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.

The player and video game interplay in the gameplay experience construct

Among the many discussions and studies related to video games, one of the most recurrent, widely debated and important relates to the experience of playing video games. The gameplay experience – as appropriated in this study – is the result of the interplay between two essential elements: a video game and a player. Existing studies have explored the resulting experience of video game playing from the perspective of the video game or the player, but none appear to equally balance both of these elements. The study presented here contributes to the ongoing debate with a gameplay experience model. The proposed model, which looks to equally balance the video game and the player elements, considers the gameplay experience to be both an interactive experience (related to the process of playing the video game) and an emotional experience (related to the outcome of playing the video game). The mutual influence of these two experiences during video game play ultimately defines the gameplay experience. To this gameplay experience contributes several dimensions, related to both the video game and player: the video game includes a mechanics, interface and narrative dimension; the player includes a motivations, expectations and background dimension. Also, the gameplay experience is initially defined by a gameplay situation, conditioned by an ambient in which gameplay takes place and a platform on which the video game is played. In order to initially validate the proposed model and attempt to show a relationship among the multiple model dimensions, a multi-case study was carried out using two different video games and player samples. In one study, results show significant correlations between multiple model dimensions, and evidence that video game related changes influence player motivations as well as player visual behavior. In specific player related analysis, results show that while players may be different in terms of background and expectations regarding the game, their motivation to play are not necessarily different, even if their performance in the game is weak. While further validation is necessary, this model not only contributes to the gameplay experience debate, but also demonstrates in a given context how player and video game dimensions evolve during video game play.