Liquid Metal (LM) Composites are a rapidly expanding field within function materials research. Composed of isolated LM droplets dispersed in an elastomer, these composites can exhibit properties that include electrical conductivity, thermal conductivity, and programmable and anisotropic mechanical properties. Microindentation is a material characterization technique that can be used to study the micron-scale droplet-droplet interactions between the inclusions in these composites. Because most microindentation systems are incapable of producing plastic/elastic deformation volumes large enough to measure the interaction between inclusion and matrix or inclusion and inclusion in these systems, a specialized microindenter is designed and detailed here. The indenter is then used to test various droplet size, spacings, and matrix material combinations to view the mechanical and electrical implications of these variables. These materials were analyzed with a basic fracture energy scaling formula. It was also found that resistivity can decrease by up to seven orders of magnitude after droplet rupture, with as little as a 20μm elastomer film separating droplets before rupture. Continued studies of these phenomena will allow us to exploit the properties of these materials in new and interesting ways. / Master of Science / When a metal which is a liquid at room temperature (eutectic gallium-indium) is dispersed inside a soft, stretchable material such as a silicone rubber, it creates a unique functional material. These materials go beyond their typical uses by having new and exciting properties such as the ability to conduct heat and electricity. Not only do these materials have these properties, but we can also control them through specific manufacturing steps. These materials are called liquid metal composites or liquid metal embedded elastomers. These materials can be used to create flexible wiring for soft electronics and robots which can bend and stretch to suit their environment. One component of the interactions that lead to these properties is the interaction between pairs of droplets of liquid metal inside of the silicone. To study these interactions, we utilize micro-indentation which produces very small and precise deformations in a material. By slowly pressing on the material, and measuring forces, displacements, and electrical resistance, we can gain a closer insight into how the interactions of droplets and rubber produce these properties. These materials can be modeled using an analysis of fracture energy, and pairs of droplets decrease electrical resistance by over 10 million times when droplets combine. By studying these interactions, we gain a greater sense of how to control the properties of these materials, and can create new wearable devices that can bend and stretch with the human body's movements.

This thesis presents an experimental apparatus and methodology for measuring the interface conductance of thermal interface materials (TIMs) as a function of clamping pressure. The experimental apparatus is a steady state characterization device based on the basic premise presented in ASTM D5470 – 06. The setup is designed to develop an approximately one dimensional heat transfer through a TIM sample which is held between two meter bars. The temperature is measured along the meter bars using resistance temperature detectors (RTDs) and the temperature drop across the interface is extrapolated from these measurements and then used to calculate the conductance of the interface. This setup and methodology was used to characterize six commercial TIMs at pressures ranging from 0.17-2.76 MPa (25-400 psi). These TIMs included: Tgrease 880, Tflex 720, Tmate 2905c, Tpcm HP105, Cho-Therm 1671, and Cho-Therm T500. The measured conductance values for the various tests ranged from 0.19 to 5.7 W/cm2K. A three dimensional FEA model of the experimental setup was created in COMSOL Multiphysics 4.2a. This model was compared to the experimental data for a single data point and showed good correlation with the measured temperatures and conductance value.

In thin films solar cells technology, many different materials have been used; however, toxic and expensive materials and techniques have been widely employed up to date. In this work, three different low/non-toxic materials were grown by means simple and cheap techniques.Cd1–xZnxS thin films with Zn concentrations of 0–5 at.% were analyzed. The effect of the addition of different molar Zn concentrations to the reaction mixture on the growth mechanism of Cd1–xZnxS thin films and the influence of these mechanisms on structural, optical and morphological properties of the films has been studied.Cd1–xZnxS thin films were synthesized by chemical bath deposition using an ammonia-free alkaline solution. Microstructural analysis by X-ray diffraction showed that all deposited films grew with hexagonal wurtzite structure and crystallite sizes decreased as the Zn concentration in the film increased. Optical measurements indicated a high optical transmission between 75 % and 90 % for wavelengths above the absorption edge. Band gap value increased from 2.48 eV to 2.62 eV, and the refractive index values for Cd1–xZnxS thin films decreased as the Zn increased. These changes in films and properties are related to a modification in growth mechanism of the Cd1–xZnxS thin films, with the influence of Zn(OH)2 formation being more important as Zn in solution increased.Characterization of ZnS thin films deposited by chemical bath in a non-toxic alkaline solution is reported. The effect of deposition technique (growth in several times) on the properties of the ZnS thin film was studied. The films exhibited a high percentage of optical transmission (greater than 80 %); as the deposition time increased a decreasing in the band gap values from 3.83 eV to 3.71 eV was observed. From chemical analysis, the presence of ZnS and Zn(OH)2 was identified and X-ray diffraction patterns exhibited a clear peak corresponding to ZnS hexagonal phase (103) plane, which was confirmed by electron diffraction patterns. From morphological studies, compact samples with well-defined particles, low roughness, homogeneous and pinhole-free in the surface were observed.On the other side, characterization of one-step electrodeposited CuInS2 thin films is reported. The effect of the complexing agent C8H5KO4 on the reduction potential of metallic ions, as well as the annealing conditions to avoid film oxidation was studied. From polarization curves, it was observed that C8H5KO4 is an appropriate complexing agent to bring the reduction potential of Cu2+ closer to In3+. XRD patterns showed films with hexagonal structure and no peaks attributed to oxide phases were observed, under a 95 % N2 + 5 % H2 atmosphere and using a carbon holder. However, others two weak peaks associated to Cu7S4 phase were identified. The CuInS2 thin films exhibited a band gap value of 1.50 eV, low optical transmission in the visible range, p-type conductivity and a charge carrier concentration of 2.3 × 10-18 cm-3. Finally, from morphological and chemical analysis, it was possible to observe a compact morphology and free of pinholes surface with a composition close to the stoichiometric one. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

Orientador: Antonio José Ramirez Londono / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-20T13:37:33Z (GMT). No. of bitstreams: 1 TorresLopez_EdwarAndres_D.pdf: 14707024 bytes, checksum: 982b5dbc99d5f7bbef2ea2c34019eea4 (MD5) Previous issue date: 2012 / Resumo: Neste trabalho foram realizadas juntas soldadas dissimilares de aço carbono AISI SAE 1020 e a liga de alumínio AA6063-T5, com 2 mm de espessura, empregando o processo de soldagem por atrito com pino não consumível (SAPNC). As juntas soldadas a topo foram realizadas empregando ferramenta de WC-14Co, com diâmetro de ombro e pino de 25,0 e 5,7 mm, respectivamente, e comprimento de pino de 1,35 mm. Foram empregadas velocidades de rotação e avanço de 300 RPM e 150 mm.min-1, respectivamente, para três deslocamentos da ferramenta: +0,5, +1,0 e +1,5 mm. A caracterização microestrutural foi realizada por meio de microscopia óptica e eletrônica de varredura e de transmissão, difração de elétrons retroespalhados (EBSD), espectrometria de raios X dispersiva em energia (X-EDS) e difração de raios X (DRX). Para relacionar os parâmetros de soldagem com a microestrutura das juntas soldadas, foram elaborados os perfis da história térmica durante a soldagem. Juntas soldadas consolidadas foram obtidas para deslocamentos tangenciais da ferramenta (DT) de +1,0 e +1,5 mm, sendo descartado o DT de +0,5 mm por resultarem em penetração heterogênea ao longo da junta. As juntas realizadas no presente trabalho podem ser consideradas como de baixo aporte térmico. Esta condição evitou a formação da denominada zona de menor dureza na zona termicamente afetada (ZTA) do lado do alumínio e de compostos intermetálicos AlxFey na interface alumínio-aço. Na zona misturada, foram obtidas evidências da presença de dois mecanismos de recristalização dinâmica diferentes. No lado de avanço da zona misturada foi identificado o mecanismo de recristalização dinâmica geométrica, enquanto no lado de retrocesso o mecanismo ativo foi recristalização dinâmica continua / Abstract: In this work dissimilar AISI SAE 1020 mild steel and aluminum alloy AA6063-T5 joints, with 2 mm thickness, were friction stir welded (FSW). The welded joints were conducted employing WC-14Co tools, with shoulder and pin diameter of 25.0 and 5.7 mm respectively, and pin length of 1.35 mm. Rotation and weld speeds of 300 RPM and 150 mm.min-1 were employed, for three tool offsets: 0.5, 1.0 and 1.5 mm. The microstructural characterization was performed through optical, scanning and transmission electron microscopy, electron backscatter diffraction (EBSD), energy dispersive X-ray spectroscopy (X-EDS) and x-ray diffraction (DRX). In order to correlate the welding parameters with the final microstructure of the joints, thermal history profiles were collected during welding. Consolidated welded joints were obtained for tool offsets (DT) of +1.0 and +1.5 mm, being discarded the +0.5 mm offset by to produce heterogeneous penetration along the welded joint. The joints made in this work can be considered as low-heat input. This condition prevented the formation of the so-called low hardness zone in heat affected zone (HAZ) aluminum side, and the formation of intermetallic compounds AlxFey in the aluminum-steel interface. In the stir zone evidences of the presence of two different dynamic recrystallization mechanisms were observed. In the advance side of the stir zone, the geometric dynamic recrystallization was identify as working mechanism, while in retreating side of the stir zone, the active mechanism is the so-called continuous dynamic recrystallization / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

The characterization of work functions and field emission stability for molybdenum and iridium oxide coatings was examined. Single emission tips and flat samples of molybdenum and iridium oxide were prepared for characterization. The flat samples were characterized using X-ray Photoelectron Spectroscopy and X-ray diffraction to determine elemental composition, chemical shift, and crystal structure. Flat coatings of iridium oxide were also scanned by Atomic Force Microscopy to examine topography. Work functions were characterized by Ultraviolet Photoelectron Spectroscopy from the flat samples and by Field Emission Electron Distributions from the field emission tips. Field emission characterization was conducted in a custom build analytical chamber capable of measuring Field Emission Electron Distribution and Fowler-Nordheim I-V plots simultaneously to independently evaluate geometric and work function changes. Scanning Electron Microscope pictures were taken of the emission tips before and after field emission characterization to confirm geometric changes. Measurement of emission stability and work functions were the emphasis of this research. In addition, use of iridium oxide coatings to enhance emission stability was evaluated. Molybdenum and iridium oxide, IrO2, were characterized and found to have a work function of 4.6 eV and 4.2 eV by both characterization techniques, with the molybdenum value in agreement with previous research. The analytic chamber used in the field emission analysis demonstrated the ability to independently determine the value and changes in work function and emitter geometry by simultaneous measurement of the Field Emission Energy Distribution and Fowler-Nordheim I-V plots from single emitters. Iridium oxide coating was found to enhance the stability of molybdenum emission tips with a relatively low work function of 4.2 eV and inhibited the formation of high work function molybdenum oxides. However, the method of deposition of iridium and annealing in oxygen to form iridium oxide on molybdenum emitters left rather severe cracking in the protective oxide coating exposing the molybdenum substrate.

Over the last decade, the interstitial alloying of niobium has proven to be essential for enabling superconducting radiofrequency (SRF) cavities to operate more efficiently at high accelerating gradients. The discovery of "nitrogen doping" was the first readily accessible avenue of interstitial alloying in which researchers saw an increase in cavity performance. However, the serendipitous nature of the discovery led to additional research to fundamentally understand the physics behind the increase in cavity performance. This knowledge gap is bridged by materials characterization. Secondary ion mass spectrometry (SIMS) is a characterization technique which has become a staple of SRF cavity characterization that details elemental concentration profiles as a function of depth into the niobium surface with submicron resolution. SIMS has been widely used by the semiconductor industry for decades but has found less application in other fields due to the difficulty to produce reproducible data for polycrystalline materials. Much effort has been given to reduce the uncertainty of SIMS results to as low as 1% - 2% for single crystals. However, less attention has been given to polycrystalline materials with uncertainty values reported between 40% - 50% The sources of uncertainty were found to be deterministic in nature and therefore could be mitigated to produce reliable results. This dissertation documents the efforts to reduce SIMS method uncertainty which has been further used to solve mysteries regarding the characterization of SRF cavities which include predictive modeling of oxygen diffusion as well as the identification of contaminants resulting from cavity furnace treatments. / Doctor of Philosophy / Particle accelerators find many uses in society in which their complexity depends on their intended purpose. These purposes vary from projecting an image as in cathode ray tube (CRT) TVs, to creating high energy x-rays for life saving cancer treatments, to researching the very fundamental principles of science and physics. The later uses particle accelerators which are very large, spanning multiple miles, and run at extremely high energies. To keep operational costs reasonable, these instruments need to run as efficiently as possible. Therefore, superconducting radiofrequency (SRF) niobium cavities are used and are responsible for propulsion of charged particles. Although, niobium SRF cavities can pass incredibly high currents with very little surface resistance, these high-end particle accelerators push the operational boundaries of efficiency. To improve the efficiency of these cavities, an optimal concentration of impurities, such as oxygen and nitrogen, are added to the niobium surface. The addition of an impurity level that is too high or too low causes the resistance to increase which translates to higher operational costs. Therefore, it is important to accurately determine the concentration of impurities within the niobium and with high depth resolution. Secondary ion mass spectrometry is a characterization method that uses a primary ion beam to impact the surface of a material to remove atoms at the very surface. The ejected atoms are then ionized into a secondary beam which can then be detected to determine the concentration and to identify the species which was removed. Historically, this instrument has yielded results with 40% - 50% uncertainty for polycrystalline metals, such as niobium, which do not sputter evenly. With SRF cavity performance depending on accurate quantitation of impurities, a more robust method is needed. Therefore, this dissertation identifies issues which cause high uncertainties for polycrystalline materials and in addition offers mitigation strategies to reduce uncertainty to below 10%. These methods were then applied to solve real problems aimed to improve the production of niobium SRF cavities.

O presente trabalho de mestrado teve como meta realizar um estudo do comportamento do cobre particulado em ensaios tribológicos do tipo pino contra disco. O cobre é atualmente utilizado em até 15% em massa das pastilhas de freios automotivos e tal utilização é responsável pela emissão de até 70% do cobre particulado presente no ar. Devido ao caráter carcinogênico do cobre, se faz necessária sua substituição. Foram realizados ensaios tribológicos pino disco com adição de diferentes meios interfaciais. Foram utilizados pares tribológicos aço/aço, em ensaios a seco de pino contra disco com adição de meio interfacial nanoparticulado de óxido de ferro, grafite e de cobre metálico em diferentes granulometrias (400 m, 20 m e 50 nm). Após os ensaios, amostras das superfícies de pinos e discos para cada uma das adições de cobre, bem como para a condição sem adição de meio interfacial, foram caracterizadas utilizando técnicas de microscopia eletrônica de varredura, de forma a entender o comportamento das partículas de cobre e sua contribuição para o coeficiente de atrito. As adições de cobre obtiveram os maiores coeficientes de atrito, e entre elas os coeficientes de atrito foram mais altos durante todos os ensaios para a adição de 50 nm, seguido de 20 m e 400 m. A análise das superfícies tribológicas em MEV mostrou heterogeneidade das superfícies ensaiadas em relação à presença de debris oxidados e camadas compactas. Observou-se a presença de cobre apenas nas superfícies ensaiadas com adição dos cobres de 50 nm e 20 m. A presença de um filme óxido compacto e contínuo foi observada apenas nas superfícies tribológicas ensaiadas sem adição de meio interfacial e com adição de cobre a 400 m. / The purpose of this work was to investigate the behaviour of particulate copper in pin on discs tribotests. Copper is present in up to 15% in mass of brake pads composition, and it is responsible for the emission of up to 70% of the particulate copper present in airborne emissions. Due to its carcinogenic character, its replacement is considered necessary. Pin on discs tribotests were performed with the addition of different interfacial medias. The tribopair used was steel/steel, in dry sliding condition with the addition of nanoparticulated magnetite, graphite, and metallic copper in different granulometries (400 m, 20 m and 50 nm). After the tribotests, samples of both pin and disc surfaces for each of the copper additions, as well as a the condition with no interfacial media addition, were characterized using scanning electronic microscope techniques, in order to understand the behaviour of copper particles and their contribution to the friction coefficient. The three copper additions presented the highest friction coefficients among all additions; the highest friction coefficient was obtained by the smallest granulometry, 50 nm, followed by 20 m and 400 m. The analysis of the tribosurfaces using SEM showed the surface heterogeneity regarding the presence of oxide debris and compact layers. The presence of copper was only observed for the additions of the copper powders of 50 nm and 20 m. The presence of an oxide continuous and compact film was only observed for the tribosurfaces with no interfacial media addition and the addition of the copper with 400 m.

A technique for admicelle-based solid phase extraction is presented in which a dialkylammonium surfactant in the hydroxide form is immobilized on silica. By converting dihexadecyldimethylammonium bromide to the hydroxide form, the surfactant is allowed to have the property of a strong base, aiding in the extraction of acidic phenols which are difficult to extract because of their differing polarities. The surfactant-silica admicelle parameters were optimized for the efficient extraction of eight phenols. Adsorbed phenols were eluted from the sorbent using small volumes of methanol. The phenols were preconcentrated from drinking water samples and were determined using high performance liquid chromatography (HPLC) coupled with a photo diode-array detector.

Stricter greenhouse gas emission limits and renewable energy requirements are expected to further increase the worldwide practices of firing biomass and co-firing biomass with coal, which are both considered more sustainable energy sources than coal-only combustion. Reuse options for the by-products of these processes -biomass ash and co-fired fly ash -remain limited. Therefore, this research examines their use as supplementary cementitious materials (SCMs) in concrete and as precursors for alkali-activated geopolymers. Toward their potential use as an SCM, after characterizing these ashes assessing their compliance with ASTM C618 requirements, their impact on early-age hydration kinetics, rheology, setting time and permeability was assessed. Furthermore, the pozzolanic reactivity and the microstructural and hydrated phase development of the cement-ash samples were analyzed. The results show that a wood biomass ash sample was not satisfactory for use as an SCM. On the other hand, the findings demonstrate that co-fired fly ashes can significantly improve the strength and durability properties of concrete compared to ordinary portland cement, in part due to their pozzolanicity. Thus, it is recommended that the ASTM C618 standard be modified to permit co-fired fly ash sources that meet existing requirements and any additional requirements deemed necessary to ensure their satisfactory performance when used in concrete. Toward their potential use in geopolymers, this study characterized the early-age reaction kinetics and rheological behavior of these materials, showing that their exothermic reactivity, plastic viscosity and yield stress are significantly influenced by the activator solution chemistry and other characteristics of the ash. Two co-fired fly ashes were successfully polymerized, with compressive strengths generally highest for ashes activated with solutions with a molar ratio of SiO₂/(Na₂O + K₂O) = 1. The results show that geopolymerization is a viable beneficial reuse for these emerging by-products. Further characterization of these materials by scanning transmission X-ray microscopy analysis revealed the heterogeneity of the aluminosilicate phase composition of the co-fired fly ash geopolymer gel at the nano- to micro-scale.

Non-crystalline thin solid films are seeing increasing interest for a wide variety of applications. However, understanding structure and compositional variations in these films is an immense challenge. Conventional bulk structural or compositional characterization techniques such as X-ray diffraction often do not provide an adequate amount of information on their own. Electron microscopy is an incredibly powerful technique for structural and compositional film characterization, but is limited to inspection of only a small volume of any given sample. Rather than using one technique alone to gain information about a specimen, the greatest success is realized when these techniques are used in concert. This dissertation illustrates the idea that statistical analysis of electron microscopy data can provide information invaluable to interpreting bulk structural and compositional data from non-crystalline films. The first set of examples include demonstration of a statistical analysis method that can be applied to electron microscopy data to determine the presence of inhomogeneity along one film axis. This analysis method is applied to understanding compositional inhomogeneity that develops during formation of amorphous oxide films from aqueous solutions. Key insights are revealed that aid interpretation of bulk film X-ray characterization and possible processing conditions that lead to the compositional inhomogeneity. The second and third sets of examples describe the importance of electron microscopy analysis for structure determination in rotationally-disordered, non-epitaxial 2D heterostructures prepared from modulated elemental reactants. The second set of examples investigates the effects of nanoarchitecture on interlayer interactions and layer structure in heterostructures with interleaved BiSe and NbSe2 layers. The BiSe layers in these compounds display an interesting structural variation that impacts the overall compound properties. The structural variation is not visible using typical X-ray diffraction experiments, but analysis of electron microscopy images provides key insight into its existence. Finally, the third set of examples investigate several SnSe-containing heterostructures that provide insight into the unusual consequences of their non-epitaxial structure and film formation from modulated elemental reactants. Electron microscopy analysis, in conjunction with other characterization techniques, was invaluable for uncovering structural and compositional details within these compounds. This work contains previously published and unpublished co-authored material. / 10000-01-01