) and Co (II) ions is divided into two stages. The first stage is the deposition of hydroxide precipitate on the heated surface by microlayer evaporation and drying out in the nucleate boiling bubble. The second is settlement by conversion of hydroxide into oxides such as NiO, NiFe₂O₄, CoO and CoFe₂O₄. The effective deposition coefficients of Ni(II) and Co (II) ions, without supplying Fe crud, are smaller than that of α-Fe₂O₃ because of the solubility of those hydroxides at a low concentration condition. Their effective deposition coefficients increase with the simulated Fe crud concentration in feedwater and saturate at a value of 0.3 which is calculated theoretically, because the Ni and Co hydroxides react with the simulated Fe crud to produce insoluble NiFe₂O₄ and CoFe₂O₄ on the heated surface. The reaction of Ni deposit with α-Fe₂O₃ does not proceed, but NiO is produced. The reaction rate of Ni deposit with the simulated Fe crud on the heated surface is higher than that of Co deposit.     

Effect of LiNO3 on Corrosion Prevention of Aluminum Wastes after Their Land Disposal

After their land disposal, LiNO₃ added to cement solidified miscellaneous wastes inhibits hydrogen gas generation due to alkaline corrosion of aluminum contained in the wastes. We considered the presence of an Li-Al preservation film prevents hydrogen gas generation, and then, we assumed a scenario in which the amount of LiNO₃ included in the waste packages is lowered by underground water penetration, resulting in dissolution of the Li-Al preservation film. This dissolution allows the alkaline underground water to reach and corrode the aluminum materials. The loss of Na₂O and K₂O in cement by underground water penetration lowers the pH, so that the aluminum corrosion in the waste packages with LiNO₃, expected when the Li-Al preservation film dissolves, is less than that without LiNO₃.

To test this scenario, we measured solubility of the Li-Al preservation film, Li⁺ ion concentration, pH variation by underground water penetration, and aluminum corrosion when the Li-Al preservation film had dissolved. The measured solubility of the Li-Al preservation film was 3 × 10^?4 _M at 283 K. At that time, pH was lowered from 12.9—13.0 to 12.2—12.3. As a result, with LiNO₃ addition the aluminum corrosion amount was reduced to 10% of that without LiNO₃ addition, because of the pH decrease.     

In situ oxidation of zirconium binary alloys by environmental SEM and analysis by AFM, FIB, and TEM

Binary Zr-alloys containing 1%Fe and 1% Ni (large precipitates) and 1% Cr and 0.6% Nb (small precipitates), as well as a pure Zr sample were exposed in situ at 130 Pa water vapour pressure at 415 °C in an environmental SEM. The surface topography and composition of each sample was characterised before in situ experiments, during and after oxidation. After oxidation the surface was characterised by SEM and EDS, AFM and TEM combined with EDS. Focused ion beam was used to prepare cross sections of the metal-oxide interface and for the preparation of TEM thin foils.The oxidation behaviour of precipitates for these alloying elements can be characterised into two large families, those which show a rapid oxidation and those which induce a delayed oxidation in comparison with the Zr-matrix.At 415 °C after 1 h of oxidation for Zr1%Fe and Zr1%Ni, the formation of protrusions could be detected at the surface, being related to underlying SPP in the oxide. On Zr1%Cr and Zr0.6%Nb unoxidised SPPs were observed in the oxide, close to the metal-oxide interface. These SPPs were, however, oxidised close to the outer surface of the oxide. The surface roughness was increased for all materials after in situ oxidation, however, only for Zr1%Fe and Zr1%Ni protrusions appeared on the surface during oxidation. It was subsequently demonstrated that these latter correspond to the position of SPPs. For Zr1%Fe the surface roughness increased more than in the other materials and on these protrusions small iron oxide crystals have been observed at the surface. These observations confirm that Fe has a different behaviour compared to the other SPP forming elements, and it diffuses out to the free surface of the material.These alloying elements being the constituents of the commercial alloys (Fe and Cr for Zircaloy-4; Fe, Cr and Ni for Zircaloy-2 and Nb for all Nb-containing alloys), this study allows to separate their individual influence and can allow a subsequent comparison to the behaviour of those more complex alloys.     

Application of Zeolites to Remove Iodine from Dissolver Off-Gas, (I)

The oxidation behavior of Zr(Fe,Cr)₂ precipitates being present at the surface of Zircaloy-4 was examined with microprobe Auger electron analysis, focussing attention on the oxidation behavior of chromium and iron in the early stage of oxidation where the oxide film was coherent. Chromium formed a thin oxide layer at the top surface of the zirconium oxide film of precipitate and remained in a metallic state inside the oxide film. Iron was oxidized via dissolution in the matrix zirconium oxide near the top surface and remained in a metallic state inside the oxide film. Such variety of chemical state of chromium and iron with depth in the oxide film was attributed to the existence of oxygen potential gradient in the oxide film.     

The Effect of Oxide Microstructure on Kinetic Transition in Out-of-pile Steam Corrosion Test for Zircaloy-2 and Nb-added Zircaloy-2

In order to study the mechanism of kinetic transition of corrosion rate for zirconium alloys, oxide films formed on Zircaloy-2 (Zry-2) and Nb-added Zircaloy-2 (0.5Nb/Zry-2) in steam at 673 K and 10.3 MPa were examined with TEM and SIMS.

Kinetic transition occurred at almost the same oxide thicknesses for both Zry-2 and 0.5Nb/Zry-2, but the corrosion rate after the transitions were quite different for the two alloys. Zircaloy-2 showed cyclical oxidation, while the weight gain of 0.5Nb/Zry-2 increased linearly.

The morphology and crystal structure were similar for the oxides of the two alloys and both the oxide films still mainly consisted of columnar grains even after the transition. Interface layers which mainly consisted of a-Zr crystallites were observed for both alloys and the oxygen content in the interface layers increased after the transition.

The solute concentrations of Fe, Cr and Ni became higher, accompanying the increase of oxygen concentrations at columnar grain boundaries in the oxide films after the transition for 0.5Nb/Zry-2. It was thought that the properties of grain boundaries of the 0.5Nb/Zry-2 oxide films changed after the transition, and the increase in oxygen diffusivity at grain boundaries caused the linear increase in weight gain.     

LiNO3 Effect on Corrosion Prevention of Aluminum with Complex Shapes

The LiNO₃ effect on aluminum corrosion prevention after land disposal of cement-solidified dry active wastes was examined quantitatively, in the event that the LiH (AlO₂)₂·5H₂O (Li-Al) preservation film was not formed on aluminum surfaces during the solidification process. It is especially probable for these bare surfaces to be left when the wastes include components of complex shapes. LiNO₃ dissolves from the waste forms into underground water to form the Li-Al preservation film. So, we thought that the LiNO₃ addition would prevent the corrosion. We measured the volume of hydrogen gas generation in mortar-soaked water during the Li-Al preservation film formation, as functions of LiNO₃ addition amount, the weight ratio of water to mortar when the mortar-soaked water was produced, and the aluminum surface area, to quantify the effect.

We found that aluminum corrosion was inversely proportional to the LiNO₃ addition. For the corrosion to be less than 10^?5m in 10³h, the initially added amount of LiNO₃ must be 1.5wt% of the sum of cement and sand. Regardless of the weight ratio of water to mortar when the mortar-soaked water was produced, hydrogen gas generation with LiNO₃ was 10% as much as that without it, in 5 x 10³h. Because of the Li-Al preservation film formation reaction, hydrogen gas generation was proportional to the cubic root of the aluminum surface area.     

The effect of alloying modifications on hydrogen uptake of zirconium-alloy welding specimens during corrosion tests

The hydrogen uptake behavior during corrosion tests for electron beam welding specimens made out of Zircaloy-4 and zirconium alloys with different compositions was investigated. Results showed that the hydrogen uptake in the specimens after corrosion tests increased with increasing Cr content in the molten zone. This indicated that Cr element significantly affected the hydrogen uptake behavior. Fe and Cr have a low solubility in α-Zr and exist mainly in the form of Zr(Fe,Cr)₂ precipitates, which is extremely reactive with hydrogen in its metallic state. It is concluded that the presence of Zr(Fe,Cr)₂ second phase particles (SPPs) is responsible for the increase in the amount of hydrogen uptake in the molten zone of the welding samples after corrosion, as Zr(Fe,Cr)₂ SPPs embedded in α-Zr matrix and exposed at the metal/oxide interface could act as a preferred path for hydrogen uptake.     

Magnetic Measurements of NiFe2O4 Formation from Iron Hydroxides and Oxide in High Temperature Water

Formation of NiFe₂O₄ from iron hydroxides and an oxide has been studied in high temperature water by in situ measurements. The five kinds of Fe compounds used in the experiments are known as components of Fe crud in BWR condensate water. Among the reactants and products, only NiFe₂O₄ shows ferromagnetism. An in situ method, using a magnetic balance, was developed to measure the mass of NiFe₂O₄ in high temperature water. The lower detection limit of this method is 0.01 mg of NiFe₂O₄ with a maximum detection error of ±2%. The iron hydroxides react with Ni(OH)₂ to form NiFe₂O₄ and α-Fe₂O₃ through a dehydration reaction in 553 K water. Amorphous iron hydroxide and γ-FeOOH react rapidly, reaching saturated values of the conversion to NiFe₂O₄ within a few hours at 553 K. The dissolved oxygen has no influence on the NiFe₂O₄ formation. The amount of generated NiFe₂O₄ decreases with the reduction of the pH value, due to dissolution of the reactant. The rate of NiFe₂O₄ formation increases with reaction temperature, while the saturated value of formed NiFe₂O₄ decreases.     

Effects of Hydrogen Peroxide on Intergranular Stress Corrosion Cracking of Stainless Steel in High Temperature Water, (V)

The difference in electrochemical corrosion potential of stainless steel exposed to high temperature pure water containing hydrogen peroxide (H₂O₂) and oxygen (O₂)is caused by differences in chemical form of oxide films. In order to identify differences in oxide film structures on stainless steel after exposure to H₂O₂ and O₂ environments, characteristics of the oxide films have been examined by multilateral surface analyses, e.g., X-ray diffraction (XRD), Rutherford back scattering spectroscopy (RBS), secondary ion mass spectroscopy (SIMS) and X-ray photoelectron spectroscopy (XPS). Preliminary characterization results of oxide films confirmed that the oxide film formed under the H2O2 environment consists mainly of hematite (α-Fe₂O₂), while that under the O₂ environment consists of magnetite (Fe₃O₄). Furthermore oxidation at the very surface of the film is much more enhanced under the H₂O₂ environment than that under the O₂ environment. It was speculated that metal hydroxide plays an important role in oxidation of stainless steel in the presence of H₂O₂. The difference in electric resistance of oxide film causes the difference in anodic polarization properties. It is recommended that several anodic polarization curves for specimens with differently oxidized films should be prepared to calculate ECP based on the Evans diagram.     

Preparation of Cr2O3 film by MOCVD as hydrogen permeation barrier

Cr₂O₃ film on structural material as hydrogen permeation barrier can be applied in many areas such as hydrogen storage devices, vacuum solar receivers and fusion reactors. In this study, the Cr₂O₃ film was prepared by MOCVD on 316L stainless steel using chromium(III) acetylacetonate as precursor. The film was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The hydrogen permeation inhibition performance of films was investigated by deuterium permeation experiment. The 366 nm thick Cr₂O₃ film on 316L could reduce the deuterium permeability by 24–117 times at 823–973 K, revealing efficient inhibition to hydrogen permeation. The Cr₂O₃ film is dense, crack-free and has a corundum structure which possesses a more stable structure than a metastable phase or an amorphous phase. Moreover, the crystalline Cr₂O₃ could be easily obtained by MOCVD at a low temperature, e.g. 773 K.