Made available in DSpace on 2015-04-22T22:08:50Z (GMT). No. of bitstreams: 1 DISSERTACAO_OTAVIO AUGUSTO PAIVA.pdf: 8701931 bytes, checksum: fa7ddfc8f71e05d7fe06a55c98faefc8 (MD5) Previous issue date: 2009-08-07 / Fundação de Amparo à Pesquisa do Estado do Amazonas / The experimental program of the present project was developed in order to evaluate the residue performance of ground plain glasses in cement based paste and mortar. Different conditions of grounding were used to generate a material with particles of the same order of magnitude of the cement particles. The ground glass residue (GGR) displayed physicalchemistry characteristics compatible to the ones of pozzolan, with relevance to the pozzolanic activity index (PAI). PAI equal to 104% was obtained, which is higher than that 75% -minimum value required by the Brazilian standard. The GGR was used in paste and mortar as a partial replacement of cement of 0%, 10%, 15% and 20% in mass, considering a waterbinder ratio of 0,4. The GGR behavior was evaluated through the X-Ray diffraction, thermal analysis, compressive strength, modulus of elasticity, porosity, water absorption, and alkaliaggregate reaction. The results did not indicate difference between the mechanical strength of the pastes with GGR and reference mixture after 28 days of curing. In mortars, the results of mechanical strength of the GGR mixtures were adequate from 7 days due to the filler and pozzolanic effects, mainly the 20% GGR mortar. In particular, the GGR provided increasing of compressive strength of 14% and 22% after 28 and 56 days of curing, respectively. / O programa experimental realizado no presente projeto foi desenvolvido de forma a avaliar o desempenho do resíduo de vidros planos moídos em pastas e argamassas a base de cimento Portland. Foram estudadas diferentes condições de moagem que possibilitassem a obtenção de um material com partículas da mesma ordem de gRandeza das partículas do cimento. O resíduo de vidro moído (RVM) apresentou características físico-químicas compatíveis às da pozolana, com destaque para o índice de atividade pozolânica. Obteve-se valor de 104%, empregando o cimento, que é superior a 75%, prescrito na norma brasileira. O RVM foi aplicado em pastas e argamassas como substituto parcial do cimento, para teores de 0%, 10%, 15%, e 20% em massa, para uma relação água-aglomerante de 0,4. O comportamento do RVM foi avaliado através de ensaios de difração de raios X, análise térmica, resistência à compressão, porosimetria, absorção, permeabilidade, módulo de elasticidade e reação álcaliagregado. Os resultados indicaram que as resistências mecânicas das pastas com RVM alcançaram o valor da resistência de referência a partir dos 28 dias. Nas argamassas foram obtidos resultados satisfatórios de resistência mecânica a partir dos 7 dias, iniciado pelo efeito de preenchimento e, posteriormente, pelo efeito pozolânico que superou os resultados de referência após os 28 dias, principalmente para o teor de 20%. Particularmente, o RVM aumentou a resistência à compressão em 14 e 22% após os 28 e 56 dias de cura, respectivamente.

The drivers of human health and changing climate are important areas of environmental and atmospheric studies. Among many environmental factors present in our biosphere, small particles, also known as ultrafine particles or UFPs, have direct and indirect pathways to affect human health and climatic processes. The rapid change in their properties makes UFPs dynamic and often challenging to quantify their effect on health and radiative forcing. To reduce uncertainty in the climate effects of UFPs and to strengthen the evidence on health effects, accurate characterizations of physical and chemical properties of UFPs are needed. In this thesis, two broad aspects of UFPs were investigated: (1) the development of particle instrumentation to study particle properties; and (2) measurement of physical and chemical properties of UFPs relevant to human health and climate. These two broad aspects are divided into four specific aims in this thesis. The measurement of UFP concentration at different locations in an urban location, from roadside to various residential areas, can be improved by using a mobile particle counter. A TSI 3786 Condensation Particle Counter (CPC) was modified for mobile battery-power operation. This design provided high-frequency, one second time resolution measurements of particle number and carbon dioxide (CO2). An independent electric power system, a central controller and robust data acquisition system, and a GPS system are the major components of this mobile unit. These capabilities make the system remotely deployable, and also offer flexibility to integrate other analog and digital sensors. A Volatility Tandem Differential Mobility Analyzer (V-TDMA) system was designed and built to characterize the volatility behavior of UFPs. The physical and chemical properties of UFPs are often challenging to measure due to limited availability of instruments, detection limit in terms of particle size and concentration, and sampling frequency. Indirect methods such as V-TDMA are useful, for small mass (<1 µg/m3), and nuclei mode particles (<30nm). Another advantage of V-TDMA is its fast response in terms of sampling frequency. A secondary motivation for building a V-TDMA system was to improve instrumentation capability of our group, thus enabling study of kinetic and thermodynamic properties of novel aerosols. Chapter four describes the design detail of the built V-TDMA system, which measures the change in UFP size and concentration during heated and non-heated (or ambient) condition. The V-TDMA system has an acceptable penetration efficiency of 85% for 10 nm and maintains a uniform temperature profile in the heating system. Calibration of V-TDMA using ammonium sulfate particles indicated that the system produces comparable evaporation curves (in terms of volatilization temperature) or volatility profiles to other published V-TDMA designs. Additionally the system is fully programmable with respect to particle size, temperature and sampling frequency and can be run autonomously after initial set up. The thesis describes a part of yearlong study to provide a complete perspective on particle formation and growth in a rural and agricultural Midwestern site. Volatility characterizations of UFPs were conducted to enable inference about particle chemistry, and formation of low volatile core or evaporation resistant residue in the UFP in the Midwest. This study addresses identification of the volatility signature of particles in the UFP size range, quantification of physical differences of UFPs between NPF1 and non-NPF events and relation of evaporation resistant residue with particle size, seasonality and mixing state. K-means clustering was applied to determine three unique volatility clusters in 15, 30, 50 and 80 nm particle sizes. Based on the proposed average volatility, the identified volatility clusters were classified into high volatile, intermediate volatile and least volatile group. Although VFR alone is insufficient to establish chemical composition definitively, least volatile cluster based on average volatility may be characteristically similar to the pure ammonium sulfate. The amount of evaporation residue at 200 °C was positively correlated with particle size and showed significant correlation with ozone, sulfur dioxide and solar radiation. Residue also indicated the presence of external mixture, often during morning and night time. Air quality science and management of an accidental urban tire fire occurring in Iowa City in May and June of 2012 were investigated. Urban air quality emergencies near populated areas are difficult to evaluate without a proper air quality management and response system. To support the development of an appropriate air quality system, this thesis identified and created a rank for health-related acute and chronic compounds in the tire smoke. For health risk assessment, the study proposed an empirical equation for estimating multi-pollutant air quality index. Using mobile measurements and a dispersion model in conjunction with the proposed air quality index, smoke concentrations and likely health impact were evaluated for Iowa City and surrounding areas. It was concluded that the smoke levels reached unhealthy outdoor levels for sensitive groups out to distances of 3.1 km and 18 km at 24 h and 1h average times. Tire smoke characterization was another important aspect of this study which provided important and new information about tire smoke. Revised emission factors for coarse particle mass and aerosol-PAH and new emission factors and enhancement ratios values for a wide range of fine particulate mass, particle size (0.001-2.5 µm), and trace gas were estimated. Overall the thesis added new instrumentation in our research group to measure various physical properties such as size, concentration, and volatility UFP. The built instruments, data processing algorithm and visualization tools will be useful in estimation of accurate concentration and emission factors of UFP for health exposure studies, and generate a fast response measurement of kinetic and thermodynamics properties of ambient particles. This thesis also makes a strong case for the development of an air quality emergency system for accidental fires for urban location. It provides useful evaluation and estimation of many aspects of such system such as smoke characterization, method of air quality monitoring and impact assessment, and develops communicable method of exposure risk assessment.

Various colloidal delivery systems, including polymeric nanoparticles, metal colloids, liposomes, and microemulsions have been reported to enhance the delivery of therapeutic agents following intranasal administration. However, the mechanisms involved in the uptake of these nanomaterials, especially those in the ultrafine size ranges (diameter < 20 nm) through nasal mucosa and their subsequent biodistribution in the body are not well characterized. The objectives of this study address the knowledge gap regarding ultrafine nanoparticle transfer in the nasal mucosa by quantifying nanoparticle uptake and biodistibution patterns in the presence and absence of known inhibitors of endocytic processes. The uptake of ~ 10 nm fluorescent quantum dots (QDs) was investigated by measuring the concentration of QDs following exposure to bovine respiratory and olfactory mucosal explants. An inductively coupled optical emission spectroscopy method was developed to measure the amount of QDs within the tissues. The results demonstrated that carboxylate-modified QDs (COOH-QDs) show ~2.5 fold greater accumulation in the epithelial and submucosal regions of the olfactory tissues compared to the respiratory tissues. Endocytic inhibitory studies showed that in respiratory tissues clathrin-dependent, macropinocytosis and caveolae-dependent endocytosis process were all involved in the uptake of COOH-QDs. Whereas in olfactory tissues, clathrin-dependent endocytosis was the major endocytic pathway involved in uptake of COOH-QDs. Additional energy-independent pathways appeared to also be active in the transfer of COOH-QDs into the olfactory mucosa. Interestingly, PEGylated quantum dots (PEG-QDs) of similar size ~15 nm were not internalized into the bovine nasal tissues. In vivo fluorescence imaging was used to study the biodistribution of quantum dots following nasal instillation in mice. These studies showed that majority of COOH-QDs remain in the nasal tissues for relatively long periods of time (up to 24 h) whereas PEG-QDs showed no such accumulation. Biodistribution studies of gold nanoparticles (~15 nm) in mice using micro-CT showed that gold nanoparticles were transferred to the posterior turbinate region and a fraction of the administered dose distributed to regions in close proximity to the olfactory bulb. Both NIR imaging and micro-CT imaging were useful tools for visualization of in vivo nanoparticle distribution. A diazepam-containing microemulsion (dispersed phase ~40 nm) was formulated to investigate the uptake mechanisms utilized for fluid-phase colloidal dispersions in the nasal mucosa. The resulting diazepam-containing microemulsion showed enhanced transfer of the drug into the bovine nasal respiratory and olfactory tissues. It is unclear if endocytosis of the fluid-phase nanodispersions played a role in drug absorption from the microemulsions in a manner similar to the uptake of solid-phase nanoparticles, however, since there was significant loss of the epithelial cell layer following exposure to the microemulsion formulation which likely altered the barrier properties of the epithelium. These studies have increased the fundamental understanding of ultrafine nanoparticle uptake in the nasal tissues and the resulting nanoparticle biodistribution patterns. While ultrafine nanoparticles may have limited application in the development of efficient drug delivery systems, an understanding of the size-dependent and tissue-dependent processes responsible for the uptake of particulates into mucosal tissues will contribute to the rational development of nanoparticulate drug delivery strategies investigating the nasal and other routes of administration.

The purpose of this study was to investigate whether or not differing base metals and filler wires used during welding processes contributed to differing amounts of ultrafine particles (UFP) and nanoparticles being emitted during the welding procedure. The study was also conducted to determine UFP and nanoparticle exposure in the breathing zones of the welders as well as the breathing zones of pipefitters and fire watchers, who commonly sit 6ft behind the welding arc. In order to determine if UFP and NP exposures differed with base metal and filler wire, all welding processes utilized the same welding machine for metal inert gas (MIG), the same wire speed, and the same voltages during each welding process. The only variation in welding procedures were cover gases used, base metals, and filler wires. Measurements gathered during welding procedures were conducted in the breathing zone of the welder and pipefitters consisted of UFP measurements taken by two different condensation particle counters (CPC), which operated in synchrony at the start and cessation of the welding process. NP measurements were taken by a NanoScan Scanning Mobility Particle Sizer (SMPS) and were also placed in the breathing zone of the welder. Lastly, particle characterization measurements for transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) were gathered using a filter attached to a high flow pump, which was placed in the breathing zone of the welder. According to the results, base metal and filler wire do emit differing amounts of NP and UFP during the welding processes. Carbon steel emits the highest amount of nanoparticles, while stainless steel emits the second highest amount, and inconel emits the least. The results also concluded that welders are exposed to a greater concentration of nanoparticles and UFPs than those experienced by pipefitters who stand 6ft from the welding arc.

Friction stir processing (FSP) is applied to produce particulate-reinforced aluminum matrix composites with ultrafine grained structure from elemental powder mixtures of Al-Cu, Al-Ti and Al-Si. The microstructures of the composites were characterized by the use of XRD, SEM and TEM. Microhardness, tensile and compressive tests were performed to evaluate the mechanical properties of these composites. The mechanisms of microstructure evolution in FSP and the strengthening mechanisms in these composites are discussed. In the Al-Si system, the Si particles were broken and uniformly distributed in the stir zone by the application of multiples-pass FSP. The average size of Si particles and Al grains were refined to below ~2

In this study, firstly, in order to achieve fine grains in solid solution strengthened AZ31 magnesium alloy by friction stir processing (FSP), various efforts have been made. It has found that with a newly designed cooling system, the microstructure of commercial AZ31 alloy can be refined dramatically by carefully controlling the FSP parameters. It is of scientific interest that nanometer grains have been observed in the resultant microstructure for the AZ alloy experienced by two-pass FSP. Besides, in order to modify the microstructure and mechanical properties, FSP is also applied to incorporate AZ31 Mg alloy with nano-ZrO2 particles, nano-SiO2 particles and different fractions of Al and Zn elements. The microstructure and mechanical properties of the modified alloy and composite samples are investigated and compared. By one-pass FSP coupled with rapid heat sink from liquid nitrogen cooling approach, the ultrafine grain size in AZ31 Mg alloy is successfully achieved. The grain boundaries are well defined and the mean grain size can be refined to 100~300 nm from the initial 75 £gm of commercial AZ31 Mg alloys sheets. The ultrafine grained structure can drastically increases the microhardness from the initial 50 up to 120 Hv, or an increment factor of 2.4 times. Furthermore, the nanometer grains can be even achieved by two passes FSP coupled with rapid heat sink. The resulting microstructure exhibits equiaxed grains ranging from 40 nm to 200 nm with an average grain size of less than 100 nm. The nanocrystalline grains can be characterized by the TEM observations and the diffraction rings in SAD patterns. The highest hardness point can reach ~150 Hv which is equal to triple of the AZ31 matrix, and the mean hardness also increases up to around 134 Hv. Bulk Mg-AZ31 based composites with 10~20 vol% of nano-ZrO2 particles and 5~10 vol% of nano-SiO2 particles are also successfully fabricated by FSP. The average grain size of the resultant composites could be effectively refined to 2~4 £gm, and it demonstrates much higher hardness values compared to commercial AZ31 billet. Moreover, for the Mg/ZrO2 composite fabricated by one pass and subsequent cooling pass FSP, the recrystallized grain size could be further refined to 0.4 £gm with the hardness value of 135 Hv. As for multi-element Mg base alloys fabricated by FSP, high fractions of Al and Zn elements can result in apparent grain refinement, this can be proved by the broadening of diffraction peaks. Multi-passes FSP can induce the appearance of intermetallic compounds, however, some of them are quasi-crystals with icosahedral point group symmetry. The average hardness of the resultant alloys reachs nearly 350 in Hv scale due to the generation of intermetallic compounds and grain refinement.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第18986号 / 工博第4028号 / 新制||工||1620 / 31937 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 辻 伸泰, 教授 田中 功, 教授 乾 晴行 / 学位規則第4条第1項該当

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第18987号 / 工博第4029号 / 新制||工||1620 / 31938 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 辻 伸泰, 教授 白井 泰治, 教授 松原 英一郎 / 学位規則第4条第1項該当

Grouting techniques have been in used for many years, but several new grout materials have surfaced in recent decades that have re-defined the boundaries of the limitations of grouting programs. Typically these applications are used for seepage control in earthen impoundments, but strength of these earthen impoundments should be considered where there is potential for movement in the grouted soil mass. This study investigated initial conditions that could affect grout application effectiveness. The initial conditions in question were soil grain size and in situ moisture content. Two grouts were used, ultrafine and acrylate, and variations in pure grout properties were studied. An apparatus was developed so that a uniform grout could penetrate the pore spaces of a soil specimen. The rate of penetration of the grout into the soil was studied. The unconfined compressive strength of the resulting grouted soil was then analyzed. In testing neat ultrafine grout, it was shown that increased water-to-cement ratios had negative effects on the stability of the grout. Increasing the water-to-cement ratio from 0.5 to 2.5 resulted in a decrease in strength by a factor of 100. An inhibitor chemical was used to increase the time for reaction in the acrylate grout. During the chemical reaction, the curing temperature and gel times were monitored. A grout mix was selected for the acrylate grout that achieved appropriate gel times. In general, this study found that the grout penetrations rates into the soil increased as the initial moisture was increased from dry conditions to a gravimetric moisture content of nine percent. In each study, increased initial moisture decreased the grouted soil strength, with decreases in strength exceeding 50 percent. Empirical relationships were realized when compared to the initial matric suction of the soil. This suggests initial matric suction may be a useful initial condition for estimating increases in soil strength upon implementation of a grouting program for both the acrylate and ultrafine grouts.

Orientador: Alessandro Roger Rodrigues / Banca: Hidekasu Matsumoto / Banca: Otávio Villar da Silva Neto / Resumo: Este trabalho apresenta um estudo sobre a influência das condições de fresamento na formação de cavaco, microestrutura, dureza e rugosidade da peça. Foi ensaiado um aço baixo carbono 0,15%C com dois tamanhos de grão distintos. Para ambos os materiais da peça, empregou-se 8 condições de usinagem variando a velocidade de corte, o avanço da ferramenta e a profundidade de usinagem visando à aplicação da Análise de Variância (ANOVA), dando-se destaque à usinagem considerada como alta velocidade de corte e convencional. Os ensaios de fresamento de topo concordante a seco foram conduzidos em um centro de usinagem CNC de 11 kW de potência e rotação do eixo-árvore de 7.500 rpm. Utilizou-se ferramenta de diâmetro 25 mm com dois insertos de metal duro revestidos com Al2O3. Os resultados apontam para uma influência dos parâmetros de corte sobre todas as variáveis de resposta, exceto a macrodureza. Velocidades de corte e profundidades de usinagem maiores causaram deformação da microestrutura do material "como recebido" próxima à superfície fresada. Os mesmos parâmetros governaram o aumento da microdureza superficial e da profundidade da camada endurecida. O material com grãos ultrafinos não apresentou deformação da microestrutura próxima à superfície fresada nem aumento de microdureza superficial. A velocidade de corte influiu apenas na profundidade da camada endurecida. A rugosidade foi inversa e diretamente influenciada pela velocidade de corte e avanço da ferramenta, respectivamente, sendo dependente também do tamanho de grão do material da peça. Os mesmos parâmetros de corte influíram de forma significativa no ângulo de deformação da microestrutura dos cavacos, cuja classificação foi dependente do material e das condições de usinagem. / Abstract: This work deals with the influence of milling conditions on chip formation, microstructure, hardness and roughness of workpiece. A 0.15%C low carbon steel with two different grain sizes was milled. For both workpiece materials eight milling conditions were employed where cutting speed, tool feed and depth of cut varied and combined aiming at Analysis of Variance application. The machining conditions considered as High-Speed Cutting (HSC) and Conventional were focused. The milling tests considering down-milling and dry conditions were carried out in a CNC machining center with 11 kW power and 7,500 rpm spindle rotation. A 25 mm diameter endmill with two inserts coated of Al2O3 was used. The results indicated the cutting parameters influenced on all output variables except the macrohardness. Greater cutting speed and depth of cut caused deformation of workpiece microstructure with 10.8 um grain size near milled surface. The same parameters governed the increase of surface microhardness and hardened layer depth. Refined grain material did neither present deformation of microstructure near milled surface nor increase of microhardness. The cutting speed influenced only on depth of hardened layer. Roughness was inverse and directly influenced by cutting speed and tool feed, respectively, and dependent on grain size of workpiece material. These parameters also influenced on deformation angle of chip microstructure which were classified as continuous for 10.8 um grain size and segmented for the ultrafine grain, in this case just for some milling conditions. / Mestre