Grain growth by Ordered Coalescence of crystallites in Ceramics Grain Growth Mechanisms, Microstructure Evolution and Sintering

Abstract: Grain growth and densification process play the two most crucial roles on the microstructure evolution and the achieved performances during sintering of ceramics. In this thesis, the grain growth of SrTiO3, BaTiO3-SrTiO3 solid solutions and Si3N4 ceramics during spark plasma sintering (SPS) were investigated by electron microscopy.SrTiO3 ceramics starting from nanopowders were fabricated by SPS. A novel grain growth mechanism was discovered and named as ordered coalescence (OC) of nanocrystals. This mechanism involved nanocrystals as building blocks and is distinguished from atomic layer epitaxial growth (AEG) in classical sintering theory. The results also revealed that the dominant grain growth mechanism can be changed by varying heating rates. Low rate (10°C/min) gives AEG, whereas high rates (? 50°C/min) yields three-dimensional coalescence of nanocrystals, i.e. OC.BaTiO3-SrTiO3 sintered bodies were made by SPS of BaTiO3 and SrTiO3 nanopowders mixtures. A novel Sr1-xBaxTiO3 “solid solution” with mosaic-like single crystal structure was manufactured by OC of the precursor crystallites. This reveals a new path for preparation of solid solution grains or composites.  Si3N4 ceramics were prepared from ?- or ?-Si3N4 nanopowders at the same SPS conditions. The anisotropic OC of precipitated ?-Si3N4 crystallites gives elongated ?-Si3N4 grains at 1650°C using ?-Si3N4 nanopowder. In contrast, AEG leads to the equi-axed ?-Si3N4 grains using ?-Si3N4 nanopowder. The metastable ?- to ?-Si3N4 phase transformation and OC accelerates anisotropic grain growth.Grain motions contribute to the densification process during pressureless sintered 3Y-ZrO2 (>87%TD) or SPS of SrTiO3 (>92%TD) ceramics. This extends the sintering range for active grain re-arrangement over that predicted by classical theory.In this thesis a new grain growth mechanism (OC) is proved by using SPS and nanopowders. By OC the microstructural evolution can be manipulated.