DOE OSTI2013
The main objectives of this project are: (1) Characterization of the thermo mechanical properties of the novel dense HTM bulk sample; (2) Development of a correlation among the intrinsic factors (such as grain size and phase distribution), and the extrinsic factors (such as temperature and atmosphere) and the thermo-mechanical properties (such as strengths and stress) to predict the performance of a HTM system (HTM membrane and porous substrate) ; and (3) Evaluation of the stability of the novel HTM membrane and its property correlations after thermal cycling. Based on all results and analysis of the thermo mechanical properties for the HTM cermet bulk samples, several important conclusions were made. The mean σfs at room temperature is approximately 356 MPa for the HTM cermet. The mean σfs value decreases to 284 MPa as the temperature increases to 850?C. The Difference difference in atmosphere, such as air or N2, had an insignificant effect on the flexural strength values at 850?C for the HTM cermet. The HTM cermet samples at room temperature and at 500?C fractured without any significant plastic deformation. Whereas, at 850?C, the HTM cermet samples fractured, preceded by an extensive plastic deformation. It seems that the HTM cermet behaves more like an elastic material such as a nonmetal ceramic at the room temperature, and more like a ductile material at increased temperature (850?C). The exothermic peak during the TG/DTA tests centered at 600?C is most likely associated with both the enthalpy change of transformation from the amorphous phase into crystalline zirconia and the oxidation of Pd phase in HTM cermet in air. The endothermic peak centered at 800?C is associated with the dissociation of PdO to Pd for the HTM cermet sample in both inert N2 environment and air. There is a corresponding weight gain as oxidation occurs for palladium (Pd) phase to form palladium oxide (PdO) and there is a weight loss as the unstable PdO is dissociated back to Pd and oxygen. The normal stress and shear stresses from the Mohr?s circle indicate that the residual stress in the HTM cermet sample is mainly as compressive residual stress in the magnitude of -135 to -155 MP, and with very little shear stress (in the magnitude of 10 MPa). The magnitude of change in the normal stress and the shear stress is insignificant in the HTM after 120 thermal cycles. However, the principle normal stress changes from compressive to tensile residual stress and there is a significant increase in the shear stress after 500 thermal cycles. The calculated value based on the equation and the Mohr?s circle is found to be consistent with the experimental value for the as-received HTM cermet samples. At some rotation (φ) angle, the residual stress was found to be as tensile stress. Most ceramic material is weak in tension, and develops microscopic cracks. With treatment of 120 thermal cycles between 50?850?C, the HTM- sample exhibited thermally-induced cracks on the surface. Visually observable cracks appeared on the surface of HTM cermet with continuous thermal cycling, after 500 thermal cycles. The XRD powder diffraction analysis indicated an increased amount of crystalline PdO crystalline in HTM cermet after 120 and 500 thermal cycles as compare to the as-received samples. The Pd crystalline peaks were found to significantly decrease in peak intensity with thermal cycling. Higher peak intensity for PdO phase was observed with increased number of thermal cycles. A Monoclinic monoclinic zirconia phase was first identified in the as-received HTM as-received sample. However, with thermal cycling treatment of both 120 and 500 thermal cycles, the M-ZrO2 phase is transformed to the tetragonal YSZ, which is consistent with the thermal analysis results by TG/DTA. Correlations of the microstructural and thermo-mechanical properties of both selected reference material and ANL-3e HTM cermet bulk sample are affected mainly by porosity and microstructural features, such as grain size and pore size/distribution. The Young?s Modulus (E-value), especially, is positively proportional to the flexural strength for materials with similar crystallographic structure. For different crystallographic materials, physical properties such as E and density are independent of mechanical properties, such as flexural strength.. Microstructural properties, particularly, grain size and crystallographic structure, and thermodynamic properties are the main factors affecting the mechanical properties at both room and high temperatures. The oxidation and the plasticity of Pd phase mainly affect the mechanical properties of HTM cermet at high temperature or with thermal cycling treatment. Changes in the residual stress and microstructure affect the mechanical properties of HTM when subjected to high temperature or thermal cycling treatment.