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A range of geochemical reactions are controlled by the interfacial characteristics of rocks and minerals. Many engineered and natural systems are affected by geochemical reactions that occur at interfaces. Asphalt-aggregate adhesion in road construction is influenced by the interfacial characteristics of the aggregate. Likewise, the remediation of nonaqueous-phase liquid contaminants, such as trichloroethylene or methyl tert-butyl ether, is controlled by the interactions between mineral surfaces and the organic liquid. Many natural systems are also influenced by reactions at interfaces. The migration of petroleum in sedimentary basins is influenced by the wettability of the surfaces of the basin pore space. Adhesion of organisms, such as bacteria or lichens, to rock surfaces is controlled by the interactions of proteins and mineral surfaces. Rock and mineral surfaces are described by surface energy. Surface energy is a thermodynamic construct defined as the amount of work required to form more of a surface. Surface energy can be divided into van der Waals, Lewis acid, and Lewis base components. The ability to predict the magnitude of surface energy components is valuable in understanding species behavior. Surface energy is controlled by three master variables: surface chemistry, surface morphology, and surface coatings. While the surface energy of a number of minerals and aggregates has been characterized, there has not yet been a comprehensive study of the surface energies of a variety of the most common minerals and aggregates using consistent methodology. In addition there has not yet been a study of the effect of these three master variables on surface energies of natural minerals and rocks. This study measured the surface energy of 22 common minerals and 7 aggregates. The samples’ bulk and surface chemistries were characterized with wavelength and energy dispersive spectra analyses on an electron microprobe and x-ray photoelectron spectroscopy. The XPS was also used to quantify the organic and inorganic coatings on the surfaces. Results showed that van der Waals surface energy is typically between 40 and 60 ergs/cm2. Polar surface energy varies by 1 to 3 orders of magnitude, and thus is likely the most important component in accounting for changes between natural minerals.

Orientadores: Sandra Cristina dos Santos Rocha, Virginia Aparecida da Silva Moris / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-13T14:24:52Z (GMT). No. of bitstreams: 1 Costa_SuzaraSantos_M.pdf: 3149435 bytes, checksum: 4253d824e6807a4d4dabe9f5337e4982 (MD5) Previous issue date: 2009 / Resumo: O leito vibrofluidizado (LVF) consiste na aplicação de vibração mecânica ao leito fluidizado convencional com o objetivo de reduzir a ocorrência de bolhas, canais preferenciais e evitar o fenômeno da de fluidização em processos como recobrimento, granulação, entre outros. A utilização do LVF é diversificada para materiais coesivos, adesivos, aglomerados e pastosos. A granulação consiste no aumento da partícula mediante a incorporação de materiais ativos e/ou inertes e é um importante processo utilizado com o objetivo de melhorar aspecto, manuseio, compactação e transporte de partículas finas. Esse processo é bastante encontrado na literatura com o uso em leitos fluidizados convencionais, contudo, o processamento de materiais que possuem forças interpartículas intensas quando sujeitos a aspersão de ligantes, torna-se difícil e dispendioso. A celulose microcristalina é originada da hidrólise ácida da celulose e utilizada, entre outros usos industriais, como estabilizante e aditivo alimentício. Na indústria farmacêutica, é um dos excipientes mais utilizados em formulações de dosagem oral. Baseado no exposto foi realizado um estudo sobre a granulação da celulose microcristalina em leito vibrofluidizado, utilizando como ligante solução de matodextrina 35%. A solução foi aspergida sobre o leito de partículas através de um sistema de atomização acoplado ao leito vibrofluidizado. Foi desenvolvido um planejamento experimental fatorial fracionário (25-1), cujas variáveis operacionais foram: amplitude (A) e frequência (f) de vibração, pressão de atomização (P), temperatura do ar de entrada (T) e vazão de solução (Q). Os níveis das variáveis de entrada no planejamento foram: 0,01m e 0,02m; 3 Hz e 6 Hz, 5 Psig e 15 Psig, 60ºC e 80ºC e 4 ml/min e 10 ml/min, respectivamente. O planejamento foi desenvolvido com 4 repetições no ponto central. Para avaliar a qualidade do produto foram analisadas três variáveis de resposta, que resultaram nas seguintes faixas: crescimento da partícula - 3,17% a 33,11%, ângulo de repouso - 8,4º a 12º e índice de aglomerados - 0,2% a 5,69%. Com o experimento estatisticamente planejado constatou-se que todas as variáveis independentes influenciaram as variáveis de resposta consideradas e, portanto, não foi possível estabelecer um planejamento completo com um número menor de variáveis. O comportamento fluidodinâmico da celulose microcristalina antes da granulação também foi estudado. As curvas obtidas refletiram um comportamento característico encontrado na literatura de leitos vibrofluidizados. A fluidodinâmica do material permitiu, embora com dificuldade, determinar a velocidade de mínima fluidização (pelo método convencional da interseção das retas em leitos fluidizados) e velocidade de mínima fluidização completa para leitos vibrofluidizados. A velocidade de mínima mistura do material também foi determinada, mas por observação visual durante os experimentos. A velocidade de operação foi estabelecida em 0,30 m/s após os ensaios preliminares de fluidodinâmica e de granulação. O produto final obtido após o processo de granulação apresentou boa escoabilidade e um aumento no seu diâmetro médio de Sauter, confirmando a granulação da celulose microcristalina e revelando o leito vibrofluidizado como equipamento promissor para efetuar o processo de granulação. / Abstract: The vibrofluidized bed (VFB) consists in applying mechanical vibration to the conventional fluidized bed to reduce the occurrence of bubbles, preferential channeling and defluidization phenomena, which are common when fluidizing cohesive, adhesive and paste materials. Granulation is used to increase particle size through incorporation of active materials and/or inert and it is a very important process to improve the appearance, handling and transport of fine particles. Granulation is usually conducted using conventional fluidized beds; however, the processing of powders having high interparticle forces, when subjected to intense spraying of binders, is difficult and expensive. Microcrystalline cellulose is a fine powder that is originated from acid hydrolysis of cellulose and is used, among other industrial uses, as a stabilizer, food additive and carrier in drugs. This work reports the analysis of wet granulation of microcrystalline cellulose in a vibrofluidized bed using an aqueous maltodextrina solution as binder. A factorial experimental design (25-1) was developed with the independent variables: vibration amplitude (A) and frequency (f), atomization pressure (P), inlet air temperature (T) and maltodextrin solution flow rate (Q). The responses analyzed were in the following levels: particle growth - 3.17% to 33.11%, angle of repose - 8.4º to 12º and percentage of lumps - 0.2% to 5.69%. The statistical analysis of the experimental design was able to determine that all the independent variables showed significant influence on the process and so it was not possible to perform an experimental design with a smaller number of variables. The fluid dynamics of the bed of microcrystalline cellulose before granulation was also analyzed and it presented the behavior of fluid dynamic curves of vibrofluidized beds found in the literature. In spite of the difficulty, the fluid dynamic curves allowed to determine the minimum fluidization velocity (conventional method of intersection of straight lines of fixed and fluidized regions) and complete minimum fluidization for vibrofluidized beds. The velocity of minimum mixture was also determined, by visual observation. The operation velocity was set at 0.30 m/s based on the dynamic tests and preliminary tests of granulation. The final product showed excellent flowability and generated an increase in its mean Sauter diameter, thus confirming the granulation of microcrystalline cellulose and showing the vibrofluidized bed as promising equipment for this process. / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

Cancer metastasis directly accounts for an estimated 90% of all cancer related deaths and is correlated with the presence of malignant cells in systemic circulation. This observed relationship has prompted efforts to develop a fluid biopsy, with the goal of detecting these rare cells in patient peripheral blood as surrogate markers for metastatic disease as a partial replacement or supplement to tissue biopsies. Numerous platforms have been designed, yet these have generally failed to support a reliable fluid biopsy due to poor performance parameters such as low throughput, low purity of enriched antigen positive cells, and insufficiently low detection thresholds to detect poor expressed surface markers of target cell populations. This work describes the development of a rapid cell sorting technology called Antigen Specific Lysis (ASL) based on photo-crosslinked polymer encapsulation to isolate tumor cells in suspension. In the first study, we characterize the chemical and structural properties of the surface-initiated polymer films formed directly on mammalian cell surfaces. Coated populations are shown to remain highly viable after coating formation. Biomolecular transport is examined though film coatings on cellular substrates using fluorescent, time-resolved confocal microscopy and diffusivity estimates are generated for these materials. In the next study, a lysis-based cell isolation platform is described in which marker positive cells can be specifically coated in a heterogeneous cell suspension. Anionic surfactants lyse virtually 100% of uncoated cells while fully encapsulated cells remain protected, and are then easily collected by centrifugation. We report that purified cells are released from polymeric coatings to yield viable and functional populations. We monitor cell response throughout the isolation process by multiple techniques, and report viability >80% after the sorting process. Lastly, we examine the response of process yield on the level of photoinitiator loading on target populations. Streptavidin-fluorochrome loading was quantitatively assessed on a panel of markers, both epithelial and mesenchymal, on representative model breast and lung cancer cells. We report that ASL is fundamentally capable of achieving 50-60% yield which is promising for fluid biopsy applications. Finally, both EpCAM and metastatic targeting strategies are then compared to covalently biotinylated samples to inform future robust targeting strategies.

Neste trabalho são apresentados os principais conceitos relacionados às pinturas texturizadas. Foram propostas diretrizes mínimas para especificação e recebimento de pinturas texturizadas acrílicas em substratos de argamassa para fachadas de edifícios. Para o estabelecimento das diretrizes foram evidenciadas as práticas adotadas através de estudos de casos e foi realizado um estudo experimental para desenvolvimento dos principais critérios de aceitação propostos. Considera-se que a especificação técnica é o ponto de partida para assegurar que as pinturas texturizadas acrílicas atendam o uso previsto. / In this work the main concepts related to textured coatings are presented. The minimal directives are proposed for specification and act of receiving of acrylic textured coatings in renderings for buildings frontages. For the establishment of the directives the practices adopted through studies of cases had been evidenced and an experimental study was carried through for development of the main considered accepted criteria. It is considered that the technical specification is the starting point to assure that the acrylic textured coatings take care of the foreseen use.

The primary focus of my work has been to prepare new solid adsorbents for solid phase microextraction (SPME) via sputtering of silicon. The orientation of the silica substrates/fibers and the sputtering pressure induced the formation of porous and columnar structures. Sputtering was performed for different times to yield fibers with different thicknesses. Piranha treatment of the surface increased the concentration of silanol groups, which underwent condensation with vapor deposited octadecyldimethylmonomethoxy silane to incorporate octadecyl chains onto the fiber surfaces. Silanized, sputtered fibers were preconditioned for 3 h at 320 °C to remove the unreacted chains. Comparison of the extraction efficiencies of 1.0 and 2.0 µm sputtered, silanized fibers with a commercial fiber (7 µm PDMS) for a series of analyte mixtures, which included alkanes, alcohols, aldehydes, esters, and amines, was demonstrated. The silanized, sputtered fiber performed better than the commercial fiber in extraction of most of the compounds. These fibers demonstrated long life as no degradation was seen even after 300 extractions. Carry-over between runs was not observed. The repeatability of the sputtered fibers was similar to commercial ones. The extraction of more than 50 compounds from a real world botanical sample using the 2.0 µm sputtered, silanized fiber was also demonstrated. In my second project, a facile method for the preparation of superhydrophobic surfaces (SHS) on glass and silicon surfaces was developed. A two-tier topography (needed for an SHS) was created in 60 min by the aggregation of nanosilica during in situ urea-formaldehyde polymerization. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) demonstrated rough topography. Vapor deposition of a low surface energy silane imparted hydrophobicity, which was confirmed by the presence of an F 1s signal in X-ray photoelectron spectroscopy (XPS). The prepared surfaces exhibited water contact angles (WCA) of greater than 150 °C with very low sliding angles. In my third project, a multilayer assembly of nitrilotris(methylene)triphosphonic acid, a corrosion inhibitor, and zirconium was constructed on alumina at room temperature. Attempts to prepare a layer-by-layer assembly at higher temperature (70 °C) was unsuccessful due to etching of the alumina surface. A suite of analytical techniques, XPS, AFM, time-of-flight secondary ion mass spectrometry, and spectroscopic ellipsometry was used to characterize these surfaces. This thesis also contains appendices of tutorial articles I wrote on modeling in ellipsometry, and data analysis tools (classical least squares and multivariate curve resolution).