• 한국재료학회지
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• 제18권11호
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• pp.597-603
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• 2008

Oxide effects experiments on massive hydriding reactions of Zr alloy with hydrogen gas were carried out at $400^{\circ}C$ under 1 atm in a $H_2$ environment with a thermo-gravimetric apparatus (TGA). Experimental results for oxide effects on massive hydriding kinetics show that incubation time is not proportional to oxide thickness. The results also show that the massive hydriding kinetics of pre-filmed Zr alloys follows linear kinetic law and that the hydriding rates are similar to that of oxide-free Zr alloys once massive hydriding is initiated. Unlikely microstructure of the oxide during incubation time, physical defects such as micro-cracks and pores were observed in the oxide after incubation time. Therefore, it seems that the massive hydriding of Zr alloys can be ascribed to short circuit paths and mechanical or physical defects, such as micro-cracks and pores in the oxide, rather than to hydrogen diffusion through the oxide resulting from the increase of oxygen vacancies in the hypo-stoichiometric oxide.

• 한국수소및신에너지학회논문집
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• 제10권4호
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• pp.197-210
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• 1999

The hydrogen storage performance and electrochemical properties of $Zr_{1-X}Ti_X(Mn_{0.2}V_{0.2}Ni_{0.6})_{1.8}$(X=0.0, 0.2, 0.4, 0.6) alloys are investigated. The relationship between discharge performance and alloy characteristics such as P-C-T characteristics and crystallographic parameters is also discussed. All of these alloys are found to have mainly a C14-type Laves phase structure by X-ray diffraction analysis. As the mole fraction of Ti in the alloy increases, the reversible hydrogen storage capacity decreases while the equilibrium hydrogen pressure of alloy increases. Furthermore, the discharge capacity shows a maxima behavior and the rate-capability is increased, but the cycling durability is rapidly degraded with increasing Ti content in the alloy. In order to analyze the above phenomena, the phase distribution, surface composition, and dissolution amount of alloy constituting elements are examined by S.E.M., A.E.S. and I.C.P. respectively. The decrease of secondary phase amount with increasing Ti content in the alloy explains that the micro-galvanic corrosion by multiphase formation is little related with the degradation of the alloys. The analysis of surface composition shows that the rapid degradation of Ti-substituted Zr base alloy electrode is due to the growth of oxygen penetration layer. After comparing the radii of atoms and ions in the electrolyte, it is clear that the electrode surface becomes more porous, and that is the source of growth of oxygen penetration layer while accelerating the dissolution of alloy constituting elements with increasing Ti content. Consequently, the rapid degradation (fast growth of the oxygen-penetrated layer) with increasing Ti substitution in Zr-based alloy is ascribed to the formation of porous surface oxide through which the oxygen atom and hydroxyl ion with relatively large radius can easily transport into the electrode surface.