The effects of in situ Ti0₂ whisker reinforcement on mechanical and thermal properties of glass-ceramics in the Li₂O-Al₂0₃-P₂0₆-Si0₂ system were investigated. When Ti0₂ whiskers, having an average aspect ratio of 28, are precipitated from the glass-ceramic matrix, (Li_0.4,Ca_0.05)AI(Si_0.75,P_0.5)_04.5, flexural strength is improved from 72 to 134 MPa. Fracture toughness, K_Ic, is increased from the 1.1 to 1.6 MPa·m^1/2 due to crack deflection by the Ti0₂ whiskers. In situ Ti0₂ whisker-reinforced glass-ceramic exhibits rising fracture resistance, K_R, with increasing crack extension. The fracture resistance, K_R, is increased from 1.89 to 2.5 MPa·m^1/2 over the crack extension range range of 40 to 200 μm. The composite shows a narrow failure strength distribution compared to the glass-ceramic without Ti0₂ whisker precipitation. The coefficient of thermal expansion (CTE) changes from -2.8x10⁻⁷/"C to -1.7xl0⁻⁷/°C due to the precipitation of Ti0₂ phase which has a positive CTE (7.3xl0⁻⁶/°C). With the matrix composition, (Li_0.41,Mg_0.035)AI(Si₀0.48</sub>,P_O.52)O₄, a three-fold increase in flexural strength was observed with a Ti0₂ content of 12 wt%. CTE value of the composite increases linearly from a negative to a positive value with increasing Ti0₂ content up to 12 wt%. The in situ composite containing 8-10 wt% Ti0₂ exhibits near zero CTE values up to l000°C. / Ph. D.

This thesis deals with the investigations on the nonlinear electrical and manganetotransport properties of polycrystalline multi-phase ceramic composites of Zno/pervoskite manganite. Multifunctional properties are studied such as the enhanced low-field magnetoresistance(LFMR). magnetically tuneable low-voltage nonlinear current-voltage (I-V) characteristics with larger nonlinearity coefficients suitable for semiconducting and magnetoelectric devices. A brief introduction on the structure-property correlations, electronic and magnetic structures, nonlinear electrical conduction, phase separation, grain size and grain boundary effects on transport properties of manganites are presented. The nonlinear current-voltage characteristics of ZnO based varistors are also summarized. The thesis describes the synthesis of the ceramics and the methodology of different techniques utilized in characterizing the samples. The phase conversions in calcium manganite with changing Ca/Mn ratios as well as the oxygen non-stoichiometry and their influence on electrical transport properties were studied. The realization of low-voltage varistors prepared from ZnO+ CaMnO3 ceramic composites was described. An energy band model consisting of n-p-n heterojunctions of n-ZnO1-γ:Mn/p-CMZO/n-ZnO1 γ:Mn has been proposed in order to explain the large nonlinearity coefficients obtained at low field-strengths of 1.8 to 12 V/mm. The detailed investigationos on the structural identification and physico-chemical analyses of Ca4Mn7Zn3O21-δ(CMZO) phases having the beta-alumina or magnetoplumbite-type structures were carried out. The thesis also embodies the magnetically tuneable nonlinear I-V characteristics and the magnetotransport properties of ZnO/La(Sr)MnO3 and ZnO/La(Ca,Sr)MnO3 ceramic composites. The present investigations demonstrate that the ferromagnetic insulating (FMI) La06 Sr04Mn1-yZnyO3(y = 3 to 8 at.%) when present as minor phase in ZnO1- γ:Mn ceramics enables in attaining magnetically tunealbe nonlinear I-V characteristics. Wherein, the dominant ZnO1- γ:Mn phase remains paramagnetic. The results also indicate that the prevalence of ferromagnetism in ZnO1-γ:Mn is not significant for realizing magnetically tuneable I-V curves. The controversial results related to the existence of ferromagnetism in ZnO(doped)leading to diluted magnetic semiconductors(DMS) have been investigated. Another novel aspect of the present work is the low-field magnetoresistive(LFMR) property of ZnO/La(Sr)MnO3 and ZnO/La(Ca.Sr)MnO3 ceramic composites which been explained on the basis of spin-polarised tunneling across the intergrain regions. The influence of Zn2+ as a diamagnetic substitutent in modifying the crystallographic phase content, electrical transport and magnetic properties of Lao6Sro4MnO3 were studied in detail. The results point towards the fact the large decrease of Tc and Ms at lower Zn contents(≤ 8 at.%)is due to the dominant role played by the excess oxygen vacancy (Vo) as an electron donor in p-type Lao6Sro4Mn1-yZnyO3-δ rather than the charge compensatively predictable values. The modifications of electronic and magnetotransport properties were carried out on Lao6Sro4MnO3 substituted with diamagnetic ions such as Mg2+ - Al3+ - Ti4+ - Nb5+ - Mo6+ or W6+ at Mn-sublattice. The TEM studies including HREM results point to the fact the large ΔT(= Tc-TM-1)is accountable in terms of charge conduction within the electronically heterogeneous phase mixtures of charge ordered insulating (CO1) bi-stripes prevailing within the charge disordered FMI phases.