To fully exploit the strengths of La2Zr2O7 pyroclores and promote them as a next-generation thermal barrier coating (TBC), the improvements of their thermally insulating property and fracture toughness are studied in this thesis. A strong phonon scattering source, rattlers, is found in Y3+-doped La2Zr2O7 pyrochlores. Rattlers dramatically flatten k (thermal conductivity)-T curves, or even make k approach the amorphous limit. The presence of rattlers is strongly dependent on (1) oversized atomic cages that are formed in pyrochlores; and (2) the occupation of smaller guest ions in those oversized cages. To maximize the rattling effect, In3+/Sc3+ ions that are much smaller than Y3+ are introduced to the La2Zr2O7 lattice. As envisaged, the smaller ions in the oversized lattice voids make k glass-like at a much lower doping content. Nevertheless, they are still not effective in reducing the high temperature plateau kmin. Instead, oxygen vacancies are very effective in reducing kmin, because they generate an electrostatic repulsion force among cations surrounding them, resulting in stronger lattice anharmonicity and weaker bonds. The plateau kmin is reduced dramatically by the filling of the B-sites in La2Zr2O7 with a 21% larger (and 50% heavier) Ce4+ guest ion rather than a 96% heavier (but similar-sized) Hf4+ ion, suggesting that a large absolute size of substitutional atoms is more effective in reducing kmin than a heavy absolute mass. This is because: (1) kmin is proportional to (E/M)0.5 (where E is the elastic modulus and M is the average atomic mass); (2) a larger size of guest ions tends to produce a weaker ionic bond and consequently, a lower E; and (3) the changing extent of E by introducing larger guest ions is much greater than that of M induced by adding heavier ones. Lastly, the fracture toughness (KIc) has been increased by dispersing the tetragonal 3 mol% Y2O3-stabilized zirconia (t-3YSZ) particulates in the La2Zr2O7 (LZ) matrix. The tendency of the dispersive t-3YSZ second phases transforming to monoclinic (m) phases strongly depends on the volume fraction introduced. For samples made from equilibrium route, they are toughened by phase transformations within the dispersive t-3YSZ second phases and a crack shielding effect arising from the residual compressive stress within the LZ matrix. An anticipated increase of KIc from ferroelastic toughening together with the residual compressive stress toughening highlights a potential to improve coating durability by depositing t’-3YSZ/LZ composite TBCs by the non-equilibrium route.

Reducing the heat losses in heavy-duty diesel engines is of importance for improving engine efficiency and reducing CO2 emissions. Depositing thermal barrier coatings (TBCs) onto engine components has been demonstrated to have great potential to reduce heat loss from the combustion chamber as well as from exhaust components. The overall aim of this thesis is to evaluate the thermal cycling lifetime and thermal insulation properties of TBCs for the purpose of reducing heat losses and thermal fatigue in heavy-duty diesel engines. In the thermal cycling test inside exhaust manifolds, nanostructured yttria-stabilized zirconia (YSZ) performed best, followed by YSZ with conventional microstructure and then La2Zr2O7. Forsterite and mullite could not withstand the thermal cycling conditions and displayed large cracks or spallation. Two sol-gel composite coatings displayed promising thermal cycling performance results in a furnace test under similar conditions. Thermal cycling testing of YSZ coatings having different types of microstructure, in a furnace at temperatures up to 800°C, indicated that the type of microstructure exerted a great influence. For the atmospheric plasma sprayed coatings, a segmented microstructure resulted in the longest thermal cycling lifetime. An even longer lifetime was seen for a plasma spray–physical vapour deposition (PS-PVD) coating. In situ heat flux measurements inside the combustion chamber indicated that plasma-sprayed Gd2Zr2O7 was the TBC material providing the largest heat flux reduction. This is explained by a combination of low thermal conductivity and high reflectance. The plasma-sprayed YSZ and La2Zr2O7 coatings provided very small heat flux reductions. Long-term testing indicated a running-in behaviour of YSZ and Gd2Zr2O7, with a reduction in heat flux due to the growth of microcracks in YSZ and the growth of macrocracks in Gd2Zr2O7. / <p>QC 20170821</p>