Joining of electronic components onto the circuit boards is done by soldering operation, during production of all electronic devices. In many countries, including Turkey, traditionally used tin-lead (Sn-Pb) solder alloys have been restricted to be used in consumer electronics appliances because of the toxic effects of lead (Pb) within these alloys. Tin-silver-copper (Sn-Ag-Cu) based alloys have been developed as the most promising candidate that can replace the Sn-Pb alloys. However, various problems have emerged with the increasing trend in use of Sn-Ag-Cu solder alloys in electronics industry, namely large intermetallic compound formation, low wettability and thermal shock resistance. Many researches have been done in the past decade to overcome these problems. The solutions are based on changing the undercooling of the solder alloy / which was determined to be done by either changing the composition of the solder alloy by micro-alloying or changing the cooling rate during soldering operation. In this thesis study Sn-3.5Ag-0.9Cu (wt. %) lead-free solder having the eutectic composition, was micro-alloyed with additions of aluminum (Al), iron (Fe) and titanium (Ti). Experimental results were compared with commercially available near-eutectic Sn-40Pb (wt. %) solder, a commercially available Sn-3.0Ag-0.5Cu (wt. %) solder and also eutectic Sn-3.5Ag.0.9Cu (wt. %) and near-eutectic Sn-3.7Ag-0.9Cu (wt. %) solders that were produced for this thesis study. In the first stage of the study, the effects of 0.05 wt. % of Al, Fe and Ti micro-alloying were investigated. When preliminary results of mechanical and thermal test were compared, Fe was found to make positive effect on shear strength and undercooling. Further research was carried out to establish a relationship between the Fe compositions and solder properties. Therefore, 0.01, 0.03, 0.07 and 0.1 wt. % Fe additions were also studied and results were reported. 0.01 wt. % and 0.07 wt. % Fe added solders were found to have a smaller undercooling, resulting with dispersed intermetallic compound (IMC) and thus has highest shear strength. Different cooling rates / 0.017, 0.17 and 1.7 &deg / C/sec were applied to solder-copper joints and microstructures were investigated. Large IMC-free microstructure was achieved by 0.01 wt. % Fe micro-alloyed solder, which was cooled with 1.7 &deg / C/sec rate. Wetting of copper substrate was found to be improved by additions of Al, Fe and Ti compared to alloy with eutectic composition of Sn-Ag-Cu alloy. Selected SAC+X alloys have been subjected to thermal shock experiments for crack formation analysis on the copper substrate-solder joints. The results showed that SAC+0.05Al solder has the higher thermal shock resistance, which no cracks were observed after 1500 cycles of thermal shock. In order to understand the insights of SAC performance, some of the lead-free solders were applied onto printed circuit boards for thermal shock resistance test. These results have indicate that the cracking may occur after thermal shock cycles due to process conditions of soldering operation (i.e. cooing rate), independent of the solder alloy composition.

Cette thèse avait pour objectif d’étudier les relations entre la microstructure de matériaux réfractaires et leurs propriétés thermomécaniques afin d’améliorer leur résistance aux chocs thermiques. En particulier, des modélisations numériques ont été réalisées afin de mieux comprendre la conception de la microstructure liée à des endommagements dus au différentiel de dilatation thermique. A cette fin, des résultats expérimentaux de matériaux simplifiés ont été utilisés comme référence pour l’approche numérique. Afin d’obtenir des résultats quantitatifs des phénomènes d’endommagement complexes, de nouveaux développements ont été apportés à une plate-forme de modélisation d’éléments discrets existante, nommée GranOO. Entre autre, une méthode de calibration direct des paramètres locaux ainsi une amélioration du concept de contrainte viriel ont été proposées. Ensuite, l’approche DEM a été appliquée afin de reproduire les endommagement thermiques lors du refroidissement des matériaux simplifiés et d’examiner leurs effets sur les propriétés apparentes. Les résultats obtenus de l’évolution du module de Young et du coefficient de dilatation thermique en fonction de température ont montré des tendances similaires avec les résultats expérimentaux. / The present thesis aimed at investigating the relationships between the microstructure of refractories and their thermomechanical properties in order to increase their thermal shock resistance. In particular, numerical modeling were carried out in order to better understand the design of microstructure involving damages due to thermal expansion mismatch during processing. For this purpose, experimental results on simplified materials were used as reference for this numerical approach. In order to obtain quantitative results of complex phenomena, new developments of an existing discrete element modeling platform, namely GranOO, were carried out. More specifically, direct calibration method of input parameters and improvement of virial stress concept were proposed. This DEM approach was then applied to reproduce thermal damages during cooling of simplified materials and to examine their effects on macroscopic properties. The obtained DEM results of evolution of Young’s modulus and thermal expansion coefficient as a function of temperature exhibited similar tendencies with experimental results

Anlagen zur Herstellung von Synthesegas (CO·H2) aus kohlenstoffhaltigen Rohstoffen werden durch hohe Temperaturen bis zu 1600 °C und Drücken bis zu 50 bar beansprucht und benötigen daher Schutz durch eine feuerfeste Ausmauerung. Zur Steigerung der Effizienz und Lebensdauer solcher Vergasungsanlagen ist die Entwicklung neuer keramischer Hochtemperaturwerkstoffe erforderlich. Solch ein Material stellt eine Al2O3-reiche Gießmasse dar, welche durch den gezielten Einsatz verschiedener ZrO2- und TiO2-Gehalte optimiert wurde. Es hat sich gezeigt, dass bereits durch die Zugabe geringer Mengen an ZrO2 bzw. TiO2 sowohl die Temperaturwechselbeständigkeit als auch die Korrosionsbeständigkeit von Al2O3 gegenüber Kohleschlacken erheblich verbessert werden kann, was auf die Ausbildung einer Spinell-Schutzschicht während des Korrosionsvorgangs zurückzuführen ist.

Anlagen zur Herstellung von Synthesegas (CO·H2) aus kohlenstoffhaltigen Rohstoffen werden durch hohe Temperaturen bis zu 1600 °C und Drücken bis zu 50 bar beansprucht und benötigen daher Schutz durch eine feuerfeste Ausmauerung. Zur Steigerung der Effizienz und Lebensdauer solcher Vergasungsanlagen ist die Entwicklung neuer keramischer Hochtemperaturwerkstoffe erforderlich. Solch ein Material stellt eine Al2O3-reiche Gießmasse dar, welche durch den gezielten Einsatz verschiedener ZrO2- und TiO2-Gehalte optimiert wurde. Es hat sich gezeigt, dass bereits durch die Zugabe geringer Mengen an ZrO2 bzw. TiO2 sowohl die Temperaturwechselbeständigkeit als auch die Korrosionsbeständigkeit von Al2O3 gegenüber Kohleschlacken erheblich verbessert werden kann, was auf die Ausbildung einer Spinell-Schutzschicht während des Korrosionsvorgangs zurückzuführen ist.

[pt] Cerâmicas termomióticas vem despertando interesse devido a sua propriedade de apresentar, sob aquecimento, uma expansão térmica baixa, próxima a zero ou negativa. Essa propriedade é proveniente de uma vibração transversal do ânion, que resulta numa aproximação de átomos em determinadas direções. A família A2M3O12 (A = um cátion trivalente e M = Mo6 positivo ou W6 positivo) apresenta uma transição de fase de monoclínica para ortorrômbica, sendo somente a fase ortorrômbica que apresenta o comportamento termomiótico. Essa família, especificamente, vem sendo bastante pesquisada, pois possui a vantagem de permitir uma vasta flexibilidade química, sem mudar de estrutura cristalina e por consequência, permitir ajustes no coeficiente de expansão térmica de acordo com a aplicação a qual o material se destina. A expansão térmica próxima à zero pode levar a uma promissora alta resistência ao choque térmico. Esse trabalho teve como objetivo, estudar as propriedades térmicas e mecânicas do Al2W3O12 que possui baixa expansão térmica positiva com o objetivo de determinar sua resistência ao choque térmico pela figura de mérito de Hasselman. Para isso, todas as suas propriedades térmicas (expansão térmica e condutividade) e mecânicas (módulo de elasticidade e resistência mecânica) foram obtidas experimentalmente apresentando um valor promissor de 120K (comparável ao da safira) para resistência ao choque térmico pela figura de mérito de Hasselman sob condições severas de aquecimento. A partir desse resultado foi desenvolvido uma segunda pesquisa com o objetivo de refinar a microestrutura e aumentar a densidade relativa da cerâmica maciça do Al2W3O12 e assim incrementar suas propriedades mecânicas. Uma síntese por co-precipitação, seguida de uma prensagem isostática e uma sinterização desenvolvida em três etapas foram implementadas, obtendo-se um aumento de 91 porcento para 96 porcento na densidade relativa, com aumento de 19 porcento no módulo de elasticidade e de 35 porcento na dureza vickers se comparados aos resultados obtidos pela amostra sinterizada anteriormente pelo método convencional de sinterização em uma etapa. No terceiro estágio desta tese foi estudada a expansão térmica de uma novo material (In0,5(ZrMg)0,75Mo3O12) com promissora expansão térmica próxima a zero (10-7 K-1), a partir do cálculo da regra das misturas. O material foi sintetizado por evaportação total.e seu coeficiente de expansão térmica intrínseco determinado in situ por difração de Raios-X foi de 1,6x10-7 K-1 na faixa de temperatura de 100 a 500 graus Celsius, enquanto o coeficiente de expansão térmica maciço, medido por dilatometria, foi de 6,68 x 10-7 K-1, na faixa de temperatura de 100 a 800 graus Celsius. Esse material apresenta uma transição de fase de monoclínica para ortorrômbica na temperatura de 82 graus Celsius o que limita seu uso como material termomiótico em temperaturas abaixo de 100 graus Celsius. / [en] Thermomiotic ceramics have been arousing interest due to their property of presenting a low, near or zero thermal expansion under hearing. This property comes from a transverse vibration of the anion, which results in an approximation of atoms in certain crystallographic axes. The A2M3O12 family (A = a trivalent cation and M = Mo6 positive or W6 positive) presents a phase transition from monoclinic to orthorhombic, with only the orthorhombic phase exhibiting thermomiotic behavior. This family is widely researched since it has the advantage of allowing a wide chemical flexibility without changing the crystalline structure and consequently allowing adjustments in the coefficient of thermal expansion according to the application, which the material is intended. Thermal expansion close to zero can lead to a promising high thermal shock resistance. This work aimed to study the thermal and mechanical properties of Al2W3O12 that has low thermal expansion with the goal of determining its thermal shock resistance by the Hasselman figure of merit. For this, all its thermal properties (thermal expansion and conductivity) and mechanical (Young modulus and mechanical strength) were obtained experimentally and presented a promising value of 120K (comparable to sapphire) for thermal shock resistance by the figure of merit of Hasselman under severe heating. A second research was developed with the goal of refining the microstructure and increasing the relative density of the Al2W3O12 bulk ceramics and thus increasing its mechanical properties. A synthesis by co-precipitation, folled by an isostatic pressing and a three steps sintering were carried out, obtaining an increase of 91 percent to 96 percent in the relative density, with increase of 19 percent in modulus of elasticity and 35 percent in Vickers hardness when compared to conventional sintering. The thermal expansion of a new material (In0,5(ZrMg)0,75Mo3O12) with promising thermal expansion close to zero (10-7 K1), calculated by mixing rule was studied in the third chapter of this thesis. The material was synthesized by total evaporation. Its intrinsic thermal expansion coefficient was determined in situ by X-ray diffraction and presented a value of 1.6x10-7 K-1 in the temperature range of 100 to 500 Celsius degrees, while the coefficient of expansion of the bulk obtained by dilatometry, was 6.68 x 10-7 K-1, in the temperature range of 100 to 800 Celsius degrees. This material presents a phase transition from monoclinic to orthorhombic at 82 Celsius degrees, which limits its use as thermomiothic material at temperatures above 100 Celsius degrees.

[pt] O principal objetivo deste trabalho foi estudar o sistema Al2-xGaxW3O12 (x = 0,2; 0,4; 0,5; 0,6; 0,7; 0,8; 1; 2) visando compreender os efeitos da substituição parcial de Al3+ (r = 0,67 Angstrom) por Ga3+ (r = 0,76 Angstrom) em relação ao coeficiente de expansão térmica da fase Al2W3O12. Foi determinado que o limite de solubilidade de Ga3+ no sistema é x = 0,5, as composições x maior ou igual 0,6 evidenciaram, por difração de raios-X (DRX), a presença de WO3 como fase secundária. Os difratogramas das composições 0,2 menor ou igual x menor ou igual 0,5, a temperatura ambiente, apresentaram exclusivamente linhas características do sistema monoclínico (P21/a). A transição para a fase ortorrômbica (Pbcn), foi evidenciada por DRX in situ e dilatometria e ocorre abaixo de 100 C em todos os casos. A temperatura de transição de fase, determinada por dilatometria, aumentou conforme foi aumentada a incorporação de Ga3+ na estrutura cristalina. A análise termogravimétrica das composições monofásicas revelou que essas fases não são higroscópicas. Embora Al1,5Ga0,5W3O12, seja a composição monofásica com maior teor de Ga, a fase Al1.6Ga0.4W3O12 foi a que apresentou o menor coeficiente de expansão térmica linear, alfa L= 1.14 K -1, uma redução de 25 por cento quando comparado ao coeficiente linear de expansão da fase Al2W3O12. O refinamento pelo método de Rietveld do padrão de difração de raios-X obtido a 100 C da Al1.6Ga0.4W3O12 ortorrômbica, confirmou que o Ga3+ substituiu o Al3+ na proporção descrita pela fórmula química nominal e evidenciou que as distorções poliédricas, Al(Ga)O6 e WO4, foram maiores do que as observadas em fases desta família. A espectroscopia de Raman corroborou as análises de DRX quanto ao limite de solubilidade, porém, evidenciando que quantidades mínimas, indetectáveis por DRX, de Al2O3 e WO3 podem estar presentes nas composições x menor ou igual 0,5, quando a síntese é realizada pelo método de reação no estado sólido. Os gráficos de Kubelka-Munk do sistema Al2- xGaxW3O12 indicaram que a substituição parcial de parcial de Ga3+ por Al3+ aumenta o intervalo de banda em x menor ou igual 0,4, no entanto, foi observada uma saliência de absorção dentro da região do visível presente em todas as amostras, interpretada como uma conseqüência da presença de WO3 monoclínica, observada na espectroscopia Raman. A síntese da fase Ga2W3O12, não foi bem sucedida, embora a entalpia de formação deste composto, calculada por meio da equação generalizada de Kapustinskii e pelo ciclo de Born-Haber, seja fortemente exotérmica, ΔHF= −10149,15 Kj. mol -1. / [en] The aim of this work was to study the Al2-xGaxW3O12 system (x = 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 2) in order to investigate the relationship between the partial replacement of Al3+ (r = 67 Angstrom) by Ga3+ (r = 0.76 Angstrom) and the coefficient of thermal expansion on the Al2W3O12 phase. It was determined as limit of solubility of Ga3+ in Al2-xGaxW3O12 the sample 𝑥 = 0.5, once it was identified in the diffraction patter WO3 as a secondary phase in 𝑥 bigger or equal 0.6. Unlike Al2W3O12 which is orthorhombic (Pbcn) at room temperature, the phases 0.2 less or equal 𝑥 less or equal 0.5 in the Al2- xGaxW3O12 appeared, at room temperature, in the monoclinic system (P21/a). The transition to orthorhombic phase (Pbcn), determined by XRPD in situ and dilatometry, was observed below 100 C for all compositions. The phase transition temperature increases as the Ga3+ content was increased in the crystalline structure. The thermogravimetric analysis of the monophasic samples showed that they were not hygroscopic. Although the monophasic composition with the highest Ga3+ content was Al1.5Ga0.5W3O12, the phase Al1.6Ga0.4W3O12 presented the lowest linear coefficient of thermal expansion, alpha l = 1.14 K -1, a reduction of 25 percent comparing with the linear coefficient of thermal expansion of the phase Al2W3O12. The Rietveld fit to the orthorhombic Pbcn space group, of the Al1.6Ga0.4W3O12 diffraction pattern taken at 100 C, confirms that Ga3+ was replaced by Al3+ in the same proportion described in the nominal chemical formula, and showed that its polyhedral distortion , Al(Ga)O6 and WO4, is in a higher amount than generally noticed for other phases in this crystal family. The Raman spectroscopy corroborated the analyzes regarding the solubility limit, although it showed that the compositions 𝑥 less or equal 0,5 could have a minimum quantities, undetectable by XRPD, of Al2O3 and WO3, when synthesized by the solid state reaction method. Kubelka-Munk graphics of Al2-xGaxW3O12 suggest that the partial replacement of Al3+ by Ga3+ increases the band gap in x less or equal 0,4, however, the absorption of Al2-xGaxW3O12 in the visible region increase, this behavior is apparently caused by the presence of WO3, as deduced by Raman spectroscopy. Attempts to synthesize Ga2W3O12 was not successful, although the enthalpy of formation of this compound, calculated by Generalized Kapustinskii equation and the Born-Haber cycle, presented a high exothermic value, ΔHF = −10149,15 Kj. mol -1.