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Register a new userHydride growth mechanism in Zircaloy-4: investigation of the partitioning of alloying elements
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The long-term safety of water-based nuclear reactors relies in part on the reliability of zirconium-based nuclear fuel. Yet the progressive ingress of hydrogen during service makes zirconium alloys subject to delayed hydride cracking. Here, we use a combination of electron back-scattered diffraction and atom probe tomography to investigate specific microstructural features from the as-received sample and in the blocky-alpha microstructure, before and after electrochemical charging with hydrogen or deuterium followed by a low temperature heat treatment at 400C for 5 hours followed by furnace cooling at a rate of 0. 5C per min. Specimens for atom probe were prepared at cryogenic temperature to avoid the formation of spurious hydrides. We report on the compositional evolution of grains and grain boundaries over the course of the samples thermal history, as well as the ways the growth of the hydrides modifies locally the composition and the structure of the alloy. We observe a significant amount of deuterium left in the matrix, even after the slow cooling and growth of the hydrides. Stacking faults form ahead of the growth front and Sn segregates at the hydride-matrix interface and on these faults. We propose that this segregation may facilitate further growth of the hydride. Our systematic investigation enables us discuss how the solute distribution affects the evolution of the alloys properties during its service lifetime.
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The interactions between {delta}-hydrides and plastic slip in a commercial zirconium alloy, Zircaloy-4, under stress were studied using in situ secondary electron microscope (SEM) micropillar compression tests of single crystal samples and ex situ digital image correlation (DIC) macroscale tensile tests of polycrystalline samples. The hydrides decorate near basal planes in orientation, and for micropillars orientated for <a> basal slip localised shear at the hydride-matrix interface is favoured over slip in {alpha}-Zr matrix due to a lower shear stress required. In contrast, for pillars oriented for <a> prismatic slip the shear stress needed to trigger plastic slip within the hydride is slightly higher than the critical resolved shear stress (CRSS) for the <a> prismatic slip system. In this case, slip in the hydride is likely achieved through <110>-type shear which is parallel to the activated <a>-type shear in the parent matrix. At a longer lengthscale, these results are used to inform polycrystalline samples analysed using high spatial resolution DIC. Here localised interface shear remains to be a significant deformation path which can both cause and be caused by matrix slip on planes closely-oriented to the phase boundaries. Matrix slip on planes nearly perpendicular to the adjacent hydride-matrix interfaces can either result in plastic slip within the hydrides or get arrested at the interfaces, generating local stress concentration. Through these mechanisms, the presence of {delta}-hydrides leads to enhanced strain localisation in Zircaloy-4 early in the plastic regime.
Proposed as blanket structural materials for fusion power reactors, reduced activation ferritic/martensitic (RAFM) steel undergoes volume expanding and contracting in a cyclic mode under service environment. Particularly, being subjected to significant fluxes of fusion neutrons RAFM steel suffers considerable local volume variations in the radiation damage involved regions. It is necessary to study the structure properties of the alloying elements in contraction and expansion states. In this paper we studied local substitution structures of thirteen alloying elements Al, Co, Cr, Cu, Mn, Mo, Nb, Ni, Si, Ta, Ti, V, and W in bcc Fe and calculated their substitutional energies in the volume variation range from -1.0% to 1.0%. From the structure relaxation results of the first five neighbor shells around the substitutional atom we find the relaxation in each neighbor shell keeps approximately uniform within the volume variation from -1.0% to 1.0% except those of Mn and the relaxation of the fifth neighbor shell is stronger than that of the third and forth, indicating that the lattice distortion due to the substitution atom is easier to spread in <111> direction than in other direction. The relaxation pattern and intensity are related to the size and electron structure of the substitutional atom. For some alloying elements, such as Mo, Nb, Ni, Ta, Ti and W, the substitutional energy decreases noticeably when the volume increases. Further analysis show that the substitutional energy comprises the energy variation originated from local structure relaxation and the chemical potential difference of the substitutional atom between its elemental crystalline state and the solid solution phase in bcc Fe. We think the approximately uniform relaxation of each neighbor shell around a substitutional atom give rise to a linear decrease in the substitutional energy with the increasing volume.
Crystal-level strain rate sensitivity and temperature sensitivity are investigated in Zircaloy-4 using combined of bending creep test, digital image correlation, electron backscatter detection and thermo-mechanical tensile tests with crystal plasticity modelling. Crystal rate-sensitive properties are extracted from room temperature microscale creep, and temperature sensitivity from thermal polycrystalline responses. Crystal plasticity results show that large microscale creep strain is observed near notch tip increased up to 50% due to cross-slip activation. Grain-level microscale SRS is highly heterogeneous, and its crystallographic sensitivity is dependent on plastic deformation rate and underlying grain-based dislocation slip activation. Pyramidal <c+a> slip and total dislocation pileups contribute to temperature-sensitive texture effect on yielding and strength hardening. A faithful reconstruction of polycrystal and accurate rate-sensitive single-crystal properties are the key to capture multi-scale SRSs.
CONSPECTUS: Two-dimensional (2D) compound materials are promising materials for use in electronics, optoelectronics, flexible devices, etc. because they are ultrathin and cover a wide range of properties. Among all methods to prepare 2D materials, chemical vapor deposition (CVD) is promising because it produces materials with a high quality and reasonable cost. So far, much efforts have been made to produce 2D compound materials with large domain size, controllable number of layers, fast-growth rate, and high quality features, etc. However, due to the complicated growth mechanism like sublimation and diffusion processes of multiple precursors, maintaining the controllability, repeatability, and high quality of CVD grown 2D binary and ternary materials is still a big challenge, which prevents their widespread use. Here, taking 2D transition metal dichalcogenides (TMDCs) as examples, we review current progress and highlight some promising growth strategies for the growth of 2D compound materials. The key technology issues which affect the CVD process, including non-metal precursor, metal precursor, substrate engineering, temperature, and gas flow, are discussed. Also, methods in improving the quality of CVD-grown 2D materials and current understanding on their growth mechanism are highlighted. Finally, challenges and opportunities in this field are proposed. We believe this review will guide the future design of controllable CVD systems for the growth of 2D compound materials with good controllability and high quality, laying the foundations for their potential applications.
Growth of mono-dispersed AlGaN nanowires of ternary wurtzite phase is reported using chemical vapour deposition technique in the vapour-liquid-solid process. The role of distribution of Au catalyst nanoparticles on the size and the shape of AlGaN nanowires are discussed. These variations in the morphology of the nanowires are understood invoking Ostwald ripening of Au catalyst nanoparticles at high temperature followed by the effect of single and multi-prong growth mechanism. Energy-filtered transmission electron microscopy is used as an evidence for the presence of Al in the as-prepared samples. A significant blue shift of the band gap, in the absence of quantum confinement effect in the nanowires with diameter about 100 nm, is used as a supportive evidence for the AlGaN alloy formation. Polarized resonance Raman spectroscopy with strong electron-phonon coupling along with optical confinement due to the dielectric contrast of nanowire with respect to that of surrounding media are adopted to understand the crystalline orientation of a single nanowire in the sub-diffraction limit of about 100 nm using 325 nm wavelength, for the first time. The results are compared with the structural analysis using high resolution transmission microscopic study.
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