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Thermodynamic and Kinetic Studies for a Refractory Materials Program

Report Number: ASD-TDR-62-204 Part III
Author(s): L. A. McClaine
Corporate Author: Arthur D. Little, Inc.
Laboratory: Air Force Materials Laboratory
Date of Publication: 1964-04
Pages: 222
Contract: AF 33(616)-7472
Project: 7350
Task: 735001
AD Number: AD0601424

Work during 1963 is reported and the work from mid-1960 reviewed on a comprehensive program of thermodynamic and kinetic studies necessary to the theoretical consideration to tempreatures of 30000K of the reactions of the zirconium and hafnium carbides and borides with oxygen- or halogen-containing atmospheres. Work presented includes: preparation of borides and carbides; low temperature heat capacity measurements on HfB2, HfC and hafnium metal; estimation of entropies at 298K for refractory diborides, nitrides, carbides, and oxides from high temperature heat content data; current status of heats of formation of the borides and carbides from oxygen and fluorine bomb calorimetry; and studies proving the feasibility of the matrix isolation technique for spectroscopy of high temperature molecules through studies on the Lithium halides. Status of electron diffraction, equilibria, and heat of solution studies of the hafnium and zirconium halides is presented. Kinetic studies completed on the oxidation and fluorination of the hafnium and zirconium carbides and diborides are presented in detail. From ac and dc electrical conductivity studies on tetragonal ZrO2, a model of the defect structure is devised and oxygen diffusion in ZrO2 is calculated.

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