Ceramic powder synthesis thermodynamics

This chapter discusses the fluid-solid and solid-solid reactions used to produce ceramic powders. The first aspect of this discussion is the spontaneity of a particular reaction for a given temperature and atmosphere. Thermodynamics is used to determine whether a reaction is spontaneous. The thermod3mamics of the thermal decomposition of minerals and metal salts, oxidation reactions, reduction reactions, and nitridation reactions is discussed because these are often used for ceramic powder synthesis. After a discussion of thermodynamics, the kinetics of reaction is given to determine the time necessary to complete the reaction. Reaction kinetics are discussed in terms of the various rate determining steps of mass and heat transfer, as well as surface reaction. After this discussion of reaction kinetics, a brief discussion of the types of equipment used for the synthesis of ceramic powders is presented. Finally, the kinetics of solid—solid interdiffusion is discussed. 

This chapter discusses four methods of gas phase ceramic powder synthesis by flames, fiunaces, lasers, and plasmas. In each case, the reaction thermodynamics and kinetics are similar, but the reactor design is different. To account for the particle size distribution produced in a gas phase synthesis reactor, the population balance must account for nudeation, atomistic growth (also called vapor condensation) and particle—particle segregation. These gas phase reactors are real life examples of idealized plug flow reactors that are modeled by the dispersion model for plve flow. To obtain narrow size distribution ceramic powders by gas phase synthesis, dispersion must be minimized because it leads to a broadening of the particle size distribution. Finally the gas must be quickly quenched or cooled to freeze the ceramic particles, which are often liquid at the reaction temperature, and thus prevent further aggregation. 

Lencka, M.M., Riman, R.E. Thermodynamic modeling of hydrothermal synthesis of ceramic powders. Chem. Mater. 5,61-70 (1993)... 

SHS is particularly suited to the synthesis of refractory ceramic powders and compacts such as carbides of Ti, Si, Cr, Ta, and B, borides of Ti, V and Cr, nitrides of B, Ti, Al, Si, sihcides of Mo, Ti and V, or even more complex compounds such as YBa2Cu307-,. The thermodynamic basis of the process, the individual types of SHS processing techniques, and the equipment and post-synthesis processing to obtain powder compacts have been reviewed by Yukhvid (1992). 

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