Dissertations / Theses on the topic 'Ceramic materials - Thermal properties'

Historically ceramic crystal laser material has had disadvantages compared to single crystal laser material. However, progress has been made in the last decade and a half to overcome the disadvantages associated with ceramic crystal. Today, because of the promise of ceramic crystal as a high power laser material, investigation into its properties, both physical and optical, is warranted and important. Thermal expansion was measured in this thesis for Nd:YAG (yttrium aluminum garnet) ceramic crystal using an interferometric method. The interferometer employed a spatially filtered HeNe at 633 nm wavelength. Thermal expansion coefficients measured for the ceramic crystal samples were near the reported values for single crystal Nd:YAG. With a similar experimental setup as that for the thermal expansion measurements, dn/dT for ceramic crystal Nd:YAG was measured and found to be slightly higher than the reported value for single crystal. Depolarization loss due to thermal gradient induced stresses can limit laser performance. As a result this phenomenon was modeled for ceramic crystal materials and compared to single crystals for slab and rod shaped gain media. This was accomplished using COMSOL Multiphysics, and MATLAB. Results indicate a dependence of the depolarization loss on the grain size where the loss decreases with decreased grain size even to the point where lower loss may be expected in ceramic crystals than in single crystal samples when the grain sizes in the ceramic crystal are sufficiently small. Deformation-induced thermal lensing was modeled for a single crystal slab and its relevance to ceramic crystal is discussed. Data indicates the most notable cause of deformation-induced thermal lensing is a consequence of the deformation of the top and bottom surfaces. Also, the strength of the lensing along the thickness is greater than the width and greater than that due to other causes of lensing along the thickness of the slab. Emission spectra, absorption spectra, and fluorescence lifetime were measured for Nd:YAG ceramic crystal and Yb:Lu2O3 ceramic crystal. No apparent inhomogeneous broadening appears to exist in the Nd:YAG ceramic at low concentrations. Concentration and temperature dependence effects on emission spectra were measured and are presented. Laser action in a thin disk of Yb:Y2O3 ceramic crystal was achieved. Pumping was accomplished with a fiber coupled diode laser stack at 938 nm. A slope efficiency of 34% was achieved with maximum output energy of 28.8 mJ/pulse.
Ph.D.
Department of Physics
Sciences
Physics PhD

In the presented thesis work, meshfree method with distance fields is applied to create a novel computational approach which enables inclusion of the realistic geometric models of the microstructure and liberates Finite Element Analysis(FEA) from thedependance on and limitations of meshing of fine microstructural feature such as splats and porosity.Manufacturing processes of ceramics produce materials with complex porosity microstructure.Geometry of pores, their size and location substantially affect macro scale physical properties of the material. Complex structure and geometry of the pores severely limit application of modern Finite Element Analysis methods because they require construction of spatial grids (meshes) that conform to the geometric shape of the structure. As a result, there are virtually no effective tools available for predicting overall mechanical and thermal properties of porous materials based on their microstructure. This thesis is a separate handling and controls of geometric and physical computational models that are seamlessly combined at solution run time. Using the proposedapproach we will determine the effective thermal conductivity tensor of real porous ceramic materials featuring both isotropic and anisotropic thermal properties. This work involved development and implementation of numerical algorithms, data structure, and software.

Electrical and thermal conductivities of the yttria-stabilised zirconia/alumina (YSZ/Al2O3) composites and the yttria-zirconia-ceria (YSZ-CeO2) solid solutions are studied in this thesis. The electrical conductivity of the YSZ/Al2O3 composites decreases with an increase in the volume fraction of Al2O3 and exhibits typical percolation behaviour. The electrical conductivity of the YSZ/Al2O3 interface is higher than that of the YSZ grain boundary, but lower than that of the YSZ grains. The thermal conductivity of the YSZ/Al2O3 composites increases with an increase in the Al2O3 volume fraction, and it can be fitted well to the Maxwell theoretical model, which indicates the absence of obvious interfacial thermal resistances in the composites. The low interfacial thermal resistance of the YSZ/Al2O3 interface is due to the 'clean' and coherent nature of the YSZ/Al2O3 interface, along with the small difference between the elastic properties of YSZ and Al2O3. The electrical conductivity of the [(ZrO2)1-x(CeO2)x]0.92(Y2O3)0.08 (0 ≤ x ≤ 1) solid solutions has a 'V-shape' variation as a function of the mole ratio of CeO2 (x). In the ZrO2-rich region (x < 0.5), CeO2 doping increases the concentration of defect associates which limits the mobility of the oxygen vacancies; in the CeO2-rich region (x > 0.5), the increase of x increases the lattice parameter, which enlarges the free channel for oxygen vacancy migration. A comparison of the YSZ-CeO2 solid solutions with the YSZ-HfO2 series indicates the ionic radius of the tetravalent dopant determines the composition dependence of the ionic conductivity of the solid solutions.The thermal conductivity of the [(ZrO2)1-x(CeO2)x]0.92(Y2O3)0.08 (0 ≤ x ≤ 1) solid solutions also has a 'V-shape' variation as a function of the mole ratio of CeO2 (x), which indicates an incorporation of Zr4+ and Ce4+ can effectively decrease the thermal conductivity of the end members YSZ and yttria-doped ceria (YDC). In the ZrO2-rich region (0 ≤ x ≤ 0.5), the thermal conductivity is almost temperature independent; in the CeO2-rich region (0.5 ≤ x ≤ 1), it decreases obviously with increasing temperature. By calculating the phonon scattering coefficients, it is concluded that the composition dependence of the thermal conductivity in the ternary solid solutions is dominated by the mass difference between Zr and Ce at the cation sites, whereas the temperature dependence is determined by the order/disorder of oxygen vacancies at the anion sites.

Thesis (M.S.)--Missouri University of Science and Technology, 2008.
Vita. The entire thesis text is included in file. Title from title screen of thesis/dissertation PDF file (viewed August 27, 2008) Includes bibliographical references.

Fundamental thermodynamic investigations have been carried out regarding the phase equilibria of La0.8Sr0.2MnO3±δ (LSM), a cathode of a solid oxide fuel cell (SOFC), utilizing the CALculation of PHAse Diagram (CALPHAD) approach. The assessed thermodynamic databases developed for LSM perovskite in contact with YSZ fluorite and the other species have been discussed. The application of computational thermodynamics to the cathode is comprehensively explained in detail, including the defect chemistry analysis as well as the quantitative Brouwer diagrams, electronic conductivity, cathode/electrolyte interface stability, thermomechanical properties of the cathode and the impact of gas impurities, such as CO2 as well as humidity, on the phase stability of the cathode. The quantitative Brouwer diagrams for LSM at different temperatures are developed and the detailed analysis of the Mn3+ charge disproportionation behavior and the electronic conductivity in the temperature range of 1000-1200°C revealed a good agreement with the available experimental observations. The effects of temperature, CO2 partial pressure, O2 partial pressure, humidity level and the cathode composition on the formation of secondary phases have been investigated and correlated with the available experimental results found in the literature. It has been indicated that the CO2 exposure does not change the electronic/ionic carriers’ concentration in the perovskite phase. The observed electrical conductivity drop is predicted to occur due to the formation of secondary phases such as LaZr2O7, SrZrO3, SrCO3 and Mn oxides at the LSM/YSZ interface, resulting in the blocking of the electron/ion transfer paths. For the thermo-mechanical properties of LSM, a new weight loss Mechanism for (La0.8Sr0.2)0.98MnO3±δ using the La-Sr-Mn-O thermodynamic database is modeled with respect to the compound energy formalism model. This newly proposed mechanism comprehensively explains the defect formation as a result of volume/weight change during the thermal cycles. According to the proposed mechanism the impact of cation vacancies regarding the volume change of cathode was explained.

Ces dernières années, les exigences de l'industrie dans le développement de nouveaux matériaux fonctionnels en mesure de résister aux conditions difficiles pendant l'opération d'usinage sont en constante augmentation. Les chercheurs doivent donc trouver de nouvelles solutions pour répondre aux besoins industriels de plus en plus sévères. L’utilisation de revêtement protecteur à la surface de l’outil de coupe est une solution très efficace. Des nouveaux matériaux architecturés sont étudiés pour leurs propriétés mécaniques, physiques et chimiques uniques assurant une résistance aux dégradations de surface dues à la corrosion, l'usure, le frottement; en particulier lorsque ces outils sont utilisés dans des environnements hostiles. Dans le cadre de cette thèse de doctorat, l'influence de la température sur la stabilité structurale de deux types de films minces déposés par PVD a été étudiée. Des films céramiques et de verre métallique ont été envisagés. Afin de préparer et optimiser ces films, le projet s’est axé sur l'étude de l'influence des conditions de dépôt sur les caractéristiques de croissance du film: composition chimique, structure, morphologie, puis sur les changements ultérieurs des principales propriétés des films minces, à savoir la résistance à l’oxydation et à la cristallisation lors de leur utilisation à hautes températures. Une démarche multi-échelle a été développée pour caractériser au mieux les couches. La première partie du travail est liée aux revêtements céramiques à base de CrN pour donner de nouvelles fonctionnalités et améliorer la surface des outils de coupe dans le but essentiel d'accroître leur durée de vie. La seconde partie du manuscrit est dédiée aux films minces de verres métalliques de Zr-Cu préparés par un procédé de co-pulvérisation magnétron PVD. Le but de cette partie consiste en l’étude de la relation entre la structure amorphe de ces films et leurs propriétés mécaniques. La conservation du caractère amorphe de ces films en température présente également un caractère essentiel. Les verres métalliques ont récemment attiré un fort intérêt car ils présentent des propriétés mécaniques intéressantes à température ambiante. Ils présentent, de ce fait, un grand potentiel pour des applications d'ingénierie en raison de leurs caractéristiques mécaniques et physico-chimiques uniques (haute limite élastique, résistance à la corrosion ...). Pour relier les propriétés mécaniques des couches à l’évolution de leurs microstructures, une partie importante de ce travail a porté sur l’observation de l’évolution de la couche au cours du chauffage au moyen de techniques de caractérisation in situ. Les films minces proposés au cours de ce travail peuvent être envisagées pour un large gamme d’application dans l’ingénierie de surface pour protéger les surfaces et améliorer la durée de vie des matériaux
In the recent years the industrial requirements to develop new functional materials able to overcome the severe conditions during machining operation are continuously increasing. Researchers then must find novel solutions to respond to their severe industrial requirements. To coat the tool surface with advanced coatings is the most efficient solution. New nanostructured materials may nowadays exhibit unique mechanical, physical and chemical properties ensuring notable degradation resistance where the surface protection of materials against corrosion, wear, friction or oxidation is a key issue, particularly when operating in hostile environments. Within the scope of this Ph.D. thesis the influence of the temperature on the structural stability of two different PVD ceramic and metallic glass thin films is proposed. The main goal consists in the development of two distinct classes of thin films, with a wide range of properties. In order to prepare these films, the project will be focused on the study on the influence of PVD deposition conditions in the particular film’s growth characteristics: chemical composition, structure, morphology and the subsequent changes in the main properties of the thin films, namely oxidation and crystallization resistance, especially. For that purpose we adopted the multiscale approach. The first part is related to the ceramic CrN-based coatings to give new functionalities and improve the tools’ surface with the primary aim to increase their lifetime. Secondly, new protective materials able to better protect the exposed surfaces against high temperature oxidation have been proposed, namely CrAlN and CrAlYN coatings as will be evidenced in this manuscript. The second part of the manuscript is dedicated to the innovative Zr-Cu thin films metallic glasses prepared by a PVD magnetron co-sputtering method with the objective to investigate the amorphization ability and their structural properties. Their excellent properties at room temperature have recently attracted attention as a new class of materials with great potential for engineering applications due to unique mechanical and physico-chemical characteristics (high elastic strain limit, corrosion resistance…). Finally, an important approach during the course of this thesis was the real time observation of the structure and surface modifications during heating by means of in situ methods. The thin films proposed during the course of the work could be straightforward used as surface engineering solutions to protect and extend the lifetime of the materials and components

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Tese (Doutoramento)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

This master´s thesis is focused on the use of primary raw materials (clays) in the brick manufacturing. These soils differ mainly CaO contect and it most often in the form of calcite. Diversity of soils is manifested primarily in the mineralogical composition after firing and the existence of anorthite in the calcium clays. In the practical part I am trying to define the optimal type of soil suitable for the production of masonry units.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico
With the recent advances in telecommunications industry in antenna area itâs increasingly required the development of ceramic materials which have high values of permittivity dielectric, low dielectric loss and a good thermal stability. Dielectric ceramics of CaCu3Ti4O12 are candidates as high values of permittivity dielectric materials and have been studied extensively. Nowadays ceramics offer materials several significant advantages in relation to others since present low production cost for electronic devices that operate of radio and microwave frequency, as well as being low weight materials, stable with temperature and extremely amenable to miniaturization. Sample preparation for structural analysis and dielectric, had the addition of CaCu3Ti4O12 to the phase MgTiO3 calcined in ratios of 4.0; 6.0; 8.0; 10.0 and 12.0 % by mass. The X-ray diffraction was important for the structural characterization of the obtained composite. The morphology of the samples was observed by Scanning Electron Microscopy (SEM). The dielectric characterization of radio frequency spectroscopy of impedance was performed which occurred two conductivity mechanisms for a sample. Models of dielectric relaxation approach the Cole-Cole and Havriliak-Negami type model. The experiments indicated that it is possible to obtain ceramic composites with good values of dielectric permittivity and low dielectric losses, resulting in scalebility and efficiency for devices designed to operate in those frequencies. Numerical simulation was performed with samples verifying good agreement with the experimental data. They studied the BiNbO4 phase doped with copper oxide and its possible applications in RF and Microwave. Addition of CaCu3Ti4O12 with MgTiO3 matrix contributed to the reduction of temperature coefficient of resonant frequency -39.25 ppm/ÂC to 9.62 ppm/ÂC, increased dielectric permittivity and dielectric loss. This thesis also presents a proposal for samples act as dielectric resonator antennas in the frequency range of 5.4 GHz to 6.1 GHz (C-band).The composites evaluated in this work has behaved properly as materials for use in microwave
Com os recentes avanÃos da indÃstria de telecomunicaÃÃes na Ãrea de antenas se faz cada vez mais necessÃrio o desenvolvimento de materiais cerÃmicos que apresentem altos valores de permissividade dielÃtrica, baixa perda dielÃtrica e uma boa estabilidade tÃrmica. CerÃmicas dielÃtricas CaCu3Ti4O12 sÃo candidatas como materiais de elevado valor de permissividade dielÃtrica e tÃm sido estudadas amplamente. Hoje as cerÃmicas oferecem vÃrias vantagens por apresentarem baixo custo de produÃÃo para dispositivos eletrÃnicos que operam em radiofrequÃncia e micro-ondas, alÃm de serem materiais de peso pequeno, estÃveis com a temperatura e extremamente passÃveis de miniaturizaÃÃo. A preparaÃÃo das amostras para anÃlise estrutural e dielÃtrica, teve a adiÃÃo de CaCu3Ti4O12 à fase MgTiO3 calcinada, em proporÃÃes de 4,0; 6,0; 8,0; 10,0 e 12,0 % em massa. A difraÃÃo de raios-X foi importante na caracterizaÃÃo estrutural dos compÃsitos obtidos. A morfologia das amostras foi estudada pela microscopia eletrÃnica de varredura (MEV). A caracterizaÃÃo dielÃtrica em rÃdio frequÃncia foi realizada por Espectroscopia de ImpedÃncia na qual se verificaram dois mecanismos de condutividade para uma das amostras analisadas. Os modelos de relaxaÃÃo dielÃtrica se aproximam do modelo do tipo Cole-Cole e Havriliak-Negami. Os experimentos realizados indicaram que à possÃvel obter compÃsitos cerÃmicos com bons valores de permissividade dielÃtrica e baixas perdas dielÃtricas, resultando em compactaÃÃo e eficiÃncia para dispositivos a serem projetados. SimulaÃÃo numÃrica foi realizada com as amostras verificando-se boa concordÃncia com os dados experimentais. Foram estudadas a fase BiNbO4 dopada com CuO e suas possÃveis aplicaÃÃes em radiofrequÃncia e micro-ondas. A AdiÃÃo de CaCu3Ti4O12 à matriz MgTiO3 contribuiu para a reduÃÃo do coeficiente de temperatura da frequÃncia de ressonÃncia de -39,25 ppm/ÂC para 9,62 ppm/ÂC, com o aumento da permissividade dielÃtrica e da perda dielÃtrica. Este trabalho de tese tambÃm apresenta uma proposta para as amostras funcionarem como antenas ressonadoras dielÃtricas na faixa de frequÃncias de 5,4 GHz a 6,1 GHz (banda C). Os compÃsitos avaliados nesse trabalho comportaram-se adequadamente como materiais para uso em micro-ondas.

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Tese (Doutorado em Tecnologia Nuclear)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Les composants d’électronique de puissance ont (et vont encore avoir !) eu une grande influence sur les secteurs de l'énergie et des transports. Ces pièces sont notamment constitués d’assemblages céramique –cuivre pour lesquels la tenue mécanique doit être maîtrisée afin de garantir dans le future une durabilité d’environ 30 ans sous l’action de cycles thermiques plus en plus grande. Une analyse des mécanismes de défaillance des assemblages DBC (Direct Bonding Copper) utilisés en électronique de puissance est étudiée (le délaminage le long de l’interface cuivre -céramique et/ou la rupture fragile de la céramique). Pour identifier le comportement élastoplastique du cuivre, nous avons montré qu’il est nécessaire d’utiliser une plaque de cuivre ayant subi l’ensemble des traitements thermiques liés au processus d’assemblage. Le comportement élastique fragile de la céramique est décrite dans le cadre d’une statistique de Weibull. Dès lors, une caractérisation du délaminage cuivre-céramique sous flexion quatre points a permis d’identifier un modèle cohésif pour l’interface. La calibration des paramètres cohésifs est menée en utilisant les données à deux échelles : i) macroscopique de force-déplacement ii) locale de suivi optique de la fissuration avec le déplacement imposé. L’intégrité mécanique des assemblages DBC pour différentes épaisseurs des couches de cuivre et de céramique a été étudié. Nous avons montré que les configurations avec un rapport proche de l’unité sont les plus dangereuses en engendrant un délaminage, qui se poursuit sous cyclage thermique. Ce dernier peut être notablement réduit en structurant le pourtour de la surface de cuivre avec des trous cylindriques répartis périodiquement. Ainsi, un modèle éléments finis permettant d’évaluer les assemblages les plus prometteurs en terme de durabilité a été établie. En l’absence de défauts géométrique, la couche de cuivre reste intègre, même dans le cas d’un délaminage dont le front induit une concentration de contrainte
The power electronics components (and still will have!) have a great influence on the energy and transport sectors. These parts are made of ceramic-copper assemblies for which the mechanical strength must be controlled to ensure durability about 30 years under the thermal cycles increasingly larger. A failure mechanisms analysis in DBC (Direct Copper Bonding) assemblies used in power electronics is studied (the delamination along the interface copper - ceramic and/or the brittle ceramic fracture). To identify the elastoplastic behavior of copper, we showed that it’s necessary to use a copper plate having undergone the heat hole treatments related to the assembly process. The ceramic gragile elastic behavior is descrobed within the Weibull statictics framework. Consequently, a copper-ceramic delamination characterization under four points bending made it possible to identify a cohesive model for the interface. The cohesive calibration parameters is carried out by using the data in two scales: i) strentgh-displacement macroscopic ii) local cracking optical follow-up with imposed displacement. The mechanical integrity of DBC assemblies of different thickness of copper and ceramic has been studied. We showed that the configurations with a ratio close to the unit are most dangerous by generating a delamination, which continues under thermal cycling. This risk of delamination can be notably reduced by structuring the copper circumference surface with cylindrical holes distributed periodically. Thus, a finite elements model allowing us to evaluate the most promising assemblies in term of durability, was estabilshed. In the absence of geometrical defects, the copper layer must remains, even in the delamination case whose face induces a concentration stress

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Tese (Doutoramento)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

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Dissertação (Mestrado em Tecnologia Nuclear)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

U ovom radu pripremljeni su različiti polimerni i keramički nanostrukturni materijali, u cilju ispitivanja uticaja vrste i udela nanopunila (čađ, fuleren, silicijum(IV)oksid, aluminijum(III)oksid i titanijum(IV)oksid) na strukturu, reološko i toplotno ponašanje kompozita, dobijenih na osnovu stirena, metilmetakrilata i akrilamida, primenom različitih metoda sinteze. Ispitivan je uticaj prisustva različitog udela nanočestica (1, 3 i 5 % m/m) na kinetiku polimerizacije stirena, i na oblast prelaska u staklasto stanje polistirenskih hibridnih materijala. Sintetisana je i serija nanokompozita polimerizacijom metilmetakrilata u prisustvu čestica (silicijum(IV)oksid, aluminijum (III)oksid i titanijum(IV)oksid) različitih dimenzija i hidrofilnosti, ali istog zapreminskog udela (1 % v/v). Na osnovu primene izotermne diferencijalno skanirajude metode (DSC), razvijen je kinetički model za opisivanje dve razičite reakcije tokom polimerizacije vinilnih monomera (reakciju prvog reda i samoubrzanje), i izračunata je debljina međufaznog sloja polimera na čestici u cilju određivanja njegovog uticaja na temperaturu prelaska u staklasto stanje hibridnih materijala. Za ispitivanje strukture i morfologije polistiren/silicijum(IV)oksid nanokompozita dobijenih metodom isparavanja rastvarača, korišdene su infracrvena spektroskopija sa Furijeovom transformacijom (FT-IR) i skanirajuda elektronska mikroskopija (SEM). Radi utvrđivanja uticaja udela hidrofobnog silicijum(IV)oksida (2, 5, 10, 15 i 30 % m/m) na toplotnu postojanost polistirenskih materijala, primenjene su istovremena termogravimetrijska i diferencijalno skanirajuda analiza (TG-DSC). Takođe, određen je uticaj veličine čestice fulerena C60 i submikronske čestice čađi na reološka svojstva polistirenskih kompozita sintetisanih taloženjem polimera iz rastvora. Ispitivanjem reološkog ponašanja hibridnih materijala, proučavan je uticaj veličine čestica, molekulske mase polimera i indeksa polidisperznosti na viskoznost polistirenskih kompozita. Na osnovu in-situ reoloških analiza polimerizacije u toku želiranja suspenzije nanočestica aluminijum(III)oksida u vodenom rastvoru monomera metakrilamida i N,N’-metilenbisakrilamida, utvrđena je jaka katalitička aktivnost površine aluminijum(III)oksida na nastajanje slobodnih radikala. Radi nalaženja veze između željenih svojstava keramičkih proizvoda i načina njihovog dobijanja, proučavan je uticaj uslova vođenja polimerizacije na slaganje čestica u dobijenom odlivku i na gustinu krajnjeg sinterovanog proizvoda.
In this work, polymeric and ceramic nanostructured materials were prepared using different methods, in order to investigate the influence of nanofiller content and its type (carbon black, fullerene, silica, alumina and titania) on the structure, rheological and thermal behavior of composites, based on styrene, methylmethacrylate and acrylamide. The effect of particles content (1, 3 and 5 wt. %) on the kinetics of styrene radical polymerization and on the glass transition temperature of polystyrene/silica composites was investigated. A series of polymethylmethacrylate nanocomposites containing 1 vol. % of silica, alumina or titania particles (differing in dimensions and surface properties) was obtained. On the basis of isothermal differential scanning calorimetry (DSC), the kinetic model for describing two reactions during vinyl monomer polymerization (first order and autoacceleration) was developed, and the thickness of interfacial layer formed on nanoparticle surface was determined, in order to investigate its influence on the glass transition temperature of polymethylmethacrylate hybrid materials. The structure and the morphology of polystyrene/silica nanocomposites prepared by solvent evaporation were investigated using Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The influence of  hydrophobic silica content (2, 5, 10, 15 and 30 wt. %) on polystyrene thermal stability was studied by simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC). The effect of fullerene C60 and submicron carbon black particle size on rheological properties of polystyrene composites prepared by the rapid coprecipitation was determined. Following the rheology of hybrid melts, the influence of filler size, molecular weight and polydispersity of polymer matrix on the viscosity of polystyrene composites was studied. On the basis of in-situ rheology analysis of polymerization process during the gelation of alumina nanoparticles suspension in aqueous solution of methacrylamide and N,N’- methylene bisacrylamide monomers, the strong catalytic activity of alumina surface on the free radicals formation was determined. In order to find the correlation between desired properties of ceramic products and their preparation procedure route, the influence of polymerization conditions on the green body structure and sintered body density was studied in details.

Thesis (Ph. D.)--University of Missouri-Columbia, 2007.
The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on October 16, 2007) Vita. Includes bibliographical references.

Commercial ceramic candle filters were exposed to harsh environments to determine the effects of alkali and steam on their long-term durability. Ceramic candle filters are composed of relatively coarse aggregates fixed by a ceramic bond. The filters studied include a clay-bonded, granular aluminosilicate candle and three types of clay-bonded, granular SiC candles. The alkali, steam, and steam-alkali corrosion of these commercial ceramic candle filters was examined at temperatures ranging from 450 to 1225°C and pressures up to 1000 psi. Results indicate that the aluminosilicate candle filters perform better than filters made from granular SiC. The SiC filters show binder degradation in steam as well as in alkali-containing environments at temperatures as low as 700°C, with oxidation of the SiC occurring in the steam environments at higher temperatures. Sodium and potassium contaminants in the steam atmospheres accelerate the degradation of both types of filter material.
Master of Science

This thesis is concerned with the microstructures and wear characteristics of eight ceramic tool materials which have been, or are currently, commercially available as indexable inserts for lathe tools. Two of the materials are alumina-based and the other six are derived from silicon nitride. The opening chapters of the thesis outline the essential features of metal cutting, the properties required of a good tool material, the development of ceramic tools and possible wear behaviour as discussed in the literature. Subsequent chapters describe the experimental procedures adopted in this work and both present and discuss the results obtained. The eight ceramics have been microstructurally characterised by the use of X-ray diffractometry, scanning electron microscopy and transmission electron microscopy. Machining tests have been performed using five common workpiece materials, spanning a range of nickel and iron contents: mild steel, stainless steel, two nickel-based superalloys and commercial purity nickel. The two alumina-based materials were found to wear in a different, less severe manner to the silicon nitride-based tools. The mechanical response to surface contacts was established using identation techniques to give hardness (as a function of contact size and temperature) and fracture toughness (as a function of temperature) to test the correlation between these properties and wear behaviour, but this proved to be unfruitful. Since other classes of tools can be subject to dissolution/diffusion wear and little is known about the compatability of these ceramics with molten metals, a second type of investigation was instigated. The involved immersing pieces of ceramic in samples of molten workpiece materials, followed by cooling, sectioning and examining in the scanning electron microscope. Vast differences in the behaviour of the materials were observed and results from these tests correlated well with machining data, indicating the importance of high temperature stability with respect to the hot workpiece. Drawing on the experimental observations made during the project, the thesis concludes with suggestions for improving and optimising ceramic tool materials for turning purposes.

Title from PDF of title page (University of Missouri--Columbia, viewed on Feb 18, 2010). The entire thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file; a non-technical public abstract appears in the public.pdf file. Thesis advisor: Dr. Stephen Lombardo. Includes bibliographical references.

In the search of clean and efficient energy sources intermediate temperature solid oxide fuel cells are among the prime candidates. What sets the limit of their efficiency is the solid electrolyte. A promising material for the electrolyte is ceria. This thesis aims to improve the characteristics of these electrolytes and help provide thorough physical understanding of the processes involved. This is realised using first principles calculations. The class of methods based on density functional theory generally ignores temperature effects. To accurately describe the intermediate temperature characteristics I have made adjustments to existing frameworks and developed a qualitatively new method. The new technique, the high temperature effective potential method, is a general theory. The validity is proven on a number of model systems. Other subprojects include low-dimensional segregation effects, adjustments to defect concentration formalism and optimisations of ionic conductivity.

Solid-state reaction and sol-gel, processing techniques were used extensively to form chemically-modified mullite solid solutions in an effort to lower their thermal expansion coefficients. TiO2, B203, CrPO4, P205, Ga203, Cr203, and WO3 and the half-breed Si02 compounds AlPas, BPO4, GaPO4, BAsO4, AIAsO4, GaAsO4, and Ge02 were chosen as the modifiers. The results indicate that, apart from Ti02, none of the substitutions made in mullite significantly change the thermal expansion properties. The solubility of 3 wt% TiO2 in mullite reduces the coefficient of thermal expansion by about 10%; That corresponds to a reduction in A1203/Si02 molar ratio ( < 1.5) compared to stoichiometric mullite (3A1203⠢2Si02). The formation of Ti02-modified mullite depends on processing condition and heat treatment. The possible mechanism of lowering the CTE of mullite by the addition of TiO2 is discussed in terms of the bond strength. The axial expansion of a Ga203-modified mullite was measured' up to 1200°C to show that the expansion is increased along the c-axis compared with that of the stoichiometric mullite.
Master of Science

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1987.
MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE.
Bibliography: leaves 109-118.
by Dodd Harrison Grande.
Ph.D.

La gestió tèrmica és un problema crític en el disseny de dispositius nanoelectrònics. Les solucions de refredament avançades i la recol·lecció eficient d'energia són clau per mantenir la tendència de productes electrònics cada vegada més petits i ràpids. Aquesta tesi se centra en la gestió tèrmica i l'ús de calor dissipada en materials emergents per a l'electrònica. En particular, els materials bidimensionals (2DM) i heteroestructures d'aquests són dels candidats més interessants per al futur de l'electrònica i s'estan investigant intensament. En aquesta tesi, s'exploren dos temes principals: (i) el transport tèrmic de 2DMs suspesos, inclòs el grafè CVD, dicalcògens de metalls de transició (TMDC) i heteroestructures de TMDC amb nitrur de bor hexagonal (hBN); i (ii) les propietats tèrmiques i de termoelectricitat de les pel·lícules primes (Bi1-xSbx)2Te3 (BST). Aquests materials s'estan considerant per interconnexions i transistors fins als THz (grafè), per a electrònica digital (TMDCs) i per a aïllament elèctric (hBN) i són ben coneguts com a generadors termoelèctrics, com ho són també materials recentment identificats com a aïllants topològics (BST). En primer lloc, l'objectiu era mesurar la conductivitat tèrmica de 2DMs utilitzant el mètode d'espectroscòpia Raman de dos làsers, recentment desenvolupat. La implementació fou dificultada per l'ús de membranes relativament petites obtingudes dels materials investigats i la seva alta conductivitat tèrmica. Demostràrem que la conductivitat tèrmica del grafè CVD és d'aproximadament 300 W/(m·K). Encara que menor que en el grafè exfoliat, això podria ser degut a les fronteres de gra i al desordre en el grafè CVD. Demostràrem també que les conductivitats tèrmiques de MoS2 i MoSe2 exfoliats (dos TMDC) són de 12 a 24 W/(m·K) i 60 W/(m·K), respectivament. I que per a membranes primes (de poques monocapes) de MoS2, la conductivitat incrementa amb el gruix. Afegint una membrana de hBN exfoliada sobre una mostra de MoS2 prèviament caracteritzada demostràrem un augment notable de la conductivitat tèrmica en l'heteroestructura de hBN/MoS2, quan s'introdueix calor al MoS2. Aquesta presenta una conductivitat tèrmica de 185 W/(m·K), gairebé un ordre de magnitud més gran que el MoS2 sol. En segon lloc, capes primes de BST crescudes mitjançant epitàxia de feix molecular s'estudiaren amb l'objectiu de correlacionar-ne les propietats termoelèctriques amb el seu nivell de Fermi, que sintonitzaria el pes relatiu del transport de volum i dels estats topològics de superfície (TSS). Primer demostràrem que és possible dissenyar l'estructura de la banda i ajustar el nivell de Fermi des de la valència fins a la banda de conducció simplement controlant la concentració de Sb. La demostració s'aconseguí utilitzant espectroscòpia de fotoemissió amb resolució angular en combinació amb conductivitat elèctrica i mesures d'efecte Hall en pel·lícules relativament primes (10 nm). S'identificà la concentració de Sb a la qual els TSSs dominen el transport i es dugueren a terme experiments termoelèctrics en les mateixes capes. No es trobà una correlació clara entre l'energia termoelèctrica i la naturalesa dels portadors de càrrega quan els TSSs eren dominants. Això indica que el transport dels TSSs té una influència limitada en les propietats termoelèctriques d'aquest material, i que per tal d'observar els efectes de superfície es necessitarien capes encara més primes. Finalment, una caracterització de les capes primes de BST usant espectroscòpia Raman demostrà variacions específiques en el comportament associat a la concentració de Sb. En particular, l'augment de la potència del làser va donar lloc a l'aparició de pics Raman no actius d'origen indeterminat. Aquests pics poden indicar la ruptura de simetries estructurals, modes de fonó de superfície o altres efectes com ara ressonàncies plasmòniques que són d'alt interès. La inesperada resposta observada en l'espectre Raman hauria de motivar investigacions addicionals.
La gestión térmica es un problema crítico en el diseño de dispositivos nanoelectrónicos. Las soluciones de enfriamiento avanzadas y la recolección eficiente de energía son clave para mantener la tendencia de productos electrónicos cada vez más pequeños y rápidos. Esta tesis se centra en la gestión térmica y el uso de calor disipado en materiales emergentes para la electrónica. En particular, los materiales bidimensionales (2DM) y las heteroestructuras basadas en ellos son candidatos muy interesantes para el futuro de la electrónica y se están investigando intensamente. La tesis trata dos temas principales: (i) el transporte térmico de 2DMs suspendidos, incluido el grafeno CVD, dicalcogenuros de metales de transición (TMDC) y heteroestructuras de TMDC con nitruro de boro hexagonal (hBN); y (ii) las propiedades térmicas y de termoelectricidad de películas delgadas de (Bi1-xSbx)2Te3(BST). Estos materiales están siendo considerados para interconexiones y transistores hasta THz (grafeno), electrónica digital (TMDCs) y aislamiento eléctrico (hBN) y son bien conocidos como generadores termoeléctricos, como también lo son materiales recientemente identificados como aislantes topológicos (BST). En primer lugar, el objetivo fue medir la conductividad térmica de 2DMs utilizando el método de espectroscopia Raman de dos láser, recientemente desarrollado. El desafío fue el uso de membranas relativamente pequeñas obtenidas y su alta conductividad térmica. Demostramos que la conductividad térmica del grafeno CVD es de aproximadamente 300 W/(m·K). Aunque menor que en el grafeno exfoliado, esto podría deberse a los bordes de grano y al desorden en grafeno CVD. Demostramos también que las conductividades térmicas de MoS2 y MoSe2 exfoliados (dos TMDC) son 12 a 24 W/(m·K) y 60 W/(m·K), respectivamente. Y que para membranas delgadas (pocas monocapas) la conductividad incrementa con su grosor. Agregando una membrana de hBN exfoliada sobre una muestra de MoS2 previamente caracterizada nos permitió demostrar un notable aumento de la conductividad térmica en la heteroestructura de hBN/MoS2, cuando se introduce calor en MoS2. Esta presenta una conductividad térmica de 185 W/(m·K), casi un orden de magnitud mayor que para MoS2. En segundo lugar, se estudiaron películas delgadas de BST crecidas mediante epitaxia de haz molecular con el objetivo de correlacionar sus propiedades termoeléctricas con su nivel de Fermi, que sintonizaría el peso relativo del transporte de volumen y de los estados topológicos de superficie (TSS). Primero demostramos que es posible diseñar la estructura de la banda y ajustar el nivel de Fermi desde la valencia hasta la banda de conducción simplemente controlando la concentración de Sb. Para ello se utilizó espectroscopia de fotoemisión con resolución angular en combinación con conductividad eléctrica y mediciones de Hall en películas relativamente delgadas (10 nm). También se identificó la concentración de Sb a la que los TSSs dominan el transporte y se llevaron a cabo experimentos termoeléctricos en las mismas películas. No se encontró una correlación clara entre la energía termoeléctrica y la naturaleza de los portadores de carga cuando los TSSs eran dominantes, indicando que el transporte de los TSSs tiene una influencia limitada en las propiedades termoeléctricas de este material y que para observar los efectos de superficie se necesitarían películas más delgadas. Finalmente, una caracterización de las películas delgadas de BST usando espectroscopia Raman demostró variaciones específicas en el comportamiento asociado a la concentración de Sb. En particular, el aumento de la potencia del láser dio lugar a la aparición de picos Raman no activos de origen indeterminado. Estos picos pueden indicar la ruptura de simetrías estructurales, modos de fonón de superficie u otros efectos tales como resonancias plasmónicas que son de alto interés, una respuesta que debería motivar investigaciones adicionales.
Thermal management is becoming a critical issue in the packaging and design of nanoelectronics. Advanced cooling solutions and efficient energy harvesting are key aspects to help keep the trend for ever smaller and faster electronics. This thesis is focused on thermal management and the use of heat waste in emerging materials for electronics. In particular, two-dimensional materials (2DM), and related heterostructures, are amongst the most intriguing prospects for future electronics and are being intensively investigated. Here, two main subjects were explored. First, the thermal transport of suspended 2DMs, including CVD graphene, transition metal dichalcogenides (TMDCs) and heterostructures of TMDCs with hexagonal boron nitride (hBN) and, second, the thermal properties and thermoelectricity of (Bi1-xSbx)2Te3 (BST) thin films. These materials are being considered for interconnects and THz transistors (graphene), digital electronics (TMDCs) and electrical insulation (hBN) and are well known as thermoelectric generators, as are also materials that have recently been identified as topological insulators (BST). In the first part, the objective was to demonstrate the measurement of the thermal conductivity of 2DMs using the recently developed two-laser Raman spectroscopy method. Its implementation was rendered difficult by the relatively small exfoliated flakes of the materials investigated and their high thermal conductivity. The thermal conductivity of CVD graphene was found to be about 300 W/(m·K). Although smaller than exfoliated graphene, it is argued that this could be due to grain boundaries and disorder. Exfoliated MoS2 and MoSe2 (two well-known TMDCs) presented thermal conductivities of 12 to 24 W/(m·K) and 60 W/(m·K). Measurements on different membranes of MoS2 further showed that the conductivity increases with the thickness in thin membranes (few monolayers). Furthermore, stacking an exfoliated hBN membrane on top of a previously characterized MoS2 sample allowed us to demonstrate a notorious increase of the thermal conductivity in the hBN/MoS2 heterostructure, when heat is introduced on MoS2. Indeed, when compared with MoS2 alone the thermal conductivity is found to be almost one order of magnitude larger, 185 W/(m·K). For the second part, BST thin films were grown by molecular beam epitaxy. The main objective was to investigate the correlation of the thermoelectric properties of these materials with the Fermi level, which would tune the relative weight of bulk and topological surface state (TSS) transport. It was first demonstrated that controlling the concentration of Sb we could engineer the band structure and tune the Fermi level from the valence to the conduction band. Such demonstration was achieved by using angle-resolved photoemission spectroscopy in combination with conductivity and Hall measurements in relatively thin (10 nm) films. The Sb concentration at which TSS dominated the transport was also identified. Thermoelectric experiments on the same films were then carried out but no clear correlation between the thermopower and the carrier nature was found when the TSSs were dominant. These results indicate that TSS transport has limited influence on the thermoelectric properties. Further studies should be carried our using even thinner films. Finally, a side characterization of the BST thin films using Raman spectroscopy demonstrated specific variations in the behaviour associated to Sb concentration. An increase of the laser power showed the emergence of non-active Raman peaks of undetermined origin. However, they can indicate the presence of broken structural symmetries, surface phonon modes or other effects such as plasmonic resonances. This interesting response is worthy of for further investigation.
Universitat Autònoma de Barelona. Programa de Doctorat en Física

A programme of work was instigated to investigate and improve the efficiency, and stability of intra-cavity étalons for the Argon ion laser, especially in the far blue to near ultra-violet wavelength region, by using sol-gel prepared silica. The original program has been modified by experiences outlined below. We have attempted to differentiate between the sol-gel derived and the high temperature prepared silica. We confirm that relatively small changes in thickness of silica monoliths can give rise to proportionally much larger changes of refractive index. Our main target has been to assess whether it is possible to make a new optical material that shows insignificant changes in optical path length or refractive index with temperature.

This research provides a comprehensive investigation in understanding the effect of the addition of graphene nano-platelets (GNP) on the mechanical, tribological and biological properties of glass/ceramic composites. We investigated two kinds of materials namely amorphous matrices like glasses (silica, bioglass) and polycrystalline matrices like ceramics (alumina). The idea was to understand the effect of GNP on these matrices as GNP was expected to behave differently in these composites. Bioglass (BG) was also chosen as a matrix material to prepare BG-GNP composites. GNP can improve the electrical conductivity of BG which can be used further for bone tissue engineering applications. The effect of GNP on both electrical conductivity and bio-activity of BG-GNP composites was investigated in detail. There were three main problems for fabricating these novel nano-composites: 1) Production of good quality graphene; 2) Homogeneous dispersion of graphene in a glass/ceramic matrix and; 3) Retention of the graphitic structure during high temperature processing. The first problem was solved by synthesising GNP using liquid phase exfoliation method instead of using a commercially available GNP. The prepared GNP were ~1 μm in length with a thickness of 3-4 layers confirmed using transmission electron microscopy. In order to solve the second problem various processing techniques were used including powder and colloidal processing routes along with different solvents. Processing parameters were optimised to fabricate glass/ceramic-GNP composite powders. Finally in order to avoid thermal degradation of the GNP during high temperature processing composites were sintered using spark plasma sintering (SPS) technique. Fully dense composites were obtained without damaging GNP during the sintering process also confirmed via Raman spectroscopy. Finally the prepared composites were characterised for mechanical, tribological and biological applications. Interestingly fracture toughness and wear resistance of the silica nano-composites increased with increasing concentration of GNP in the glass matrix. There was an improvement of ~45% in the fracture toughness and ~550% in the wear resistance of silica-GNP composites with the addition of 5 vol% GNP. GNP was found to be aligned in a direction perpendicular to the applied force in SPS. In contrast to amorphous materials fracture toughness and scratch resistance of alumina-GNP composites increased only for small loading of GNP and properties of the composites decreased after a critical concentration. There was an improvement of ~40% in the fracture toughness with the addition of only 0.5 vol% GNP in the alumina matrix while the scratch resistance of the composite increased by ~10% in the micro-ductile region. Electrical conductivity of the BG-GNP composite was increased by ~9 orders of magnitude compared to pure BG. In vitro bioactivity tests performed on BG-GNP composites confirmed that the addition of GNP to BG matrix also improved the bioactivity of the nano-composites confirmed using XRD analysis. Future work should focus on understanding electrical and thermal properties of these novel nano-composites.

Catalysis has an effect on almost every aspect of our lives. They are used to help grow the food we eat, clean the water we drink and produce the fuels our civilisation is so dependent upon. Homogeneous catalysts, those in the same phase as the reaction medium, are highly selective as a result of their tuneable nature, for example through changes to ligands in a metal complex. However, their separation from the reaction medium can become a problematic, costly, non-green issue, overcome through the use of heterogeneous catalysts which can be removed and recycled by simple separation techniques such as filtering and sedimentation. A major limitation on understanding the behaviour of heterogeneous catalysts is the presence of different active sites due to different exposed crystal surface, concentration of defects and morphological variations. With such considerations, the first section of this thesis focuses on the synthesis of discrete and well-defined nanostructured materials (ceria and titanate) using a single-step hydrothermal method. Nanostructured ceria with different morphologies (particles, rods and cubes), present a high oxygen storage capacity and thermal stability. Their oxidation catalytic activity was assessed using CO oxidation as a model reaction as a function of their physical and chemical properties, tuned by morphological control at the nanoscale. An inverse relationship is observed between crystallite size and rates of reaction normalised per surface area. Smaller crystallites present a constrained geometry resulting in a higher concentration of defects, highly active catalytically due to their unsatisfied coordination and high surface energy. The surface to bulk oxygen ratio generally increased as the surface area increased, however, ceria nanorods present a higher surface oxygen content than that which would be predicted according to their surface area, likely due to the selective exposure of the (110) and (100) dominating crystal surfaces presenting more facile oxygen atoms in their surface. Additionally a relationship between surface to bulk oxygen ratios and activation energies was also ascribed to the more facile nature of oxygen atoms on these surfaces and their more readily formed oxygen vacancies as a result. This activity is as a result of the formation of oxygen vacancies being the rate-controlling step. The thermal stability of nanostructured ceria (particles, rods and cubes) was also studied to investigate their performance under cyclic high temperature applications. For this, the materials were pre-treated at 1000 °C under different atmospheres (inert, oxidative and reducing). In all cases, the materials sinter, consequently resulting in a dramatic decrease in surface area. Interestingly, their catalytic activity per surface area towards CO oxidation, seems to be maintained, although those materials pre-treated under inert and oxidising atmospheres became inactive in consecutive catalytic runs. However, nanostructured ceria pre-treated at 1000 °C under hydrogen appeared to maintain its activity per surface area. The presence of hydrogen during thermal treatment does not only facilitate the removal of surface oxygen, but also the bulk oxygen, resulting in a rearrangement of the structure that facilitates its catalytic stability. Titanate nanotubes were shown to be inactive for CO oxidation and thus were used in the second part of this thesis as a support for platinum nanoparticles to study the effect of the structure and metal-support interaction on the resulting catalytic activity. The study focuses on the effect of different loading methods (ion exchange and incipient wetness impregnation) of platinum nanoparticles on the resulting metal particle size, dispersion, metal-support interaction and consequently their resulting catalytic activity. Ion exchange consistently resulted in smaller nanoparticles with a lower dispersion of sizes and more active catalyst, both in terms of turnover frequency values and activation energy, compared with incipient wetness impregnation. The catalytic activity of the platinum supported on titanate nanotubes increases as the metal particle size decreases to a size value (between 1 and 2.5 nm) below which a dramatic decrease in activity is observed. Despite initial differences in catalytic activity between the different catalysts, it was observed that after initial reactions to 400 °C, the activation energy was independent of metal loading weight and was instead inherent of the loading method, suggesting the presence of similar active sites.

Many modern technologies are enabled by the use of thin films and/or nanostructured composite materials. For example, many thermoelectric devices, solar cells, power electronics, thermal barrier coatings, and hard disk drives contain nanostructured materials where the thermal conductivity of the material is a critical parameter for the device performance. At the nanoscale, the mean free path and wavelength of heat carriers may become comparable to or smaller than the size of a nanostructured material and/or device. For nanostructured materials made from semiconductors and insulators, the additional phonon scattering mechanisms associated with the high density of interfaces and boundaries introduces additional resistances that can significantly change the thermal conductivity of the material as compared to a macroscale counterpart. Thus, better understanding and control of nanoscale heat conduction in solids is important scientifically and for the engineering applications mentioned above. In this dissertation, I discuss my work in two areas dealing with nanoscale thermal transport: (1) I describe my development and advancement of important thermal characterization tools for measurements of thermal and thermoelectric properties of a variety of materials from thin films to nanostructured bulk systems, and (2) I discuss my measurements on several materials systems done with these characterization tools. First, I describe the development, assembly, and modification of a time-domain thermoreflectance (TDTR) system that we use to measure the thermal conductivity and the interface thermal conductance of a variety of samples including nanocrystalline alloys of Ni-Fe and Co-P, bulk metallic glasses, and other thin films. Next, a unique thermoelectric measurement system was designed and assembled for measurements of electrical resistivity and thermopower of thermoelectric materials in the temperature range of 20 to 350 °C. Finally, a commercial Anter Flashline 3000 thermal diffusivity measurement system is used to measure the thermal diffusivitiy and heat capacity of bulk materials at high temperatures. With regards to the specific experiments, I examine the thermal conductivity and interface thermal conductance of two different types of nanocrystalline metallic alloys of nickel-iron and cobalt-phosphorus. I find that the thermal conductivity of the nanocrystalline alloys is reduced by a factor of approximately two from the thermal conductivity measured on metallic alloys with larger grain sizes. With subsequent molecular dynamics simulations performed by a collaborator, and my own electrical conductivity measurements, we determine that this strong reduction in thermal conductivity is the result of increased electron scattering at the grain boundaries, and that the phonon component of the thermal conductivity is largely unchanged by the grain boundaries. We also examine four complex bulk metallic glass (BMG) materials with compositions of Zr₅₀Cu₄₀Al₁₀, Cu_46.25Zr_44.25Al_7.5Er₂, Fe₄₈Cr₁₅Mo₁₄C₁₅B₆Er₂, and Ti_41.5Zr_2.5Hf₅Cu_42.5Ni_7.5Si₁. From these measurements, I find that the addition of even a small percentage of heavy atoms (i.e. Hf and Er) into complex disordered BMG structures can create a significant reduction in the phonon thermal conductivity of these materials. This work also indicates that the addition of these heavy atoms does not disrupt electron transport to the degree with which thermal transport is reduced.
Ph. D.

Thermometric analyses provide extremely useful information about heated archaeological materials and fire-damaged modern structures. A number of non-luminescence thermometry methods have been developed for analysing pottery firing temperatures. However, many of these methods are limited in analysis range and accuracy, or are time consuming, expensive and complex. In addition to these techniques there are a number of thermoluminescence (TL) thermometry methods but they are also limited in analysis range and the majority have been developed for specific thermometry problems. The aim of this study was to investigate the use of thermoluminescence (TL) and photostimulated luminescence (PSL) methods to develop rapid, precise, inexpensive thermometry techniques that were applicable to a wide range of thermal events and materials from archaeological and modern contexts. A basic theoretical treatment of luminescence kinetics in silicate systems was undertaken to develop an understanding of TL glow curve alterations arising from thermal exposure. Kinetic studies showed that a combination of temperature and duration parameters is expected for single trap systems. Kinetic theory was developed to produce a new first order multi-trap system which provides a theoretical means of separating temperature and time components, which may be applicable to synthetic phosphors. Additionally heat transfer solutions were investigated to examine the temperature distribution in heated solids and TL instrumentation. Isothermal annealing experiments on IAEA-F-1 potassium feldspar showed a highly precise progressive thermal exposure monitor, whereby the position of the first rise of an annealed TL glow curve is characterised by a linear increase in temperature and a logarithmic increase in time. First order kinetic simulations and initial rise measurements demonstrated a continuous linear distribution of traps in IAEA-F-1 feldspar. Using a high temperature TL system (maximum temperature 700°C) the progressive thermometry method was successfully applied to separated feldspar minerals and polymineral samples from archaeological (ceramics, burnt stones and hearthstones) and modern (fire damaged concrete) materials. PSL excitation spectroscopy showed potential thermometric behaviour but for some samples the sensitivity of the system was too low. Pulsed infra-red PSL showed there may be a limited trap distribution over which a small range of thermal exposures will operate. Combined TL/PSL measurements showed it may be possible to deconvolute temperature and time parameters.

Research on alternative energies has become an area of increased interest due to economic and environmental concerns. Green energy sources, such as ocean, wind, and solar power, are subject to predictable and unpredictable generation intermittencies which cause instability in the electrical grid. This problem could be solved through the use of short term energy storage devices.

Capacitors made from composite polymer:nanoparticle thin films have been shown to be an economically viable option. Through thermal vapor deposition, we fabricated dielectric thin films composed of the polymer polyvinylidine fluoride (PVDF) and the ceramic nanoparticle titanium dioxide (TiO₂). Fully understanding the deposition process required an investigation of electrode and dielectric film deposition. Film composition can be controlled by the mass ratio of PVDF:TiO₂ prior to deposition. An analysis of the relationship between the ratio of PVDF:TiO₂ before and after deposition will improve our understanding of this novel deposition method.

X-ray photoelectron spectroscopy and energy dispersive x-ray spectroscopy were used to analyze film atomic concentrations. The results indicate a broad distribution of deposited TiO₂ concentrations with the highest deposited amount at an initial mass concentration of 17% TiO₂.

The nanoparticle dispersion throughout the film is analyzed through atomic force microscopy and energy dispersive x-ray spectroscopy. Images from these two techniques confirm uniform TiO₂ dispersion with cluster size less than 300 nm. These results, combined with spectroscopic analysis, verify control over the deposition process.

Capacitors were fabricated using gold parallel plates with PVDF:TiO ₂ dielectrics. These capacitors were analyzed using the atomic force microscope and a capacohmeter. Atomic force microscope images confirm that our gold films are acceptably smooth. Preliminary capacohmeter measurements indicate capacitance values of 6 nF and break down voltages of 2.4 V.

Our research on the deposition process will contribute to the understanding of PVDF/TiO₂ composite thin films. These results will lead to further investigation of PVDF/TiO₂ high density energy storage capacitors. These capacitors can potentially increase the efficiency of alternative energy sources already in use.

Solid-state reaction and sol-gel processing methods were used to prepare samples of (Ca_{1 - X,}Mg_X)Zr₄(PO₄)₆(CZP-CMZP) where x = 0.0-0.4. CMZP is a member of the NaZr₂(PO₄)₃ (NZP) class of ceramics and is being investigated for heat engine applications. Linear thermal expansion was determined with a dual push rod dilatometer and axial thermal expansion by high temperature X-ray diffraction and least squares refinement. Thermal diffusivity was determined with the laser flash method and specific heat by differential scanning calorimetry. Thermal conductivity was found by the product of the thermal diffusivity, specific heat, and bulk density of each sample. Results indicate that CMZP samples exhibit very low α̅_L values which become more positive as Mg²⁺ content is increased. Thermal expansion anisotropy (from room temperature to 1000°C) is significantly reduced by the addition of Mg²⁺. Samples where x = 0.4 exhibit the lowest anisotropy with α_a being essentially zero (hexagonal system). The thermal conductivity of CMZP samples is very low (0.56 W/m K at 200°C). Thermal conductivity values were observed to decrease with increasing Mg²⁺ content. The materials structure and cation site selection are discussed in relation to the observed properties.
Master of Science

The main subject of this PhD Thesis is the manufacturing of titanium dioxide multifunctional coatings by means of two spraying technologies: Cold Gas Spray (CGS) and Atmospheric Plasma Spray (APS). The characteristics of each spraying technique are a key factor to be able to understand the behaviour of the deposited material. Moreover, the process conditions strongly affect the functional response and activity of the metal oxide layers in different application sectors. The starting scope of the PhD thesis consisted in developing nanostructured TiO2 anatase coatings by LP-CGS technique. Using this method, no melting of material feedstock is needed for being deposited and this fact is fundamental because it is possible to preserve this metastable active anatase phase at room temperature. The large specific surface of this nanometric feedstock is useful for applying it in the field of heterogeneous photocatalysis and degradation of contaminants. In order to avoid clogging phenomena of the nanometric powder and not suitable deposition of only ceramic particles, mechanical blends were prepared with ductile materials which flow properly in the pipelines. The presence of anatase phase on the top surface of the final coatings determines their photocatalytic behaviour. Samples successfully degraded NOx gases in less than half an hour (FEAM Grupo de Fotocatálisis y Espectroscopia Aplicada al Medioambiente, Universidad de Las Palmas de Gran Canaria). A second research topic regarded different TiO2 materials with the objective to test them in photoelectrocatalysis. Three commercial powders (TiO2 rutile, TiO2 anatase and TiO2-x) onto Inconel alloy and carbon steel substrates were studied. The influence of APS thermally-activating technique is explained towards the non-stoichiometric secondary phases that are formed. The performance of the coatings as photoanodes in the solar photoelectrocatalysis (SPEC) treatment of a model azo dye was explored (Group LEMMA Laboratori d’Electroquímica de Materials i del Medi Ambient, Universitat de Barcelona). The functional role of these materials has an important added value in the environmental field because of the possibility to achieve cleaner waters in the smart cities of the future. The third purpose of this research was to deposit metal oxides based on titanium dioxide by APS for being applied as electrodes in real batteries. Hydrogen contained in the plasma jet of APS is able to reduce TiO2 metal oxide feedstock, create oxygen vacancies and non stoichiometric compounds such as titanium sub-oxides (TiO2-x) or Magnéli phases (TinO2n-1) during the in-flight interaction of the particles with the jet stream. This lack of oxygen in the crystal structure of TiO2 powder leads to a donor level to the conduction band; therefore a corrosion-resistance ceramic material with an enhanced conductivity was obtained. Coatings were manufactured onto stainless steel, aluminium films, carbon-polymer composite and nickel foam. Four TiO2-x plates onto aluminium substrates were applied as electrodes in a laboratory scale battery. Cyclic voltammograms curves and charge/discharge cycle of the lead acid battery were carried out and gave excellent results (Faculty of Engineering and the Environment, University of Southampton). The fourth objective of this doctorate consisted in developing new functional gas sensors by means of APS technology. It was determined to build-up the sensing layer on a thin ceramic substrate. This fact permits to increase the working temperature respect to polymeric or metallic substrates. Spraying conditions were accurately selected to reach good deposition and not to damage the brittle substrate. The APS process offered also the advantage to increase the quantity of oxygen vacancies in titanium dioxide powder in order to enhance its conductivity and sensing function. Satisfactory performances were obtained testing the response of the device in front of various target gases and sensing efficiency was deeply studied (Group MIND Micro-nanotecnologías y nanoscopias para dispositivos electrónicos y fotónicos, Universitat de Barcelona).
El tema principal de esta tesis doctoral es la fabricación de recubrimientos multifuncionales de dióxido de titanio mediante técnica de proyección fría (CGS) y proyección por plasma atmosférico (APS). Cada producto en forma de recubrimiento funcional encontró su sector de aplicación: i) fotocatálisis en fase gaseosa, ii) fotoelectrocatálisis en fase liquida, iii) electrodos para baterías y iv) sensores de gas. El primer objetivo de esta tesis doctoral consistió en el desarrollo de recubrimientos nano-estructurados de TiO2 anatasa mediante técnica de proyección fría CGS. La grande superficie específica de este material nanométrico es útil para su aplicación en el campo de la fotocatálisis heterogénea. Fueron preparadas unas mezclas mecánicas entre materiales nano-cerámicos y poliméricos con adecuada fluidez para el sistema de alimentación CGS. Las muestras obtenidas degradaron los gases NOx en breve tiempo y con elevadas eficiencias tanto con luz UV como con luz visible (FEAM Grupo de fotocatálisis y Espectroscòpia Aplicada al Medioambiente, Universidad de Las Palmas de Gran Canaria). El segundo propósito de esta investigación consistió en proyectar tres diferentes tipos de TiO2 (100% anatasa, 100% rutilo y sub-óxidos) por tecnología APS y evaluar las actividades fotocatalíticas en fase liquida. El rendimiento de los recubrimientos aplicados como fotoánodos fue analizado con el proceso SPEC Solar Photoelectrocatalysis. El estudio llevó a la conclusión que los recubrimientos con mayor parte de fases cristalinas (anatasa y rutilo), mayor rugosidad 3D de superficie y adecuado espesor presentan mejor desempeño fotoelectrocatalítico. (Grupo LEMMA Laboratori d’Electroquímica de Materials i del Medi Ambient, Universitat de Barcelona). La tercera finalidad de este trabajo fue depositar óxidos metálicos por APS para ser aplicados como electrodos en baterías reales. El hidrógeno contenido en el flujo de plasma de APS es capaz de reducir el óxido metálico TiO2 de partida, crear vacantes de oxígeno y compuestos no estequiométricos como sub-óxidos de titanio (TiO2-x) o fases de Magnéli (TinO2n-1). Esta falta de oxígeno aumenta la conductividad del material que además resiste bien contra la corrosión. Fueron fabricados recubrimientos sobre acero inoxidable, láminas de aluminio, material compuesto de polímero reforzado con carbono y espuma de níquel. Cuatro placas de TiO2-x sobre sustratos de aluminio se aplicaron como electrodos en una batería de escala de laboratorio. Se realizaron las curvas de voltametría cíclica y los ciclos de carga/descarga de la batería de plomo y los resultados fueron excelentes (Facultad de Ingeniería y Medio Ambiente, Universidad de Southampton). El último objetivo de este doctorado consistió en el desarrollo de nuevos sensores de gas funcionales a través de la tecnología de APS. Se estableció hacer crecer la capa sensorica sobre un sustrato cerámico delgado para poder aumentar la temperatura de trabajo. Las condiciones de proyección fueron seleccionadas para alcanzar una buena deposición, no dañar el sustrato y aumentar la cantidad de vacantes de oxígeno. La detección fue analizada a diferentes temperaturas de trabajos y los rendimientos fueron satisfactorios (Grupo MIND Micronanotecnologies I Nanoscòpies per Dispositius electrònics i fotònics, Facultad de Física, Universitat de Barcelona).

Abstract The thesis describes the development of a novel LTCC material system for RF and microwave telecommunication purposes. The work has been divided into three parts. In the first section, the compositional and firing properties of this novel LTCC dielectric have been studied as well as its thermomechanical and dielectric properties. The second section describes the multilayer component preparation procedure for the ceramic material including tape casting and lamination parameters and the selection of the conductor paste. In the last section, the novel LTCC material system has been used to demonstrate its properties in RF multilayer resonators and a bandpass filter. The dielectric material for the novel LTCC system was prepared using magnesium calcium titanate ceramic, the firing temperature of which was decreased to 900°C by the addition of a mixture of zinc oxide, silicon oxide and boron oxide. The powder was made without any prior glass preparation, which is an important process advantage of this composition. The fired microstructure was totally crystalline with high density (3.7 Mg m-3) and low porosity (0.5 %). The mechanical properties were virtually identical to the values of the commercial LTCCs, but the higher thermal expansivity makes it most compatible with alumina substrates. The dielectric values were also good. The permittivity was 8.5 and the dissipation factor (0.9·10-3 at 8 GHz) less than that of the commercial LTCCs. Furthermore, the temperature coefficient of the resonance frequency was demonstrated to be adjustable between the range of +8.8 ... -62 ppm/K with a simple compositional variation of titanium oxide. The slurry for the tape casting was prepared using poly(vinyl butyral) -base organic additives and the 110 μm thick tapes had a smooth surface (RA < 0.5 μm). The multilayer components were prepared using 20 MPa lamination pressure, 90°C temperature and 1 h dwell time. The most suitable conductor paste for this composition was found to be commercial silver paste (duPont 6160), which produced satisfactory inner and outer conductor patterns for multilayer components. Finally, resonators with a resonant frequency range of 1.7 ... 3.7 GHz were prepared together with a bandpass filter suitable for the next generation of telecommunication devices. This demonstration showed the potential of the developed novel LTCC material system at high RF frequencies.

Thesis (Ph.D.)--Chemical Engineering, Georgia Institute of Technology, 2009.
Committee Chair: Prof. Sankar Nair; Committee Co-Chair: Prof. Samuel Graham; Committee Member: Prof. Amyn S. Teja; Committee Member: Prof. Mo Li; Committee Member: Prof. Peter Ludovice.