Micro-texture of extruded Zr-2.5Nb tubes

We report the micro-texture of two extruded Zr-2.5Nb tubes determined using scanning electron microscopy combined with electron back-scattering diffraction (SEM/EBSD) and transmission electron microscopy and selected area diffraction (TEM/SAD). The pole figures determined by SEM/EBSD correspond well with bulk pole figures previously determined by X-ray diffraction (XRD). Three components of texture are seen to correlate with the shape and morphology of the α-grains and their contained dislocation substructures. The first component corresponds to elongated alpha grains containing a high density of a and c + a dislocations in which the c-axis is oriented at a relatively high angle to the long dimension of the α-grains as viewed in transverse section; these grains comprise a texture component with the c-axes in the radial transverse plane, tilted towards the radial direction. The second component corresponds to elongated α-grains containing a low dislocation density in which the c-axis is oriented parallel to the long dimension of the alpha grains: these grains also comprise a texture component with the c-axis in the radial/transverse plane, but predominantly in the transverse direction. The final component corresponds to colonies of Widmanstätten-like α-grains that are transformed from the β-phase: the majority of these grains have their c-axes in the axial direction. These grain have very low dislocation densities and are probably developed during cooling, after extrusion.     

In situ investigation of U(IV)-oxide surface dissolution and remineralization by electrochemical AFM

Surface chemical processes of UO₂ are investigated on a nanoscopic scale by electrochemical atomic force microscopy (ECAFM) using a home-developed electrochemical cell. Dissolution reactions of the solid surface and subsequent remineralization are observed at the solid-water interface under different redox conditions and carbonate concentrations. The local dissolution rates vary between different grain faces, grain boundaries and etch pits. A correlation between dissolution rates and the grain orientations relative to the specimen surface can be demonstrated by electron backscatter diffraction (EBSD). Remineralization under oxidizing conditions occurs mainly at grain faces with higher dissolution rates. The remineralized products are particles of 200-900 nm in diameter and exhibit a tabular morphology. Profound knowledge of the UO₂ surface chemistry on a nanoscale may help to clarify the related mechanisms explaining the macroscopically observed dissolution rates.     

Effect of prior thermal treatment on the microchemistry and crack propagation of proton-irradiated AISI 304 stainless steels

The effect of prior thermal treatment on crack growth was investigated on proton-irradiated Type 304 stainless steel (SS) of initially solution annealed (SA) and thermally sensitized (SEN) conditions. The Cr depletion profiles were measured by field emission gun transmission electron microscopy/energy dispersive spectroscopy (FEGTEM/EDS) in an attempt to correlate grain boundary chromium composition with the measured crack growth rate. The results showed that the crack growth of the 1-dpa-irradiated SEN 304SS is substantially higher than that of SA 304SS with the same irradiation dose. The unirradiated SEN material initially started with a shallow Cr depletion profile near grain boundary. After 1 dpa irradiation with proton, the Cr depletion profile becomes narrower and deeper. In contrast, the grain boundary Cr concentration in the SA specimen at the same irradiation dose was higher than that of the SEN specimen, mainly due to an initial Cr enriched condition. Consequently, the irradiated SEN specimen exhibited a higher degree of sensitization in electrochemical potentiokinetic reactivation test and faster crack growth rate in the stress corrosion crack test. The absence of irradiation enhanced crack growth in heavily thermal-sensitized 304SS is probably attributed to slower radiation-induced Cr depletion as a result of pre-existing thermally induced grain boundary Cr depletion. It is a clear indication that the inverse Kirkendall effect was hampered by the back diffusion of Cr due to initially depleted Cr concentration gradient near grain boundary.     

Tungsten erosion in the baffle and outboard regions of the ITER-like ASDEX Upgrade divertor

Similar to the design of the next-step device ITER, ASDEX Upgrade is equipped with vertical divertor targets with adjacent baffles extending towards the main chamber. In ITER, it is intended to employ tungsten as a plasma-facing material in this baffle area. Tungsten-coated graphite tiles were installed in the divertor baffle and the outboard side regions of ASDEX Upgrade for a full experimental campaign. The erosion behavior of tungsten was investigated by scanning electron microscopy and by measuring the thickness of the tungsten coatings before and after exposure. The coatings had an initial thickness of approximately 450 nm. Two distinct erosion mechanisms were observed: in the outer baffle region a reduction of the coatings’ thickness up to 100 nm was determined after about 6300 s of plasma discharge. On the roof baffle and on the inner baffle modules, no clear reduction of the film thickness was found. In the tracks of arcs, however, the tungsten coatings were completely removed. This represents an erosion of 5-10% of the tungsten-coated surface area in this region.     

Luminescence properties of zirconium oxide films

Various luminescence techniques have been applied in the characterisation of the zirconium oxide film formed on the metal matrix. Our investigation shows that some alloying elements in the zirconium alloys show characteristic emissions which could be used to study their distribution in the zirconium oxide. While the origin and detailed mechanism of luminescence in the zirconium oxide system is not well established, cathodoluminescence (CL) and thermoluminescence results from this study support the theory that oxygen vacancies in complexes with impurities are responsible for the intrinsic luminescence in the oxide system. The specific oxygen vacancy and impurity complex is reported in literature as the T-defect, having an energy of 2.2 eV. To aid in interpretation of the CL data, optical transmission properties of the oxides were also measured. The latter investigation showed the thickness of the oxide illuminated by the CL technique is greatly dependent on the optical transmission properties of the oxide, and it ranges from 20 μm for pure zirconium or low-alloyed zirconium oxides to less than 3 μm for oxides of alloys with more absorbing, or higher alloying element concentrations. The 20 μm depth of illumination is significantly deeper than the electron penetration depth, which suggests a secondary source of excitation, possibly characteristic X-rays emitted by the specimen. These combined properties of the oxide and technique can result in CL images showing structural contrast not easily seen during SEM or optical microscopy of oxidised surfaces.     

Towards a more comprehensive microstructural analysis of Zr-2.5Nb pressure tubing using image analysis and electron backscattered diffraction (EBSD)

Zr-2.5Nb pressure tubes used in CANDU (CANada Deuterium Uranium) reactors have a very complex microstructure, with two major crystallographic phases, α and β. These phases include a fair amount of deformation from the extrusion process and the cold working (∼25%) performed at the end of the manufacturing process. This microstructure (texture, grain aspect ratio, etc.) changes along the tube’s length and differs from tube to tube. In order to better understand the deformation mechanisms, these microstructural differences must be statistically characterized. Scanning electron microscopy combined with direct image analysis or with electron backscattered diffraction (EBSD) are good techniques for carrying out such a measurement. However it is not possible, using specimen preparation methods specific for each of these techniques, to reveal all of the grain and phase boundaries. We have thus developed post-treatment algorithms to be able to partially analyze the revealed Zr-2.5Nb microstructure. The first algorithm was used for image analysis treatments of micrographs taken at 5 kV on the radial-tangential plane of etched samples using a reactive ion etch (RIE, CF₄ + O₂). The second was developed for EBSD grain mapping and can be used to characterize α-Zr grain shape and orientation. The two techniques are complementary: EBSD gives information about the micro-texture and the relationship between the microstructure and micro-texture while image analyses of SEM micrographs reveal the direction and distribution of the α-Zr lamellae more easily and over a greater sample area than EBSD. However, the SEM micrographs that were used did not reveal any grain boundary (only phase boundary). An analysis of EBSD grain maps reveals that the average α-Zr grain size, mainly in the elongated direction (tangential), is smaller than what is normally obtained from an image analysis of SEM micrographs. The grain size distribution of type I α-Zr grains (deformed original (prior) α-Zr) and type II (stress-induced β-Zr → α-Zr phase transformation) is also shown to be different for sizes greater than 0.4 μm².     

Correlation between microstructure and corrosion behavior of Zr-Nb binary alloy

To investigate the correlation between microstructure and corrosion characteristics of Zr-Nb alloy, the microstructural observation and corrosion test with the change of cooling rate from beta temperature and the variation of Nb content were performed. The oxide characterization was also carried out by synchrotron XRD and TEM. When the Nb is contained less than solid solution limit (0.6 wt%) in Zr matrix, the difference of corrosion rate was not observed in spite of showing the significant changes of microstructures with cooling rate. While, when the Nb content in the alloy is more than 0.6 wt%, the corrosion properties were deteriorated with increasing the supersaturated Nb concentration in matrix and increasing the area fraction of β_Zr. Also it was observed that the supersaturated Nb in matrix was more effective to decrease the corrosion resistance than the β_Zr phase in the same Nb containing alloy, while the equilibrium Nb concentration below solubility limit in the matrix played an important role to enhance the corrosion resistance. During the corrosion testing in steam at 400 °C, the formation of β_Nb phase in water-quenched specimen would result in the reduction of Nb concentration in matrix. Thus, the corrosion resistance is enhanced with the formation of β_Nb phase. It is suggested from this study that the equilibrium Nb concentration below solubility limit in α matrix would be a more dominant factor in the enhancement of corrosion resistance than β phase (β_Nb or β_Zr), supersaturated Nb, precipitate, and internal microstructure such as twin, dislocation and plate.     

Influence of ageing heat treatment on alloy A-286 microstructure and stress corrosion cracking behaviour in PWR primary water

The influence of ageing heat treatment on alloy A-286 microstructure and stress corrosion cracking behaviour in simulated Pressurized Water Reactor (PWR) primary water has been investigated. A-286 microstructure was characterized by transmission electron microscopy for ageing heat treatments at 670 °C and 720 °C for durations ranging from 5 h to 100 h. Spherical γ′ phase with mean diameters ranging from 4.6 to 9.6 nm and densities ranging from 8.5 × 10²² m⁻³ to 2 × 10²³ m⁻³ were measured. Results suggest that both the γ′ phase mean diameter and density quickly saturate with time for ageing heat treatment at 720 °C while the γ′ mean diameter increases significantly up to 100 h for ageing heat treatment at 670 °C. Grain boundary η phase precipitates were systematically observed for ageing heat treatment at 720 °C even for short ageing periods. In contrast, no grain boundary η phase precipitates were observed for ageing heat treatments at 670 °C except after 100 h. Hardening by γ′ precipitation was well described by the dispersed barrier hardening model with a γ′ barrier strength of 0.23. Stress corrosion cracking behaviour of A-286 was investigated by means of constant elongation rate tensile tests at 1.5 × 10⁻⁷ s⁻¹ in simulated PWR primary water at 320 °C and 360 °C. In all cases, initiation was transgranular while propagation was intergranular. Grain boundary η phase precipitates were found to have no significant effect on stress corrosion cracking. In contrast, yield strength and to a lesser extent temperature were found to have significant influences on A-286 susceptibility to stress corrosion cracking.     

Spent fuel radionuclide source term model for assessing spent fuel performance in geological disposal. Part II: Matrix alteration model and global performance

In the framework of the research conducted on the long term evolution of spent nuclear fuel under geological disposal conditions, a source term model has been developed to evaluate the instantaneous release of radionuclides (RN) (instant release fraction, IRF) and the delayed release of the RN which are embedded within the matrix. This model takes into account most of the scientific results currently available except the effect of hydrogen and the current knowledge of the uncertainties. IRF was assessed by considering the evolution with time of the RN inventories located within the fuel microstructure to which no confinement properties can be allocated over the long term (gap, rim, grain boundaries). This allows for bounding values for the IRF as a function of time of canister breach and burnup. The matrix radiolytic dissolution was modeled by a simple kinetic model neglecting the recombination of radiolytic species and the influence of aqueous ligands. The oxidation of the UO₂ matrix was assumed not to be kinetically controlled. Spent fuel performance was therefore demonstrated to mainly depend on the reactive surface area.     

Microstructure of TRISO coated particles from the AGR-1 experiment: SiC grain size and grain boundary character

Pre-irradiation SiC microstructures in tristructural-isotropic (TRISO) coated fuel particles from the Advanced Gas Reactor Fuel Development and Qualification program’s first irradiation experiment (AGR-1) were quantitatively characterized using electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM). From EBSD, it was determined that only the cubic polymorph of as-deposited SiC was present and the SiC had a high fraction of coincident site lattice (CSL) Σ3 grain boundaries. Additionally, the local area misorientation (LAM), which is a qualitative measurement of strain in the SiC lattice, was mapped for each sample fuel variant. The morphology of the SiC/IPyC interfaces were characterized by TEM following site-specific focused ion beam (FIB) specimen preparation. It was determined that the SiC layer had a heavily faulted microstructure typical of chemical vapor deposition (CVD) SiC and that the average grain diameter increased radially from the SiC/IPyC interface for the samples manufactured with similar CVD conditions, while the last sample showed a nearly constant grain size across the layer.     

Detection of intergranular cracking susceptibility due to hydrogen in irradiated austenitic stainless steel with a superconducting quantum interference device (SQUID) sensor

To investigate the detection method of intergranular (IG) cracking susceptibility by hydrogen in irradiated austenitic stainless steel (SS), magnetic and mechanical properties were examined after two repeats of hydrogen charging and discharging (hydrogen treatment) in Type 304 SS which had been irradiated during use in different reactor cores. The residual magnetic flux density (Br) was measured with a superconducting quantum interference device sensor and Br increased with increased neutron fluence and repeated hydrogen treatments. Elongation decreased with an increase of Br and IG cracking appeared above Br of 2×10⁻⁵ T for this measuring method after repeated hydrogen treatments. These phenomena would be caused by hydrogen-induced martensite phase being formed on grain boundaries. It was thought the appearance of IG cracking susceptibility due to hydrogen in irradiated SS could be predicted by measuring the Br of the steel.     

Laser annealing in combination with mass spectroscopy, a technique to study deuterium on tokamak carbon samples, a tool for detritiation

In this study, a method is presented based on mass spectroscopy to measure the areal density of deuterium on a graphite surface exposed to tokamak discharges. The studied sample was cut from a bumper limiter exposed in the TEXTOR tokamak and annealed by a 1 J Excimer laser (KrF). The energy used was 400 mJ cm⁻², which is below the threshold for ablation, 1 J cm⁻². The release of HD and D₂ was measured by a mass spectroscopy set-up and no other species released from the sample were detected in this experiment. The amount of D released from the sample after 20 laser pulses was measured to 7 × 10¹⁶ D atoms per cm⁻² (for this particular sample) and most of the hydrogen at the surface was released in the first pulse, as checked by nuclear reaction analysis (NRA) techniques, which gave changes of the amount of deuterium before and after laser annealing. The sensitivity in this experiment was 5 × 10¹⁴ atoms per cm⁻² for HD and 5 × 10¹³ atoms per cm⁻² for D₂.     

Isolating the effect of radiation-induced segregation in irradiation-assisted stress corrosion cracking of austenitic stainless steels

Post-irradiation annealing was used to help identify the role of radiation-induced segregation (RIS) in irradiation-assisted stress corrosion cracking (IASCC) by preferentially removing dislocation loop damage from proton-irradiated austenitic stainless steels while leaving the RIS of major and minor alloying elements largely unchanged. The goal of this study is to better understand the underlying mechanisms of IASCC. Simulations of post-irradiation annealing of RIS and dislocation loop microstructure predicted that dislocation loops would be removed preferentially over RIS due to both thermodynamic and kinetic considerations. To verify the simulation predictions, a series of post-irradiation annealing experiments were performed. Both a high purity 304L (HP-304L) and a commercial purity 304 (CP-304) stainless steel alloy were irradiated with 3.2 MeV protons at 360 °C to doses of 1.0 and 2.5 dpa. Following irradiation, post-irradiation anneals were performed at temperatures ranging from 400 to 650 °C for times between 45 and 90 min. Grain boundary composition was measured using scanning transmission electron microscopy with energy-dispersive spectrometry in both as-irradiated and annealed samples. The dislocation loop population and radiation-induced hardness were also measured in as-irradiated and annealed specimens. At all annealing temperatures above 500 °C, the hardness and dislocation densities decreased with increasing annealing time or temperature much faster than RIS. Annealing at 600 °C for 90 min removed virtually all dislocation loops while leaving RIS virtually unchanged. Cracking susceptibility in the CP-304 alloy was mitigated rapidly during post-irradiation annealing, faster than RIS, dislocation loop density or hardening. That the cracking susceptibility changed while the grain boundary chromium composition remained essentially unchanged indicates that Cr depletion is not the primary determinator for IASCC susceptibility. For the same reason, the visible dislocation microstructure and radiation-induced hardening are also not sufficient to cause IASCC alone.     

2024铝合金冷轧板材的中子衍射织构表征与力学性能分析

2024铝合金是Al-Cu-Mg系铝合金的代表材料,在航空航天领域有重要应用,其力学性能受到晶粒择优取向（织构）的影响。本研究利用中子衍射与电子背散射（EBSD）技术表征了不同冷轧变形量下2024铝合金板材的晶粒形貌与取向分布,基于拉伸实验进行了特征力学性能测试,研究了织构与力学性能的关联性。拉伸试验结果表明板材沿轧向方向屈服强度最优,沿与轧向呈45°方向延伸率最优;通过中子衍射测得{111}极图定性分析了板材沿宏观方向力学性能变化趋势,结果与拉伸测试结果一致。研究表明,相对于EBSD,中子衍射能更好表征粗晶粒材料中晶粒取向的分布,反映材料体织构,从而可用于定性判断其力学性能,为优化材料工艺、提高服役性能提供有效支撑。     

Comparison of the air oxidation behaviors of Zircaloy-4 implanted with yttrium and cerium ions at 500 °C

As a valuable process for surface modification of materials, ion implantation is eminent to improve mechanical properties, electrochemical corrosion resistance and oxidation behaviors of varieties of materials. To investigate and compare the oxidation behaviors of Zircaloy-4, implantation of yttrium ion and cerium ion were respectively employed by using an MEVVA source at the energy of 40 keV with a dose ranging from 1×10¹⁶ to 1×10¹⁷ ions/cm². Subsequently, weight gain curves of the different specimens including as-received Zircaloy-4 and Zircaloy-4 specimens implanted with the different ions were measured after oxidation in air at 500 °C for 100 min. It was obviously found that a significant improvement was achieved in the oxidation behaviors of implanted Zircaloy-4 compared with that of the as-received Zircaloy-4, and the oxidation behavior of cerium-implanted Zircaloy-4 was somewhat better than that of yttrium-implanted specimen. To obtain the valence and the composition of the oxides in the scale, X-ray photoemission spectroscopy was used in the present study. Glancing angle X-ray diffraction, employed to analyze the phase transformation in the oxide films, showed that the addition of yttrium transformed the phase from monoclinic zirconia to tetragonal zirconia, yet the addition of cerium transformed the phase from monoclinic zirconia to hexagonal zirconia. In the end, the mechanism of the improvement of the oxidation behavior was discussed.     

Effect of β phase, precipitate and Nb-concentration in matrix on corrosion and oxide characteristics of Zr-xNb alloys

The corrosion test and oxide characterization were performed on the specimens having different Nb-content in the range of 0-5 wt%. The specimens were heat-treated at 570 °C for 500 h to get the α+β_Nb phase and at 640 °C for 10 h to get the α+β_Zr phase after β-quenching. The corrosion tests were carried out at 360 °C. In the low Nb-contents of 0.1-0.2 wt% where Nb was soluble in the matrix without the formation of Nb-containing precipitates or β phase, the samples showed the excellent corrosion resistance and their corrosion resistance was not affected by heat-treatment. The corrosion resistance was improved by the stabilization of tetragonal ZrO₂ and columnar oxide structure when all added Nb was soluble in the matrix to equilibrium concentration. In the high Nb-contents of 1.0-5.0 wt%, the corrosion rate was very sensitive to the annealing condition. The transformation of oxide crystal structure from tetragonal ZrO₂ to monoclinic ZrO₂ and oxide microstructure from columnar to equiaxed structure was accelerated in the samples having β_Zr phase, while retarded in the sample having β_Nb phase. This means that the formation of β_Nb phase resulted in the reduction of Nb concentration in the α matrix, thus the corrosion resistance was enhanced with the formation of β_Nb phase. From the corrosion test and oxide characterization, it is suggested that the equilibrium concentration of Nb in the α matrix would be a more dominant factor to enhance the corrosion resistance than the Nb-containing precipitates, supersaturated Nb, and β phase (β_Nb or β_Zr).     

Design feasibility study of a divertor component reinforced with fibrous metal matrix composite laminate

Fibrous metal matrix composites possess advanced mechanical properties compared to conventional alloys. It is expected that the application of these composites to a divertor component will enhance the structural reliability. A possible design concept would be a system consisting of tungsten armour, copper composite interlayer and copper heat sink where the composite interlayer is locally inserted into the highly stressed domain near the bond interface. For assessment of the design feasibility of the composite divertor concept, a non-linear multi-scale finite element analysis was performed. To this end, a micro-mechanics algorithm was implemented into a finite element code. A reactor-relevant heat flux load was assumed. Focus was placed on the evolution of stress state, plastic deformation and ductile damage on both macro- and microscopic scales. The structural response of the component and the micro-scale stress evolution of the composite laminate were investigated.     

In-pile electrochemical measurements on AISI 304 and AISI 306 in PWR conditions – Experimental results

In-pile electrochemical measurements were performed in order to investigate the effect of radiation on the electrochemical corrosion behaviour of AISI 304 and AISI 316 in PWR primary water (400 ppm B and 2 ppm Li) at 300 °C. The corrosion potential was continuously monitored during the whole irradiation period. Polarization resistance measurements and electrochemical impedance spectroscopy were performed at regular intervals. Polarization curves were recorded halfway through and at the end of each reactor cycle. All measurements were performed on both an in-flux and an out-of-flux 3-electrode electrochemical cell, each containing a platinum high-temperature reference electrode and an yttrium-stabilized zirconia (YSZ) reference electrode. The results show a small influence of radiation on the corrosion potential. However, the impedance data show a marked difference between in-flux and out-of-flux. The Nyquist diagram shows one semi-circle and one flattened semi-circle of which a branch leaps off indicating an R-(R//C)-(CPE//RW) type equivalent circuit.     

Corrosion behavior of Fe-Ni-Cr alloys in the molten salt of LiCl-Li2O at high temperature

At Korea Atomic Energy Research Institute (KAERI), we investigated the corrosion behavior of a series of Fe-Cr-Ni alloys with different chromium contents in molten LiCl and molten LiCl-25wt%Li₂O mixture at temperatures ranging from 923 to 1123 K. In molten LiCl, dense protective scale of LiCrO₂ grows outwardly while corrosion is accelerated by addition of Li₂O to LiCl. The basic fluxing of Cr₂O₃ by Li₂O would be the cause of accelerated corrosion. Because of low oxygen solubility and very high Li₂O activity in the molten LiCl-Li₂O mixture, Cr is preferentially corroded while Ni remains stable and thus, corrosion rate of the alloys in molten LiCl-Li₂O mixture increases with an increase in Cr content.     

Investigation of electrorefining of metallic alloy fuel onto solid Al cathodes

This work concerned the electrorefining of UZr and UPuZr alloys on a solid aluminium cathode, in the LiCl-KCl eutectic melt containing U³⁺, Pu³⁺, Np³⁺, Zr²⁺ or Zr⁴⁺, Am³⁺, Nd³⁺, Y³⁺, Ce³⁺ and Gd³⁺ chlorides. During constant current electrolyses, the use of a cathodic cut-off potential (−1.25 V versus Ag/AgCl) allowed to selectively deposit actinides (mainly U), while lanthanides remained in the salt. The aim was to determine the maximal load achievable on a single aluminium electrode. The total exchange charge was 4300 C, which represents the deposition of 3.72 g of actinides in 4.17 g Al, yielding a composition of 44.6 wt% An in Al. It was shown that the melting of the cathode contributed to increase the total amount of actinides deposited on the aluminium.