The Physical Chemistry of Nucleation of Sub-micrometer Non-oxide Ceramic Powders via Sub-oxide Vapour-phase Reduction Reaction

"Fine ceramic powders (<500 nm) exhibit exceptional physical and mechanical properties in engineered structural ceramics. The production of fine powders, in particular the non-oxide ceramics, via a cheaper route than the organic solvent route has been rather elusive. This paper examines the physical chemistry of sub-oxide vapour-phase reduction reaction for the nucleation of non-oxide ceramic phase. Well known vapour species eg SiO and BO in the production of technical ceramic powders (SiC, BN) are particularly discussed for understanding the nucleation process of SiC and BN ceramic phases respectively. The regimes of partial pressures and temperatures are particularly 'identified. The calculated nucleation rate as a function of the temperature is compared with the experimental results on powder morphology. The production of amorphous and nanocrystalline h-BN powders is discussed in the context of substrate structure and thermodynamic parameters.IntroductionThe physical and mechanical properties of ceramic components are strongly dependent on the powder particle size and morphology used for their fabrication. For example the strength (Os) of the structural ceramic components increases with decreasing average grain-size (d) in accordance with the Hall-Petch relationship: Os = 0""0 + k/(d)1/2. Here k is an empirical constant which can be established from the graphical relationship. However as the particle size approaches submicrometer-size range, the dependence of strength on the particle size becomes more complex [1]. The design of ceramic components based on nanometer-size particles have recently become an important field which can offer ceramic materials with properties comparable to their metal counterparts. Several materials based on these concepts have been developed and reported by Niihara [2]. For example, the Al2O 3-SiC nanocomposite, having average B-SiC grain size 0.3-2um with intragranular SiC particulates of 5-10 nm has unusually high strengths (1100 MN/m2) at low and elevated temperatures combined with enhanced fracture toughness (> 4 MN-ml.5) which is an unusual combination in structural ceramics. Besides mechanical properties, as the particle size of ceramic powders approaches the nanometer-size range, the charge transport properties also improve by many times. The effect of particle size on the electrical conductivity of Si3N4-TiN composites has been well documented [3.4]. The size of ceramic particulates without doubt plays a pivotal role in determining the properties of ceramic components."