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Title: Effect of processing conditions and second-phase additives on thermoelectric properties of SrTiO3 based ceramics
Author: Srivastava, Deepanshu
ISNI:       0000 0004 7429 6668
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2016
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Oxide ceramics have been increasingly researched for high temperature thermoelectric (TE) applications. SrTiO3 based materials are promising candidates due to its chemical and thermal stability. In this study, oxide ceramics of composition (1-x)SrTiO3-(x)La1/3NbO3 (0 smaller or equal to x smaller or equal to 0.3) were prepared by single-step solid state sintering in Ar/5%H2 at 1700 K. The density of all the samples prepared was above 90%. All the samples were predominantly single-phase compositions crystallised with a cubic structure in Pm ̅3m space group. The impact of oxygen deficiency, A-site vacancies and mixed oxidation states of Ti3+/Nb4+ on electrical and thermal transport properties was assessed. Optimum TE properties were obtained for x=0.2 (Sr0.8La0.067Ti0.8Nb0.2O(3-delta) = L2), which has 13.4% A-site vacancies. The ZT values improved from 0.2 to 0.27 at 1000 K, with an increase in sintering time from 8 hours to 48 hours, due to increased carrier concentration. Complex interplay of oxygen vacancies and excess donor substitution on A/B-sites of L2 (substituting 5-10% Sr/Ti with La/Nb) exhibited 35% improvement in ZT values, whilst maintaining the A-site vacancies and core-shell structures within grains, which reduced the thermal conductivity by ~50% compared to undoped SrTiO3 samples, due to strong phonon scattering. A facile method to incorporate metallic inclusions (2.5 wt% Fe/Cu) at grain boundaries in L2 ceramics is demonstrated. The modified compositions displayed a maximum ZT of ~0.37 at 1000 K for L2 samples containing metallic inclusions due to increased carrier concentration (5.5 x 10^21 carriers/cm^3) and carrier mobility (2.4 cm^2/(V.s).The addition of graphene/Graphene Oxide (GO) flakes in L2 ceramics has been investigated to improve the electrical conductivity of L2 composites without significantly increasing the thermal conductivity. Spark plasma sintering (SPS) of the composite powders at 1473 K and 50 MPa produced dense samples (>95% relative density) with a homogeneous dispersion of graphene/GO flakes, for loadings smaller or equal to 1.0 wt%. The effect of interaction and distribution of graphene/GO flakes within the ceramics on TE properties is investigated. The composite samples demonstrate anisotropic ZT values, with 20% improvement in the direction normal to the orientation of graphene flakes. A novel sintering method has been proposed which has strong industrial potential. The L2 based composites were sintered in Air at 1700 K (ramp rate: ±300 K/min), whilst samples were covered uniformly. Strong reducing conditions and evolution of secondary phases in the microstructure helped achieve, the very low electrical resistivity of ~3.0 x 10^(-6) ohm.m at room temperature. Secondary phases, sub-micron voids in the grains and A-site vacancies reduced the lattice thermal conductivity (~2.0 W/m.K), comparable to the lowest lattice thermal conductivity achievable (~1.5 W/m.K) at 1000 K and obtain a maximum ZT of 0.4 at 1000 K for L210G-Air/C composites.
Supervisor: Freer, Robert ; Kinloch, Ian Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: SPS ; Solid state sintering ; Figure of merit ; Ceramic Graphene composites ; Bulk Ceramic ; Thermoelectrics ; SrTiO3