Laser assisted directional solidification of zirconia-based eutectics

Directionally solidified zirconia-based eutectic (DSE) fibres were obtained using the laser floating zone (LFZ) method. Two systems were investigated: zirconia-barium zirconate and zirconia-mullite. The purpose was to take advantage of zirconia properties, particularly as an ionic conductor and a mechanical rein-forcement phase. The influence of processing conditions in the structural and microstructural characteristics and their consequences on the electrical and mechanical behaviour were the focus of this thesis. The novel zirconia-barium zirconate eutectic materials were developed in order to combine oxygen ionic conduction through zirconia with protonic conduction from barium zirconate, promoting mixed ionic conduction behaviour. The mi-crostructure of the fibres comprises two alternated regions: bands having coarser zirconia-rich microstructure; and inter-band regions changing from a homogeneous coupled eutectic, at the lowest pulling rate, to columnar colony microstructure, for the faster grown fibres. The bands inter-distance increases with the growth rate and, at 300 mm/h, zirconia dendrites develop enclosed in a fine-interpenetrated network of 50 vol.% ZrO2-50 vol.% BaZrO3. Both phases display contiguity without interphase boundaries, according to impedance spec-troscopy data. Yttria-rich compositions were considered in order to promote the yttrium incorporation in both phases, as revealed by Raman spectroscopy and corroborated by the elemental chemical analysis in energy dispersive spectros-copy. This is a mandatory condition to attain simultaneous contribution to the mixed ionic conduction. Such results are supported by impedance spectrosco-py measurements, which clearly disclose an increase of total ionic conduction for lower temperatures in wet/reduction atmospheres (activation energies of 35 kJ/mol in N2+H2 and 48 kJ/mol in air, in the range of 320-500 ºC) compared to the dry/oxidizing conditions (attaining values close to 90 kJ/mol, above 500 ºC). At high temperatures, the proton incorporation into the barium zirconate is un-favourable, so oxygen ion conduction through zirconia prevails, in dry and oxi-dizing environments, reaching a maximum of 1.3x10-2 S/cm in dry air, at ~1000 ºC. The ionic conduction of zirconia was alternatively combined with another high temperature oxygen ion conductor, as mullite, in order to obtain a broad elec-trolytic domain. The growth rate has a huge influence in the amount of phases and microstructure of the directionally solidified zirconia-mullite fibres. Their microstructure changes from planar coupled eutectic to dendritic eutectic mor-phology, when the growth rate rises from 1 to 500 mm/h, along with an incre-ment of tetragonal zirconia content. Furthermore, high growth rates lead to the development of Al-Si-Y glassy phase, and thus less mullite amount, which is found to considerably reduce the total ionic conduction of as-grown fibres. The reduction of the glassy phase content after annealing (10h; 1400 ºC) promotes an increase of the total ionic conduction (≥0.01 S/cm at 1370 °C), raising the mullite and tetragonal zirconia contents and leading to microstructural differ-ences, namely the distribution and size of the zirconia constituent. This has important consequences in conductivity by improving the percolation pathways. A notable increase in hardness is observed from 11.3 GPa for the 10 mm/h pulled fibre to 21.2 GPa for the fibre grown at 500 mm/h. The ultra-fine eutectic morphology of the 500 mm/h fibres results in a maximum value of 534 MPa for room temperature bending strength, which decreases to about one-fourth of this value at high temperature testing (1400 ºC) due to the soft nature of the glassy-matrix.

Severe plastic deformation of Al–Zn alloys

In this work, the R&D work mainly focused on the mechanical and microstructural analysis of severe plastic deformation (SPD) of Al–Zn alloys and the development of microstructure–based models to explain the observed behaviors is presented. Evolution of the microstructure and mechanical properties of Al–30wt% Zn alloy after the SPD by the high–pressure torsion (HPT) has been investigated in detail regarding the increasing amount of deformation. SPD leads to the gradual grain refinement and decomposition of the Al–based supersaturated solid solution. The initial microstructure of the Al–30wt% Zn alloy contains Al and Zn phases with grains sizes respectively of 15 and 1 micron. The SPD in compression leads to a gradual decrease of the Al and Zn phase grain sizes down to 4 microns and 252 nm, respectively, until a plastic strain of 0.25 is reached. At the same time, the average size of the Zn particles in the bulk of the Al grains increases from 20 to 60 nm and that of the Zn precipitates near or at the grain boundaries increases as well. This microstructure transformation is accompanied at the macroscopic scale by a marked softening of the alloy. The SPD produced by HPT is conducted up to a shear strain of 314. The final Al and Zn grains refine down to the nanoscale with sizes of 370 nm and 170 nm, respectively. As a result of HPT, the Zn–rich (Al) supersaturated solid solution decomposes completely and reaches the equilibrium state corresponding to room temperature and its leads to the material softening. A new microstructure–based model is proposed to describe the softening process occurring during the compression of the supersaturated Al–30wt% Zn alloy. The model successfully describes the above–mentioned phenomena based on a new evolution law expressing the dislocation mean free path as a function of the plastic strain. The softening of the material behavior during HPT process is captured very well by the proposed model that takes into consideration the effects of solid solution hardening and its decomposition, Orowan looping and dislocation density evolution. In particular, it is demonstrated that the softening process that occurs during HPT can be attributed mainly to the decomposition of the supersaturated solid solution and, in a lesser extent, to the evolution of the dislocation mean free path with plastic strain.