Tungsten will be a key material for the plasma-facing components in future fusion devices. Its mechanical performance under neutron irradiation will strongly influence the lifetime of these devices. Pure tungsten has been subjected to a variety of irradiating species - tungsten ions, helium ions and fission neutrons - between 500°C and 900°C and the change in mechanical properties measured by micro-mechanical testing methods. Pure tungsten has been ion-irradiated using self-ions and helium ions at 500°C and 800°C. Nanoindentation has been performed on all specimens, and the 800°C specimens have been tested at temperatures up to 750°C using high-temperature nanoindentation. The irradiation temperature has no effect on the hardening of tungsten. Hardening from self-ion irradiation has not saturated by 4.5 dpa with an increase in hardness of 3.3 GPa. The hardening from helium implantation is only 0.73 GPa, and a comparison with literature shows that this hardening only depends on the concentration of the injected helium. The difference is likely due to the much smaller defect size of helium-vacancy clusters when compared to dislocation loops. High-temperature nanoindentation shows that helium-implanted tungsten softens rapidly, with the hardening from the radiation damage becoming negligible above 450°C. Self-ion implanted tungsten does not soften by 650°C, again likely due to the size difference of the defects. Micro-mechanical tests - namely micro-cantilever bending - have been used to investigate the plastic and fracture characteristics of tungsten before and after irradiation. Plastic behaviour is dominated by size effects due to the 3 μm depth of the implanted layers, which makes nanoindentation a better method for investigating radiation damaged layers. In fracture testing, fracture is rarely seen. Using the yield stress to calculate fracture toughness, the hardening from irradiation damage results in an increase in fracture toughness from 2.2 MPa√m to 6.0 MPa√m. The work of deformation at 1% is also increased after irradiation from 7.2 x 10^-11 Nm to 2.8 x 10^-10 Nm, implying that the implanted damage is not leading to an increase in embrittlement by reducing K^1c. Neutron irradiated tungsten also shows an increase in fracture toughness after irradiation from 6.5 MPa√m to 14.5 MPa√m. However, the BDTT increases by ∼ 100°C in poly-crystal tungsten and ∼ 500°C in single-crystal tungsten. The difference in BDTT does not exist in the unimplanted material. The change after irradiation is likely due to the fine (˜ 3 μm) grain size and 900°C irradiation temperature causing a significant amount of the displacement damage to be absorbed at the grain boundaries. The hardness of neutron irradiated and ion irradiated tungsten is very close: 10.4 GPa and 11.2 GPa respectively, demonstrating the ions are likely well-representing the neutron damage in pure tungsten.

Sn-based solder alloys are extensively used in electronic devices to form interconnects between different components to provide mechanical support and electrical path. The formation of a reliable solder interconnects fundamentally relies on the metallurgic reaction between the molten solder and solid pad metallization in reflowing. The resultant IMC layer at the solder/pad metallization interface can grow continuously during service or aging at an elevated temperature, uplifting the proportion of IMCs in the entire solder joint. However, the essential mechanical properties of interfacial IMC (i.e. Cu6Sn5, Cu3Sn) layers, such as Young s modulus and hardness, are drastically different in comparison with Sn-based solder and substrate. Therefore, the increasing fraction of interfacial IMCs in the solder joint can lead to significant deformation incompatibility under exterior load, which becomes an important reliability concern in the uses of solder joints for electronic interconnects. In the past decades, extensive research works were implemented and reported regarding the growth of interfacial IMC layers and its effect on the mechanical integrity of solder joints. But, the following fundamental issues in terms of mechanical and microstructural evolution in the uses of solder joints still remain unclear, demanding further research to elaborate: (1) The protrusion of IMCs: Though the growth of interfacial IMC layers along the diffusion direction in solder joints were studied extensively, the growth of IMCs perpendicular to the diffusion direction were reported in only a few papers without any further detailed investigation. This phenomena can crucially govern the long-term reliability of solder interconnects, in particular, in the applications that require a robust microstructural integrity from a solder joint. (2) Fracture behaviour of interfacial IMC layers: The fracture behaviour of interfacial IMC layers is a vital factor in determining the failure mechanism of solder joints, but this was scarcely investigated due to numerous challenges to enable a potential in-situ micro-scale tests. It is therefore highly imperative to carry out such study in order to reveal the fracture behaviour of interfacial IMC layers which can eventually provide better understanding of the influence of interfacial IMC layers on the mechanical integrity of solder joints. (3) Volume shrinkage: The volume shrinkage (or solder joint collapse) induced by the growth of interfacial IMC layers was frequently ascribed as one of the main causes of the degradation of mechanical reliability during aging due to the potentially resulted voids and residual stress at the solder/substrate interface. However, very few experimental works on the characterisation of such type of volume shrinkage can be found in literatures, primarily due to the difficulties of observing the small dimensional changes that can be encountered in the course of IMCs growth. (4) Residual stress: The residual stress within solder joints is another key factor that contributes to the failure of solder joints under external loads. However, the stress evolution in solder joints as aging progresses and the potential correlation between the residual stress and the growth of interfacial IMC layers is yet to be fully understood, as stress/strain status can fundamentally alter the course of total failure of a solder joint. (5) Crack initiation and propagation in solder joints: Modelling on the mechanical behaviour of solder joints is often undertaken primarily on the stress distribution within solder joints, for instance, under a given external loading. But there is lack of utilising numerical analysis to simulate the crack initiation and propagation within solder joints, thus the effect of interfacial IMC layers on the fracture behaviour of the solder joints can be elaborated in further details. In this thesis, the growth of interfacial IMCs in parallel and perpendicular to the interdiffusion direction in the Sn99Cu1/Cu solder joints after aging was investigated and followed by observation with SEM, with an intention of correlating the growth of IMCs along these two directions with aging durations based on the measured thickness of IMC layer and height of perpendicular IMCs. The mechanism of the protrusion of IMCs and the mutual effect between the growth of IMCs along these two directions was also discussed. The tensile fracture behaviour of interfacial Cu6Sn5 and Cu3Sn layers at the Sn99Cu1/Cu interface was characterised by implementing cantilever bending tests on micro Cu6Sn5 and Cu3Sn pillars prepared by focused ion beam (FIB). The fracture stress and strain were evaluated by finite element modelling using Abaqus. The tensile fracture mechanism of both Cu6Sn5 and Cu3Sn can then be proposed and discussed based on the observed fracture surface of the micro IMC pillars. The volume shrinkage of solder joints induced by the growth of interfacial IMC layers in parallel to the interdiffusion direction in solder joint was also studied by specifically designed specimens, to enable the collapse of the solder joint to be estimated by surface profiling with Zygo Newview after increased durations of aging. Finite element modelling was also carried out to understand the residual stress potentially induced due to the volume shrinkage. The volume shrinkage in solder joints is likely to be subjected to the constraint from both the attached solder and substrate, which can lead to the build-up of residual stress at the solder/Cu interface. Depth-controlled nanoindentation tests were therefore carried out in the Sn99Cu1 solder, interfacial Cu6Sn5 layer, Cu3Sn layer and Cu with Vickers indenter after aging. The residual stress was then evaluated in the correlation with aging durations, different interlayers and the locations in the solder joint. Finally, finite element models incorporated with factors that may contribute to the failure of solder joints, including microstructure of solder joints, residual stress and the fracture of interfacial IMC, were built using Abaqus to reveal the effect of these factors on the fracture behaviour of solder joints under applied load. The effect of growth of IMC layer during aging on the fracture behaviour was then discussed to provide a better understanding of the degradation of mechanical integrity of solder joints due to aging. The results from this thesis can facilitate the understanding of the influence of interfacial IMC layers on the mechanical behaviour of solder joints due to long-term exposure to high temperatures.

O objetivo deste estudo foi avaliar a dureza de um cimento resinoso dual autoadesivo (RelyX U200) e um cimento resinoso dual convencional (RelyX ARC) fotoativados sob materiais restauradores indiretos, utilizando unidades fotoativadoras com diferentes comprimentos de ondas (LED Elipar Freelight 2, LED Bluephase, Laser AccuCure 3000TM), por meio de teste de nanoendentação. Para a obtenção dos espécimes foram utilizados incisivos bovinos que após profilaxia, foram submetidos a cortes no limite amelo-cementário para a separação da porção coronária. Após inclusão, os espécimes foram submetidos ao desgaste para exposição de dentina e padronização do substrato. Para simular clinicamente restaurações indiretas foram confeccionadas peças em cerâmica IPS e.max® Press (Ivoclar Vivadent) e em resina composta indireta SR Adoro (Ivoclar Vivadent) que foram cimentadas nas superfícies dentinárias. Os espécimes foram seccionados longitudinalmente em baixa velocidade e constante irrigação e polidos em politriz. Foi estabelecido um grupo controle positivo, no qual o cimento foi fotoativado sem a interposição de material restaurador indireto e um grupo controle negativo, no qual, após a cimentação do material restaurador indireto, a fotoativação foi suprimida, ocorrendo apenas a polimerização química do cimento. Todos os espécimes foram armazenados em água destilada a 37°C durante 7 dias e após esse período, foram submetidos ao teste de nanoendentação na linha de cimentação, com o auxílo do ultra-microdurômetro (Shimadzu Dynamic Ultra Micro Hardness Tester). O ciclo aplicado foi de 100mN. Foram realizadas cinco nanoendentações em cada espécime, cujas médias resultaram nos valores de cada superfície. Os resultados obtidos foram submetidos à Análise de Variância e Teste de Tukey (p<0,05). Podese concluir que o cimento RelyX ARC apresentou maiores valores de dureza do que o RelyX U200 e este foi mais dependente da fotoativação para alcançar uma polimerização adequada. A dureza dos cimentos resinosos avaliados foi influenciada negativamente pela interposição do material restaurador indireto e apenas os LEDs foram capazes de manter o mesmo grau de polimerização dos cimentos quando interposto um material restaurador indireto. / This study aimed to evaluate the hardness of a dual cure self-adhesive resin cement (RelyX U200) and a dual cure conventional resin cement (RelyX ARC) light curing units with different wavelengths (Elipar Freelight 2 LED, Bluephase LED, AccuCure 3000TM Laser) through nanoindentadion test. To obtain the specimens bovine incisors were used after prophylaxis. The tooth were sectioned at the limit amelocement for the separation of the coronal portion. After inclusion, the dentin surface of the specimens were exposed to standardize the substrate. To clinically simulate indirect restorations ceramic pieces were made (IPS e.max® Press/Ivoclar Vivadent) and indirect composite resin (SR Adoro/Ivoclar Vivadent) were cemented on dentin surfaces. The specimens were sectioned longitudinally at low speed with constant irrigation and polished. A positive control group was stablished, in which the cement was light cured without the interposition of indirect restorative material, and a negative control group, in which, after cementation of the indirect restorative material, the light curing was removed, occurring only the chemical polymerization of the cement. All specimens were stored in distilled water at 37°C for 7 days. Nanoindentadion hardness of the cement layer was measured under 100mN load (Shimadzu Dynamic Ultra Micro Hardness Tester). Five nanoindentations in each specimen were obtained, which resulted in the average values of each surface. Data were statistically analyzed using ANOVA and Tukey test (p<0,05). RelyX ARC pesented higher values of hardness than RelyX U200 and this was more dependent on the polymerization. The hardness of the evaluated resin cements was negatively influenced by the interposition of an indirect restorative material and only the LEDs were able to maintain the same degree of polymerization of the cement when an indirect restorative material was used.

En rupture avec les approches classiques de métallurgie consistant à allier un ou deux éléments majoritaires avec d'autres éléments en proportions minoritaires, un nouveau concept de matériaux est né : des alliages multi-composants formant une solution solide et pour lesquels tous les composants sont fortement concentrés. Ces nouveaux alliages, appelés alliages à haute entropie, présentent des propriétés mécaniques prometteuses, telles qu'une résistance mécanique élevée combiné à une grande ductilité. Par définition, ce nouveau concept de matériau rend possible l'exploration d'un champ quasi-infini de compositions chimiques. Toutefois, la stabilité thermodynamique de ces systèmes est mal connue, limitant fortement le choix des compositions. Dans ce contexte, le premier objectif de cette étude était de déterminer le domaine d'existence de la solution solide cubique à faces centrées (cfc) pour le système Co-Cr-Fe-Mn-Ni. Pour cela, la stabilité de phase cfc a été étudiée théoriquement et expérimentalement. En utilisant l'approche Calphad (Calculation of PHAse Diagram) et une nouvelle base de données (TCHEA-1), les phases stables de 10 626 compositions ont pu être calculées, à plusieurs températures. La comparaison entre calculs et résultats expérimentaux indique que la solution solide cfc est correctement décrite par cette base de données. Ainsi, il a été montré que la phase cfc est stable sur une large gamme de composition, décrite intégralement. Il est désormais possible de choisir une composition formant une solution solide stable à haute température pour ce système. Des calculs DFT (Density Functional Theory) ont ensuite permis d'analyser l'évolution de l'enthalpie de mélange en fonction de la composition mais aussi du nombre d'éléments. Des différences notables ont pu être constatées avec les prédictions faites par la base de données TCHEA-1. De plus, ces calculs ont mis en avant l'absence d'interaction ternaire et quaternaire pour le système d'étude. Ensuite, l'influence de la composition sur le durcissement par solution solide a été étudiée, pour permettre l'optimisation des propriétés mécaniques. Ainsi, l'évolution des propriétés structurelles et mécaniques des alliages multi-composants a été étudiée expérimentalement. Vingt-cinq alliages du système Co-Cr-Fe-Mn-Ni formant une solution solide cfc ont été traités. Le paramètre de maille a été mesuré par rayons X tandis que la dureté et le module d'élasticité ont été étudiés par nano-indentation. Le rôle de chaque élément sur le comportement mécanique fut ainsi explicité. Finalement, un modèle permettant d'estimer le durcissement de solution solide pour ce système est étudié / For a long time, development of alloys was restricted to one principal element, or two, with minor elements added for performance optimization. In 2004, a new concept of materials was born: multi-component alloys forming a solid-solution and in which all components are very concentrated. These new alloys, named high entropy alloys, can combine high mechanical resistance and large ductility. By definition this new material concept should make it possible to explore an almost infinite field of chemical compositions. But in the meantime, the thermodynamic stability of these systems was poorly known and severely limits the choice of alloy compositions. In this context, the first objective of this study was to fully determine the composition range of existence of a unique fcc solid solution within the multi-component Co-Cr-Fe-Mn-Ni system. To address this problem, the phase stability was theoretically and experimentally investigated. Using the Calphad approach and a new database (TCHEA-1), the stable phases of 10 626 compositions could be calculated, at several temperatures. The comparison between calculation and experimental results indicates that the fcc solid solution is accurately described by this database. Finally, it was shown that the fcc phase is stable over a wide range of composition, which was completely described. Now, it is possible to choose a priori a composition which will form a solid solution within this system. The heat of mixing of the fcc phase were compared between density functional theory (DFT) and Calphad calculations for binaries, ternaries, quaternaries and quinary systems. Significant differences were found with the predictions made by the TCHEA-1 database. In addition, these calculations have highlighted the absence of ternary and quaternary interaction for the Co-Cr-Fe-Mn-Ni system. However, the influence of the composition on the fcc solid solution strengthening was not fully understood, which limits mechanical optimization. So, the evolution of structural and mechanical properties of multi-components alloys was experimentally investigated. Several alloys from the Co-Cr-Fe-Mn-Ni system forming a unique fcc solid solution were processed. The lattice parameter was measured by XRD while the hardness and elastic modulus were measured by nano-indentation. The role of each element on the mechanical behaviour is presented. Finally, a model to assess the solid solution strengthening for this system is studied

Made available in DSpace on 2017-07-24T19:22:10Z (GMT). No. of bitstreams: 1 Yasmine Bitencourt Emilio Mendes.pdf: 6295050 bytes, checksum: ec73165b3475fb2d502d87ebf6e6717e (MD5) Previous issue date: 2010-02-11 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The aim of this study was to assess the effect of different modes of application of a conventional adhesive system AdperTM Single Bond [SB] and of two self-etch adhesives AdperTM SE Plus [SE] and AdheSE® [AD] and influence of dentin depth on mechanical properties of hardness and elastic modulus of adhesive layer using the nanoindentation technique. The surfaces occlusal of 48 caries-free human third molars were removed and the smear layer standardized for the obtaining of a flat superficial dentin surface, in two levels: superficial dentine (DS) or deep dentine (DP). The adhesives were applied on the dentin surface in two layers, under active (AA) or passive (PA) application and photoactivated (10 s / 500 mW/cm2). After composite build-ups were constructed incrementally and were stored in water by 24 h. The teeth were sectioned in perpendicular direction to obtain specimens in form of bonded sticks with a cross-sectional area of 0.8 ± 0.1mm2, separating the central bonded sticks of each tooth for they be fastened in sample holder and metallographic polishing. The test of nanoindentation was made on composite resin, adhesive system and dentin regions. The results of hardness and elastic modulus (GPa) of adhesive layer were analyzed by a three-way ANOVA and Tukey’s multiple comparison tests (α=0.05) and also took place the two-way ANOVA for each adhesive separately. The mean and standard deviation of hardness and elastic modulus values of composite resin (GPa) were respectively (0.94 ± 0.05) and (13.41 ± 0.52). In dentin, the hardness was (0.89 ± 0.06) and the elastic modulus (17.51 ± 0.71). In the adhesive layer, the highest hardness (0.32 ± 0.02) and elastic modulus (5.54 ± 0.47) of SB were obtained in DS group. The elastic modulus in the adhesive layer of SE (4.11 ± 0.10) was lowest in AA group. For the adhesive layer of AD, just the mode of application was statistically significant (p=0.0041), being AA (0.29 ± 0.01) larger than PA (0.26 ± 0.01) (p=0.0042). It was concluded that: 1) passive application in superficial dentine got greaters values of hardness and modulus of elasticity of the SB and of SE, 2) the active application in deep dentine resulted in bigger values of the properties in study of SB, 3) active application significantly influenced the values of hardness in the area of the adhesive layer of the AD ones in such a way in superficial dentine how much in deep, but didn’t influence the modulus. / O objetivo deste trabalho foi avaliar o efeito da forma de aplicação do sistema adesivo convencional AdperTM Single Bond 2 [SB] e dos sistemas adesivos autocondicionantes AdperTM SE Plus [SE] e AdheSE® [AD] e da profundidade dentinária nas propriedades mecânicas de dureza e módulo de elasticidade da camada adesiva por meio do teste de nanoindentação. As superfícies oclusais de 48 terceiros molares humanos hígidos foram seccionadas e a smear layer padronizada para a obtenção de uma superfície dentinária plana, em dois níveis: dentina superficial (DS) ou dentina profunda (DP). Os adesivos foram aplicados sobre a superfície dentinária em duas camadas de forma ativa (AA) ou forma passiva (AP) e fotoativados (10 s / 500 mW/cm2). Em seguida, foram restaurados incrementalmente e armazenados em água destilada por 24h. Os dentes foram seccionados em eixos “x” e “y” para obtenção de espécimes em forma de palitos de aproximadamente 0,8 + 0,1 mm2 de secção transversal, separando o palito central de cada dente para serem fixados em porta-amostra e polidos metalograficamente. O teste de nanoindentação foi realizado nas regiões da resina composta, camada adesiva e dentina. Os valores de dureza e módulo de elasticidade (GPa) da camada adesiva foram submetidos a uma análise de variância de três fatores e ao teste de Tukey para contraste das médias (α=0,05), e também realizou-se a análise de variância de 2 fatores para cada adesivo isoladamente. As médias e os desvios padrões da dureza e do módulo de elasticidade (GPa) da resina composta foram respectivamente (0,94 ± 0,05) e (13,41 ± 0,52). Em dentina, a dureza foi (0,82 ± 0,06) e o módulo de elasticidade (17,51 ± 0,71). Para o grupo do SB na camada adesiva, os maiores valores de dureza (0,32 ± 0,02) e módulo de elasticidade (5,54 ± 0,47) foram obtidos no grupo DS. O módulo de elasticidade da camada adesiva do SE (4,11 ± 0,10) foi menor para o grupo AA. Para a região da camada adesiva do AD, apenas a forma de aplicação foi estatisticamente significante (p=0,0041), sendo a AA (0,29 ± 0,01) maior que a AP (0,26 ± 0,01) (p=0,0042). Concluiu-se que: 1) aplicação passiva em dentina superficial obteve maiores valores de dureza e módulo de elasticidade do SB e do SE, 2) a aplicação ativa em dentina profunda resultou em maiores valores das propriedades em estudo do SB, 3) aplicação ativa influenciou significativamente os valores de dureza na região da camada adesiva do AD tanto em dentina superficial quanto em profunda, porém não influenciou o módulo de elasticidade.

Submitted by Eunice Novais (enovais@uepg.br) on 2018-09-06T21:57:41Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) EVELYN PATRICIA SANTOS ARIAS.pdf: 1455330 bytes, checksum: 8883f664c636c5ec3e0625c691880784 (MD5) / Made available in DSpace on 2018-09-06T21:57:41Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) EVELYN PATRICIA SANTOS ARIAS.pdf: 1455330 bytes, checksum: 8883f664c636c5ec3e0625c691880784 (MD5) Previous issue date: 2018-04-24 / O objetivo deste estudo foi avaliar o grau de conversão, dureza e o módulo de elasticidade de três resinas Bulk Fill e duas resinas convencionais. Foram testadas as resinas Bulk Fill: Filtek™ Bulk Fill (FBP), Tetric N-Ceram Bulk Fill (TBF), Filtek™ Bulk Fill Flow (FBF); e adicionalmente duas resinas compostas convencionais: Empress Direct (ED) e Filtek™ Z350XT (Z350). Quarenta e cinco amostras cilíndricas (5 × 4 mm) foram confeccionadas a partir de cada um dos materiais por meio de uma matriz metálica. As matrizes foram preenchidas em incremento único para as resinas compostas Bulk Fill e em dois incrementos para as resinas compostas incrementais. As amostras foram armazenadas à seco no escuro à temperatura ambiente por 24 h antes da realização dos testes. O grau de conversão (GC) foi determinado utilizando a Espectroscopia de Infravermelho com Transformada de Fourier (FTIR). O teste de nanoindentação foi realizado nas superfícies de cada espécime, para obtenção da dureza (H) e módulo de elasticidade (E). Os dados foram submetidos a ANOVA 1 fator e teste de Tukey (α=0.05). Quanto o GC%, o maior foi obtido pelo grupo Z350 (69,92  3,5), e o grupo FBF (60,68  2,1) apresentou o valor significativamente inferior quando comparado com os outros grupos. Quanto os valores da nanodureza (GPa), os grupos FBF (0,3  0,02) e ED (0,3  0,01) apresentaram os menores valores de nanodureza e os grupos Z350 (0,9  0,04 ) e FBP (0,8  0,05 ) apresentaram os maiores valores de nanodureza. Quanto os valores do módulo de elasticidade (GPa), o grupo FBP apresentou os maiores valores de módulo de elasticidade (17,7  0,5) e o grupo FBF apresentou os menores valores de módulo de elasticidade (8,6  0,4). Conclui-se assim, que o compósito incremental (Filtek™ Z350XT) apresentou o maior desempenho do GC e o compósito Bulk Fill (Filtek™ Bulk Fill Flow) exibiu os menores valores de módulo de elasticidade e nanodureza. / The aim of this study was to evaluate the degree of conversion, hardness and elastic modulus of three Bulk Fill composites and two incremental-fill composites. The resin-composites: Filtek™ Bulk Fill (FBP), Tetric N-Ceram Bulk Fill (TBF), Filtek™ Bulk Fill Flow (FBF); and two incremental-fill composites: Empress Direct (ED), Filtek ™ Z350XT (Z350) were tested. Forty-five cylindrical specimens (5 × 4 mm) were made from each material in a metallic mold. Mold was filled in one increment for the Bulk Fill composites and in two increments for the incremental-fill composites. Specimens were stored dry in dark at room temperature for 24 h before testing. Degree of conversion (DC) was determined using Fourier transform infrared spectroscopy (FTIR). Nanoindentation was performed on the surfaces of each specimen, to obtain the hardness (H) and elastic modulus (E). Data for DC and H and E were analyzed by one-way ANOVA, Tukey's test (all at p<0,05). Z350 group (69.92  3.5) showed the highest DC% and FBF group (60,68  2,1) showed the lowest values when compared with the other groups. FBF (0.3  0.02) and ED (0,3  0,01) groups showed the lowest values for nanohardness (GPa) and Z350 (0,9  0,04 ) and FBP (0,8  0,05) groups showed the highest values for nanohardness. FBP group (17,7  0,5) showed the highest values for elastic modulus and FBF group (8.6  0.4) showed the lowest values for elastic modulus (GPa). It was concluded that incremental-fill composite (Filtek™ Z350XT) showed the highest performance DC and Bulk Fill composite (Filtek™ Bulk Fill Flow) showed the lowest values for elastic modulus and nanohardness.

Butt fusion welding process is an extensively used method of joining for high density polyethylene (HDPE) pipe. With the increasing number of HDPE resin and pipe manufacturers and the diversity of industries utilising HDPE pipes, a wide range of different standards have evolved to specify the butt fusion welding parameters with inspection and testing methods, to maintain quality and structural integrity of welds. There is a lack of understanding and cohesion in these standards for the selection of welding parameters; effectiveness, accuracy, and selection of the test methods and; correlation of the mechanical properties to the micro and macro joint structure. The common standards (WIS 4-32-08, DVS 2207-1, ASTM F2620, and ISO 21307) for butt fusion welding were used to derive the six welding procedures. A total of 48 welds were produced using 180 mm outer diameter SDR 11 HDPE pipe manufactured from BorSafe™ HE3490-LS black bimodal PE100 resin. Three short term coupon mechanical tests were conducted. The waisted tensile test was able to differentiate the quality of welds using the energy to break parameter. The tensile impact test due to specimen geometry caused the failure to occur in the parent material. The guided side bend specimen geometry proved to be too ductile to be able to cause failures. A statistical t-test was used to analyse the results of the short term mechanical tests. The circumferential positon of the test specimen had no impact on their performance. Finite element analysis (FEA) study was conducted for the long term whole pipe tensile creep rupture (WPTCR) test to find the minimum length of pipe required for testing based on pipe geometry parameters of outer diameter and SDR. Macrographs of the weld beads supplemented with heat treatment were used to derive several weld bead parameters. The FEA modelling of the weld bead parameters identified the length to be a key parameter and provided insight into the relationship between the geometry of the weld beads and the stresses in the weld region. The realistic bead geometry digitised using the macrographs contributed a 30% increase in pipe wall stress due to the stress concentration effect of the notches formed between the weld beads and the pipe wall. The circumferential position of the weld bead had no impact on the pipe wall stresses in a similar manner to the results of the different mechanical tests. IV Nanoindentation (NI) and differential scanning calorimetry (DSC) techniques were used to study the weld microstructure and variation of mechanical properties across the weld at the resolutions of 100 and 50 microns, respectively. NI revealed signature 'twin-peaks and a valley' distribution of hardness and elastic modulus across the weld. The degrees of crystallinity obtained from DSC followed the NI pattern as crystallinity positively correlates with the material properties. Both techniques confirm annealing of the heat affected zone (HAZ) material towards the MZ from the parent material. The transmission light microscopy (TLM) was used to provide dimensions of the melt zone (MZ) which displays an hour glass figure widening to the size of the weld bead root length towards the pipe surfaces. Thermal FEA modelling was validated using both NI and TLM data to predict the HAZ size. The HAZ-parent boundary temperature was calculated to be 105 ⁰C. The 1st contribution of the study is to prove the existence of a positive correlation between the heat input calculated from FEA and the energy to break values obtained from the waisted tensile test. The 2nd contribution providing the minimum length of pipe for WPTCR based on the pipe dimensions. The 3rd contribution is the recommendation for the waisted tensile test with the test using the geometry designed to minimise deformation of the loading pin holes. The 4th contribution related the weld bead parameters to pipe wall stresses and the effect of notches as stress concentrators. The 5th contribution is a new method of visualising a welding procedure that can be used to not only compare the welding procedures but also predict the size of the MZ and the HAZ. The 6th contribution of the study is the proposal of new weld bead geometry that consist of the MZ bounded by the HAZ, for butt fusion welded joints of HDPE pipes.

The importance of studying the physico-chemical properties of nano-dimensional materials has gained significant attention in the fields of semiconductors, pharmaceuticals, materials science, and atmospheric chemistry owing to the differences in physical properties between macro- and nano-dimensional solids. Nonetheless, direct studies of physical properties of materials at nanoscale is limited in part due to their inherent size constraints and experimental limitations. However, development of atomic force microscopy (AFM) led to the implementation of methods to characterize a wide range of physical properties, including – but not limited to – mechanical properties, electrical properties, viscoelastic properties, and surface tension. Herein, the dissertation focuses on AFM-based method development for characterization of atmospheric particles as well as understanding the relationship between structure and physical properties of organic solids at both macro- and nano-dimensions. In the atmospheric chemistry realm, the combined aerosol effect on the climate and environment has significant uncertainty in part due to lack of direct characterization of their physico-chemical properties. The difficulty in assessing the physical and chemical properties arises due to the presence of diversified aerosol sources, which in turn influences the size, morphology, phase states and chemical compositions. Sea spray aerosols (SSAs) are the second-largest source of aerosols in the atmosphere. Studying SSAs – especially in submicrometer-dimensions – requires high-resolution microscopy techniques such as AFM. AFM can be used for imaging of individual aerosols, quantifying organic volume fraction for core-shell morphologies, measuring water uptake, quantifying surface tension of individual droplets, and measuring mechanical and viscoelastic properties of materials. Herein, we employed AFM-based morphology and force spectroscopy studies to correlate the 3D morphology, phase state, and viscoelastic properties of selected single-component chemical systems found in sea spray aerosol (SSA). We established a quantitative framework toward differentiation of the solid, semisolid and liquid phase states of individual particles by utilizing both relative indentation depth (RID) and viscoelastic response distance (VRD) data obtained from the force−distance plots. Moreover, we established a semi-quantitative and quick phase assessment by measuring the aspect ratio (AR) that refers the extent of particle spreading as a result of impaction. Overall, the established AFM-based quantitative and semi-quantitative phase identification method can be utilized to assess the phases of aerosols irrespective of chemical identity. Next, we investigated the factors that may control the electrical and mechanical properties of pharmaceutical and organic semiconducting materials in nano- and macro-dimensions. Understanding the structure-property relationship of materials, especially in the nano-dimension, is necessary for proper drug design and development of organic semiconducting materials. In this context, cocrystals provide a means to modulate the physico-chemical properties of organic solids. For example, the modulation of the mechanical properties is important in the pharmaceutical industry for improving the tabletability. The mechanical properties may be affected by packing arrangement, interaction strength and type, and atomic and chemical composition. Herein, we report the influence of alkane and alkene functional groups on the mechanical properties of organic solids based on salicylic acid (SA). The approach affords both isostructural and polymorphic solids. The isostructural alkane functional solid exhibits a two-fold larger Young’s modulus (YM) compared to the cocrystal with the alkene, where the YM refers to the stiffness of the material. Here, the higher YM values are attributed to the presence of a bifurcated weak C-H···O interactions involving the alkane and neighboring SA molecules. On the other hand, in the case of alkene polymorphisms, molecular packing with column arrangement shows higher YM values compared to the herringbone arrangements. Thus, functional groups and crystal arrangements influence the stiffness of the solid organic cocrystals. Moreover, we report the modulation of mechanical properties of salicylic acid (SA) through cocrystallization by variation of propane and butane functionality with bipyridine coformers. We show that the variation of propane and butane functionality in bipyridine coformer with salicylic acid leads to synthesis of cocrystal and salt-cocrystal, respectively. The AFM nanoindentation study revealed that the Young’s modulus values follow the order salicylic acid < cocrystal << salt-cocrystal. The highest Young’s modulus values of the salt-cocrystal, among the studied systems, are attributed to the presence of strong N+–H···O– and O–H···O– interactions. On the other hand, higher Young’s modulus values of the propane-based cocrystal compared to the macro-dimensional salicylic acid are attributed to the stronger O–H ···N hydrogen bonding. Thus, homologous alkane functional groups can influence the mechanical properties of the organic solid crystals. Additionally, in situ solid-solid polymorphic phase transformation and nucleation of a metastable and elusive polymorph of SA cocrystals in combination with 4,4’-bipyridine were studied. Understanding the solid-solid phase transformations and nucleation mechanisms are important for proper control over the parameters associated with the synthesis of targeted crystalline solids with desired crystal structure. Using in situ powder X-ray diffraction (PXRD) and terahertz time domain spectroscopy (THz-TDS) data we showed that the Form II polymorph transforms to Form I over time. AFM imaging and nanoindentation techniques were utilized to follow and quantify in real-time the solid-solid polymorphic transformation of the metastable Form II to the thermodynamically stable Form I on a single crystal basis. AFM in situ single crystal data revealed that the metastable Form II has a rod-shaped morphology and relatively high elasticity (Young’s modulus), which transforms to prism-shaped nanocrystals of much smaller sizes with significantly reduced elasticity. The AFM imaging reveals that the single crystals on the order of 80-150 nm to undergo catastrophic changes in morphology that are consistent with cracking and popping owing to a release of mechanical stress during the transformation. The nucleation mechanism for the polymorphic transformation is not spatially localized and occurs over the entire crystal surface. The higher mechanical properties of the metastable Form II is due to the presence of the additional interlayer C-H···O interactions. Furthermore, we have studied the electrical properties of boron-based cocrystals. More specifically, cocrystallization of a nonconductive 2,4-difluorophenylboronic ester catechol adduct of a 4,4’-bipyridine (BEA) host with two aromatic semiconducting guests (pyrene and tetrathiafulvalene) generated conductive cocrystals with variable charge carrier mobilities. Charge carrier mobilities of the cocrystals with either pyrene or tetrathiafulvalene were measured using conducting probe AFM (CP-AFM). The incorporation of π-rich aromatic guests through face-to-face and edge-to-face π-contacts results in electrically conductive cocrystals. The cocrystal with tetrathiafulvalene as a guest shows approximately 7 times higher charge carrier mobility than the cocrystal with pyrene. Overall, the current dissertation demonstrates the AFM-based method development and applications towards materials characterization to measure the morphological, electrical, mechanical, and phase-states at both nano- and macro-dimensions. The high spatial precision of the methods developed enables us to better understand the controlling factors for materials design and processing across nano- and macro-dimensions.

Thin films are used for a variety of applications, which can include electronic devices, optical coatings and decorative parts. They are used for their physical, electrical, magnetic, optical and mechanical properties, and many times these properties are required simultaneously. Obtaining these desired properties starts with the deposition process and they are verified by a number of analysis techniques after deposition. A DC magnetron sputter system was used here to deposit tungsten films, with film thickness and residual stress uniformity being of primary interest. The film thickness was measured to vary by up to 45 % from the center to outer edge of a 4" wafer. Ar pressure was found to influence the thin film residual stress with lower Ar pressures leading to compressive residual stress (-1.5 GPa) and higher Ar pressures leading to tensile residual stress (1 GPa). Residual stress measurements of the tungsten films were made using a wafer curvature technique and X-ray diffraction. The results of the two techniques were compared and found to be within 20 %. Nanoindentation was used to analyze the mechanical properties of several types of thin films that are commonly used in microelectronic devices. Thin film reduced modulus, hardness, interfacial toughness and fracture toughness were some of the mechanical properties measured. Difficulties with performing shallow indents (less than 100 nm) were addressed, with proper calibration procedures for the indentation equipment and tip area function detailed. Pile-up during the indentation of soft films will lead to errors in the indentation contact depth and area, leading to an overestimation of the films' reduced modulus and hardness. A method was developed to account for pile-up in determining the indentation contact depth and calculating a new contact area for improving the analysis of reduced modulus and hardness. Residual stresses in thin films are normally undesired because in extreme cases they may result in thru-film cracking or interfacial film delamination. With the use of lithography techniques to pattern wafers with areas of an adhesion reducing layer, thin film delamination was controlled. The patterned delamination microchannels may be used as an alternative method of creating microchannels for fluid transport in MEMS devices. Delamination morphology was influenced by the amount of residual stress in the film and the critical buckling stress, which was primarily controlled by the width of the adhesion reducing layers.

Nanostructured materials have received a surge of interest in recent years since it has become apparent that reducing the size of a material often leads to heightened mechanical behavior. From a fundamental standpoint, this stems from the confinement of dislocations. Applications in microelectromechanical devices, lithium ion batteries, gas sensing and catalysis are realized by combining the improvements in mechanical behavior from material size reduction with the heightened chemical activity offered by materials with a high surface-area-to-volume ratio. In this study, films of nanoporous Si-Mg were produced through magnetron sputtering, followed by dealloying using an environmentally benign process with distilled water. The film composition and structure was characterized both at the surface and throughout the film thickness, while the mechanical behavior was explored with nanoindentation. Dispenser cathodes operate via thermionic emission and are an important area of interest in vacuum electron devices. While scientists have known for many years what elemental constituents are used to manufacture dispenser cathodes of excellent emission behavior, a fundamental understanding has yet to be realized. In this study, components of a scandate cathode that exhibited excellent emission behavior were characterized and used to inform the study of model thin films. Isolating relevant components of the scandate cathode for careful study could help inform future breakthroughs in understanding the working mechanism(s) of the scandate cathode. The structure, composition and electronic behavior of model W-Al alloy films were characterized experimentally and compared to computation. Moreover, a unique vacuum chamber was designed to activate modern thermionic dispenser cathodes, observe residual gas species present, and measure the work function through various state-of-the-art techniques.