Aerogels are extremely high surface area, low density materials with applications including thermal and acoustic insulators, radiation detectors and cometary dust particle traps. However, their low density and aggregate structure makes them extremely fragile and practically impossible to machine or handle without breaking. This has led to the development of aerogel composites with enhanced mechanical properties through the addition of polymers or surface modifiers. To date, attempts to strengthen aerogels have come with significant increases in density and processing time. Here I will describe our search for a solution to these problems with our invention using methyl cyanoacrylate chemical vapor deposition (CVD) to strengthen silica, aminated silica and bridged polysilsesquioxane aerogels. This approach led to a strength improvement of the composites within hours and the strongest composite prepared had a 100x strength improvement over the precursor aerogel. We also developed the first approach to control the molecular weight of the polymers that reinforce silica aerogels using surface-initiated atom transfer radical polymerization (SI-ATRP). Although PMMA reinforcement of silica aerogels improved the mechanical properties, further strength improvements were achieved by cross-linking the grafted PMMA. Additionally, we developed the first silica aerogels reinforced with polyaniline nanofibers that were strong and electrically conductive. Reinforcing silica aerogels with polyaniline allowed them to be used as a sensor for the detection of protonating and deprotonating gaseous species. Finally we developed a new approach for the synthesis of silica and bridged polysilsesquioxane spheres using a surfactant free synthesis. This approach allowed for the first in-situ incorporation of base sensitive functionalities during the sol-gel polymerization.

abstract: This dissertation presents a systematic study of the sorption mechanisms of hydrophobic silica aerogel (Cabot Nanogel®) granules for oil and volatile organic compounds (VOCs) in different phases. The performance of Nanogel for removing oil from laboratory synthetic oil-in-water emulsions and real oily wastewater, and VOCs from their aqueous solution, in both packed bed (PB) and inverse fluidized bed (IFB) modes was also investigated. The sorption mechanisms of VOCs in the vapor, pure liquid, and aqueous solution phases, free oil, emulsified oil, and oil from real wastewater on Nanogel were systematically studied via batch kinetics and equilibrium experiments. The VOC results show that the adsorption of vapor is very slow due to the extremely low thermal conductivity of Nanogel. The faster adsorption rates in the liquid and solution phases are controlled by the mass transport, either by capillary flow or by vapor diffusion/adsorption. The oil results show that Nanogel has a very high capacity for adsorption of pure oils. However, the rate for adsorption of oil from an oil-water emulsion on the Nanogel is 5-10 times slower than that for adsorption of pure oils or organics from their aqueous solutions. For an oil-water emulsion, the oil adsorption capacity decreases with an increasing proportion of the surfactant added. An even lower sorption capacity and a slower sorption rate were observed for a real oily wastewater sample due to the high stability and very small droplet size of the wastewater. The performance of Nanogel granules for removing emulsified oil, oil from real oily wastewater, and toluene at low concentrations in both PB and IFB modes was systematically investigated. The hydrodynamics characteristics of the Nanogel granules in an IFB were studied by measuring the pressure drop and bed expansion with superficial water velocity. The density of the Nanogel granules was calculated from the plateau pressure drop of the IFB. The oil/toluene removal efficiency and the capacity of the Nanogel granules in the PB or IFB were also measured experimentally and predicted by two models based on equilibrium and kinetic batch measurements of the Nanogel granules. / Dissertation/Thesis / Ph.D. Chemical Engineering 2011

Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro Tecnológico, Programa de Pós-Graduação em Ciência e Engenharia de Materiais, Florianópolis, 2014. / Made available in DSpace on 2015-02-05T20:11:03Z (GMT). No. of bitstreams: 1 328020.pdf: 2315066 bytes, checksum: 49dc7933d28c046dd7b9eae203b97a54 (MD5) Previous issue date: 2014 / Um modelo estocástico para crescimento de aerogéis inorgânicos é proposto e simulado através de um método de Monte Carlo. Partículas de sol interagem em um espaço discreto tridimensional através de um potencial central de longo alcance. Alguns mecanismos relacionados ao processo de gelificação são considerados (agregação, difusão, dissociação) e regidos através de um algoritmo de Metropolis-Hastings adaptado. A topologia da rede formada é analisada para diferentes condições iniciais de processamento (densidade de partículas de sol, temperatura de equilíbrio e taxa de dissociação no sistema). A simulação do método proposto mostra a existência de uma transição de fase (sol-gel) observada através da divergência de um parâmetro de ordem para uma dada temperatura crítica. São identificadas duas características topológicas das redes em estados onde ocorreu crescimento de gel. As propriedades morfológicas da estrutura porosa, como área superficial, porosidade, distribuição de tamanho de poros, e razão área-volume, apresentam coerência com os resultados obtidos pela análise da complexidade de redes.<br> / Abstract : A stochastic model for the growth of inorganic aerogels is studied using aMonte Carlo simulation technique. Sol particles interact in a three-dimensionallattice via a long-range central potential. The model accounts for some gelationrelated mechanisms (aggregation, diffusion, and dissociation) coupledby an adapted Metropolis-Hastings algorithm. The topology of the obtainedgel networks is analyzed for different initial processing conditions, such asconcentration of sol particles, equilibrium temperature, and system particlesdissociation rate. Simulation results show the existence of a sol-gel transitionshowed by the divergence of an order parameter when the system reachessome critical temperature. We have identified two major networks topologiesfor gel states. Morphological properties of the porous structure (surfacearea, porosity, pore size distribution, and surface area-to-volume ratio) are inagreement with the network complexity analysis.

Tese (doutorado) - Universidade Federal de Santa Catarina, Centro Tecnológico, Programa de Pós-Graduação em Engenharia Elétrica, Florianópolis, 2015 / Made available in DSpace on 2016-04-19T04:11:41Z (GMT). No. of bitstreams: 1 338179.pdf: 2584757 bytes, checksum: 5179faef93b715ae0c506c9570af8a4d (MD5) Previous issue date: 2015 / Sistemas de conversão fotovoltaicos são considerados uma das opções mais promissoras de energia renovável. Um dos grandes problemas das tecnologias fotovoltaicas convencionais está no alto custo de processamento. Neste contexto as células solares sensibilizadas por corante têm atraído uma atenção considerável, porém em sua constituição há eletrólitos líquidos, o que torna essa célula instável devido à degradação do mesmo, e para superar esta instabilidade, as células solares no estado sólido estão sendo estudadas. Nesta tese, foram desenvolvidos dois tipos de células solares no estado sólido: 1º. Filmes de pontos quânticos de CdTe foram depositados sobre um filme de tinta de aerogel de TiO2 e assim foi estudada sua atividade em células solares de absorventes extremamente finos (ETA); 2º Com o intuito de aumentar a eficiência dessas células produzidas, e diminuir o custo do processamento, foram desenvolvidas as células solares a base de perovskitas organometálicas (PVOM), onde é possível chegar a eficiências em torno de 20%. Uma tinta a base de aerogel de TiO2 foi utilizada com o intuito de aumentar a superfície de contato e assim depositar sobre essa tinta, uma maior concentração de perovskita (PVOM). Essa tinta de aerogel de TiO2 foi utilizada como camada transportadora de elétron, e para evitar o curto circuito existente pela presença de buracos nesse filme, uma fina camada de pasta de TiO2 foi depositada. As células solares contendo aerogel de TiO2 tiveram uma eficiência na conversão do fóton incidente em corrente em função do comprimento de onda (IPCE) superior comparadas a células solares contendo pasta de TiO2. Os aerogéis de TiO2 e a tinta a base de aerogel foram caracterizadas a partir de microscopia eletrônica de transmissão (MET-100kV), Análise de área superficial (BET), Espectrometria de infravermelho com transformada de Fourier (FTIR), Termogravimétrica (TG), Difração de raio-X (DRX), Espectrofotometria na região do UV-vis. A elevada superfície de contato no filme contendo a tinta de aerogel de TiO2 foi detectada na análise de Perfilometria. Os pontos quânticos sintetizados foram caracterizados a partir da espectrometria de infravermelho com transformada de Fourier (FTIR), Espectrofotometria na região do UV-vis e Espectroscopia de Fotoluminescência (PL). Para caracterizar as células solares e avaliar sua eficiência, curvas J×V foram realizadas e assim foram determinados: tensão de circuito aberto (VOC), densidade de corrente de curto circuito (JSC), fator de preenchimento (FF) e espectros de IPCE também foram realizados. A tinta a base de aerogel mostrou-se bastante promissora para células solares ETA e perovskita, pois a mesma facilita o processo de interpenetração da camada a ser depositada.<br> / Abstract : Photovoltaic conversion systems are considered one of the most promising options of renewable energy. A major problem of conventional photovoltaic technologies is the high cost of processing. In this context solar cells dye-sensitized have attracted considerable attention, but its constitution comprises liquid electrolytes, which makes this cell unstable, due to its degradation, and to overcome this instability, solid state solar cells are being studied. In this thesis it was developed two types of solid state solar cells: 1. Films of CdTe quantum dots were deposited on a TiO2 aerogel ink film and thus was studied solar cells extremely thin absorbers (ETA) activity; 2. In order to increase the efficiency of these cells produced, and decrease the cost of processing, researched solar cells at higher descent in the world, solar cells perovskites high performance where you can reach efficiencies of around 20%. A TiO2 aerogel ink film was used in order to increase the contact surface and thus deposited on this ink, a higher concentration of perovskite (PVOM). This TiO2 aerogel ink was used as the electron carrier layer, and to prevent existing short circuit by the presence of holes in the film, a thin layer of TiO2 paste was deposited. The solar cells containing TiO2 aerogel had a conversion efficiency of incident photon current as a function of wavelength (IPCE) higher compared to solar cells containing TiO2 paste. The TiO2 aerogels and TiO2 aerogel ink, were characterized from transmission electron microscopy (TEM-100kV), surface area analysis (BET), Fourier transform infrared spectrometry (FTIR), thermogravimetry (TG), X-ray Diffraction (XRD), spectrophotometry in the UV-vis region. The high contact surface of the film containing the TiO2 aerogel ink was detected in the profilometry analysis. The synthesized quantum dots were characterized from Fourier transform infrared spectrometry (FTIR), spectrophotometry in the UV-vis region and photoluminescence spectroscopy (PL). To characterize solar cells and evaluate their efficiency, J × V curves were carried out and so were determined: open circuit voltage (VOC), short circuit current (JSC), fill factor (FF) and IPCE spectra were also conducted. TiO2 aerogel ink proved to be very promising for solar cells ETA and perovskite, as it facilitates the interpenetration process the layer to be deposited.

Doctor of Philosophy / Department of Mechanical and Nuclear Engineering / Douglas S. McGregor / The 3He gas shortage for neutron detection has caused an increase in research efforts to develop viable alternative technologies. 3He neutron detectors cover areas ranging from 10–1000 cm2 in cylindrical form factors and are ideal for many nuclear applications due to their high intrinsic thermal neutron detection efficiency (> 80%) and gamma-ray discrimination (GRR ≤ 1 x 10-6) capabilities. Neutron monitoring systems for nuclear security applications include Radiation Portal Monitors (RPM’s), backpack, briefcase, and hand-held sensors. A viable replacement technology is presented here and compares three neutron detectors, each with different neutron absorber materials, to current 3He standards. These materials include Li and/or B silica aerogels, LiF impregnated foams, and metallic Li foils. Additionally, other neutron absorbing materials were investigated in this work and include LiF coated Mylar, B foils, BN coated carbon foam, and BN coated plastic honeycomb. From theoretical calculations, the Li foil material showed the greatest promise as a viable 3He alternative, thus a majority of the research efforts were focused on this material. The new neutron detector was a multi-wire proportional counter (MWPC) constructed using alternating banks of anode wires and 95% enriched 6Li foils sheets spaced 1.63 cm apart. In total, six anode banks and five layers of foil were used, thus an anode wire bank was positioned on each side of a suspended foils. Reaction products from the 6Li(n,α)3H reaction were able to escape both side of a foil sheet simultaneously and be measured in the surrounding gas volume concurrently. This new concept of measuring both reaction products from a single neutron absorption in a solid-form absorber material increased the intrinsic thermal neutron detection efficiency and gamma-ray discrimination compared to coated gas-filled detectors. Three different sizes of Li foil MWPC neutron detectors were constructed ranging from 25–1250 cm2 and included detectors for RPM’s, backpacks, and hand-held systems. The measured intrinsic thermal neutron detection efficiency of these devices was approximately 54%, but it is possible to exceed 80% efficiency with additional foils. The gamma-ray discrimination abilities of the detector exceeded 3He tubes by almost three orders of magnitude (GRR = 7.6 x 10-9).

O petróleo é uma matéria-prima de grande valor econômico. Buscando a substituição de matérias-primas não-renováveis, óleos vegetais vêm sendo usados cada vez mais como matéria-prima para combustíveis e polímeros. Derramamentos durante o manuseio de óleos são graves problemas ambientais. Fibras vegetais são usadas há muito tempo para a sorção de óleos em derramamentos. Resíduos de madeira na forma de serragem já são usados como sorventes de óleos, sendo um recurso barato e disponível. Entretanto, as características hidrofílicas das fibras vegetais reduzem sua capacidade de sorção de óleos. Os aerogéis de celulose tornaram-se um produto de grande interesse nessa área devido à sua alta porosidade (95 a 99%), baixa massa específica (0,004 to 0,15 g.cm-3) e alta área superficial (>60,m².g-1), além da abundância e sustentabilidade da celulose. O objetivo deste trabalho foi desenvolver um aerogel hidrofóbico de nanofibras de celulose a partir de resíduos da indústria moveleira (Pinus elliottii var. elliottii) processados por hidrólise ácida com explosão a vapor para a sorção de petróleo e óleos vegetais. No processo de explosão a vapor a melhor condição experimental foi observada para uma razão volumétrica de ácido acético e ácido nítrico 15:2:1 a 120°C e 30 minutos com rendimento superior a 90% em celulose e a remoção completa da hemicelulose e da lignina. Após a liofilização foi obtido um aerogel com massa específica 0,046 0,0013 g.cm-3 e porosidade 97,08 0,08%. A hidrofobização do aerogel gerou um ângulo de contato de 138,78º 0,78º. O aerogel mostrou capacidade de sorção máxima experimental (CSME) de 19,55 0,10 góleo.gaerogel-1 para petróleo e 13,73 0,62 góleo.gaerogel-1 para o óleo vegetal. A produção de nanofibras de celulose deu-se através de meios físicos (moagem) e a hidrofobização foi efetuada por modificação superficial das fibras com organosilanos (MTMS) por deposição a vapor. Na hidrólise do resíduo da indústria moveleira dois reagentes ácidos (ácido acético e ácido nítrico) foram testados individual e simultaneamente, com variações de temperatura, tempos e quantidade de reagente. A fração sólida rica em celulose obtida foi cominuída em moinho de pedras por 5 horas a 2500 rpm em uma suspensão com 1,5% m/m. O gel obtido foi congelado por 48 horas a -20ºC para posterior liofilização a -40ºC por 50 horas. Os aerogéis obtidos na liofilização foram tratados com o organosilano via deposição em fase vapor por 5 horas a 70ºC. O resíduo da indústria moveleira foi caracterizado quanto ao teor de celulose, hemicelulose, lignina, cinzas, extrativos e umidade. O processo de explosão a vapor foi caracterizado através do rendimento individual dos seus componentes (celulose e hemicelulose). Ensaios de massa específica aparente, ângulo de contato, porosidade, caracterização morfológica por microscopia eletrônica de varredura de emissão de campo, ensaios de sorção de óleos e cinética de sorção em meio homogêneo e heterogêneo de sorção de petróleo e óleo de soja foram realizados para caracterizar o aerogel. Modelos cinéticos de pseudoprimeira, pseudossegunda e pseudoenésima ordem foram ajustados aos dados experimentais em suas formas lineares e não-lineares. A sorção em meio homogêneo de petróleo foi bem ajustada com o modelo linear de pseudoprimeira ordem. A sorção de óleo vegetal foi bem ajustada tanto pelo modelo de pseudoprimeira ordem quanto pelo modelo de pseudossegunda ordem. Os modelos na forma não-linear indicaram um melhor ajuste dos dados experimentais pelo modelo de pseudoenésima ordem (n=0,95) para o petróleo e pelo modelo de pseudoprimeira ordem para o óleo vegetal. Os ajustes cinéticos mostraram que em meio heterogêneo a CSME se mantém constante em relação ao meio homogêneo, mas foi observada uma menor taxa de sorção. / Submitted by cmquadros@ucs.br (cmquadros@ucs.br) on 2018-02-01T18:30:09Z No. of bitstreams: 1 Dissertacao Pablo Beluck de Oliveira.pdf: 3113740 bytes, checksum: c1c0b51adf3c34f0f55f7579081223d8 (MD5) / Made available in DSpace on 2018-02-01T18:30:10Z (GMT). No. of bitstreams: 1 Dissertacao Pablo Beluck de Oliveira.pdf: 3113740 bytes, checksum: c1c0b51adf3c34f0f55f7579081223d8 (MD5) Previous issue date: 2018-02-01 / Ministério do Trabalho e Emprego, MTE. / Petroleum is a feedstock of great economic value. Due to the aim for non-renewable feedstocks substitution, vegetable oils have been used ever more as a feedstock for fuels and polymers. Spills during oil handling are serious environmental problems. Vegetable fibers have been used for a long time now as oil sorbents during spills. Wood residues as sawdust are currently used as oil sorbents, being a cheap and available resource. However, the hydrophilic profile of vegetable fibers reduce their capacity of oil sorption. Cellulose aerogels have become a product of great interest in the oil spill remediation field due to their high porosity (95 to 99%), low specific mass (0,004 to 0,15 g.cm-3) and high surface area (>60,m².g-1), besides cellulose abundance and sustainability. The objective of this work was to develop a hydrophobic aerogel from nanocellulose nanofibers obtained from furniture industry residues (Pinus elliottii var. elliottii) processed via steam explosion acid hydrolysis for petroleum and vegetable oil sorption. In the steam explosion process the best experimental condition was observed for a volumetric acetic acid and nitric acid ratio of 15:2:1 at 120ºC and 30 minutes with a cellulose yield higher than 90% and complete removal of hemicellulose and ligning. After lyophilization an aerogel of specific mass 0,046 0,0013 g.cm-3 and porosity 97,08 0,08% was obtained. Aerogel hydrophobization yielded a contact angle of 138,78º 0,78º. The aerogel exhibited a top experimental sorption capacity (CSME) of 19,55 0,10 goil.gaerogel-1 for petroleum and 13,73 0,62 goil.gaerogel-1 for vegetable oil. Cellulose nanofibers were produced by physical means (grinding) and hydrophobization was accomplished via vapor-phase deposition of organosilane (MTMS). In wood residue hydrolysis two acids were tested (nitric acid and acetic acid) simultaneously and individually, with variations of temperature, time and reagent amount. The solid fraction rich in cellulose was grinded in a rock mill for 5 hours at 2500 rpm in a 1,5% m/m suspension in water. The obtained gel was frozen for 48 hours at -20ºC for lyophilization at -40ºC for 50 hours. The aerogels obtained by lyophilization were treated with organosilane via vapor-phase deposition for 5 hours at 70ºC. The furniture industry residue was characterized as for its amounts of cellulose, hemicellulose, lignin, ashes, extractives and humidity. The process of steam explosion was characterized through the yields of individual components (cellulose and hemicellulose). Procedures like specific mass, contact angle, porosity, morphological characterization by scanning electron microscope with field emission gun, oil absorption tests and absorption kinetic in homogeneous and heterogeneous medium of petroleum and soy oil absorption were performed to characterize the aerogel. Kinetic models of pseudo-first, pseudo-second and pseudo-nth order were fitted to experimental data in their linear and non-linear forms. The absorption in homogeneous medium of petroleum was well fitted by pseudo-first linear kinetic model. Absorption of vegetable oil was well fitted by both pseudo-first and pseudo-second models. Models in non-linear form indicated a better fit for experimental data by the pseudo-nth order model (n=0,95) for petroleum and by pseudo-first order for vegetable oil. Kinetic adjusts showed that in heterogeneous medium CSME is maintained, but sorption rate is smaller.

abstract: Post-combustion carbon capture is a viable option for reducing CO2 greenhouse gas emissions, and one potentially promising technology for this route is adsorption using chemically and physically based sorbents. A number of exceptional CO2 sorbents materials have been prepared including metal organic frameworks, zeolites, and carbon based materials. One particular group of capable materials are amine based solid sorbents that has shown to possess high adsorption capacities and favorable adsorption kinetics. A key variable in the synthesis of an amine based sorbent is the support which acts as the platform for the amine modification. Aerogels, due to their high porosities and surface areas, appear to be a promising support for an amine modified CO2 sorbent. Therefore, in order to develop a commercially viable CO2 sorbent, particulate aerogels manufactured by Cabot Corporation through an economical and proprietary ambient drying process were modified with amines using a variety of functionalization methods. Two methods of physical impregnation of the amino polymer TEPA were performed in order to observe the performance as well as understand the effects of how the TEPA distribution is affected by the method of introduction. Both samples showed excellent adsorption capacities but poor cyclic stability for lack of any covalent attachment. Furthermore the method of TEPA impregnation seems to be independent on how the polymer will be distributed in the pore space of aerogel. The last two methods utilized involved covalently attaching amino silanes to the surface silanols of the aerogel. One method was performed in the liquid phase under anhydrous and hydrous conditions. The materials developed through the hydrous method have much greater adsorption capacities relative to the anhydrous sample as a result of the greater amine content present in the hydrous sample. Water is another source of silylation where additional silanes can attach and polymerize. These samples also possessed stable cyclic stability after 100 adsorption/regeneration cycles. The other method of grafting was performed in the gas phase through ALD. These samples possessed exceptionally high amine efficiencies and levels of N content without damaging the microstructure of the aerogel in contrast to the liquid phase grafted sorbents. / Dissertation/Thesis / Doctoral Dissertation Chemical Engineering 2014

O petróleo é uma matéria-prima de grande valor econômico. Buscando a substituição de matérias-primas não-renováveis, óleos vegetais vêm sendo usados cada vez mais como matéria-prima para combustíveis e polímeros. Derramamentos durante o manuseio de óleos são graves problemas ambientais. Fibras vegetais são usadas há muito tempo para a sorção de óleos em derramamentos. Resíduos de madeira na forma de serragem já são usados como sorventes de óleos, sendo um recurso barato e disponível. Entretanto, as características hidrofílicas das fibras vegetais reduzem sua capacidade de sorção de óleos. Os aerogéis de celulose tornaram-se um produto de grande interesse nessa área devido à sua alta porosidade (95 a 99%), baixa massa específica (0,004 to 0,15 g.cm-3) e alta área superficial (>60,m².g-1), além da abundância e sustentabilidade da celulose. O objetivo deste trabalho foi desenvolver um aerogel hidrofóbico de nanofibras de celulose a partir de resíduos da indústria moveleira (Pinus elliottii var. elliottii) processados por hidrólise ácida com explosão a vapor para a sorção de petróleo e óleos vegetais. No processo de explosão a vapor a melhor condição experimental foi observada para uma razão volumétrica de ácido acético e ácido nítrico 15:2:1 a 120°C e 30 minutos com rendimento superior a 90% em celulose e a remoção completa da hemicelulose e da lignina. Após a liofilização foi obtido um aerogel com massa específica 0,046 0,0013 g.cm-3 e porosidade 97,08 0,08%. A hidrofobização do aerogel gerou um ângulo de contato de 138,78º 0,78º. O aerogel mostrou capacidade de sorção máxima experimental (CSME) de 19,55 0,10 góleo.gaerogel-1 para petróleo e 13,73 0,62 góleo.gaerogel-1 para o óleo vegetal. A produção de nanofibras de celulose deu-se através de meios físicos (moagem) e a hidrofobização foi efetuada por modificação superficial das fibras com organosilanos (MTMS) por deposição a vapor. Na hidrólise do resíduo da indústria moveleira dois reagentes ácidos (ácido acético e ácido nítrico) foram testados individual e simultaneamente, com variações de temperatura, tempos e quantidade de reagente. A fração sólida rica em celulose obtida foi cominuída em moinho de pedras por 5 horas a 2500 rpm em uma suspensão com 1,5% m/m. O gel obtido foi congelado por 48 horas a -20ºC para posterior liofilização a -40ºC por 50 horas. Os aerogéis obtidos na liofilização foram tratados com o organosilano via deposição em fase vapor por 5 horas a 70ºC. O resíduo da indústria moveleira foi caracterizado quanto ao teor de celulose, hemicelulose, lignina, cinzas, extrativos e umidade. O processo de explosão a vapor foi caracterizado através do rendimento individual dos seus componentes (celulose e hemicelulose). Ensaios de massa específica aparente, ângulo de contato, porosidade, caracterização morfológica por microscopia eletrônica de varredura de emissão de campo, ensaios de sorção de óleos e cinética de sorção em meio homogêneo e heterogêneo de sorção de petróleo e óleo de soja foram realizados para caracterizar o aerogel. Modelos cinéticos de pseudoprimeira, pseudossegunda e pseudoenésima ordem foram ajustados aos dados experimentais em suas formas lineares e não-lineares. A sorção em meio homogêneo de petróleo foi bem ajustada com o modelo linear de pseudoprimeira ordem. A sorção de óleo vegetal foi bem ajustada tanto pelo modelo de pseudoprimeira ordem quanto pelo modelo de pseudossegunda ordem. Os modelos na forma não-linear indicaram um melhor ajuste dos dados experimentais pelo modelo de pseudoenésima ordem (n=0,95) para o petróleo e pelo modelo de pseudoprimeira ordem para o óleo vegetal. Os ajustes cinéticos mostraram que em meio heterogêneo a CSME se mantém constante em relação ao meio homogêneo, mas foi observada uma menor taxa de sorção. / Ministério do Trabalho e Emprego, MTE. / Petroleum is a feedstock of great economic value. Due to the aim for non-renewable feedstocks substitution, vegetable oils have been used ever more as a feedstock for fuels and polymers. Spills during oil handling are serious environmental problems. Vegetable fibers have been used for a long time now as oil sorbents during spills. Wood residues as sawdust are currently used as oil sorbents, being a cheap and available resource. However, the hydrophilic profile of vegetable fibers reduce their capacity of oil sorption. Cellulose aerogels have become a product of great interest in the oil spill remediation field due to their high porosity (95 to 99%), low specific mass (0,004 to 0,15 g.cm-3) and high surface area (>60,m².g-1), besides cellulose abundance and sustainability. The objective of this work was to develop a hydrophobic aerogel from nanocellulose nanofibers obtained from furniture industry residues (Pinus elliottii var. elliottii) processed via steam explosion acid hydrolysis for petroleum and vegetable oil sorption. In the steam explosion process the best experimental condition was observed for a volumetric acetic acid and nitric acid ratio of 15:2:1 at 120ºC and 30 minutes with a cellulose yield higher than 90% and complete removal of hemicellulose and ligning. After lyophilization an aerogel of specific mass 0,046 0,0013 g.cm-3 and porosity 97,08 0,08% was obtained. Aerogel hydrophobization yielded a contact angle of 138,78º 0,78º. The aerogel exhibited a top experimental sorption capacity (CSME) of 19,55 0,10 goil.gaerogel-1 for petroleum and 13,73 0,62 goil.gaerogel-1 for vegetable oil. Cellulose nanofibers were produced by physical means (grinding) and hydrophobization was accomplished via vapor-phase deposition of organosilane (MTMS). In wood residue hydrolysis two acids were tested (nitric acid and acetic acid) simultaneously and individually, with variations of temperature, time and reagent amount. The solid fraction rich in cellulose was grinded in a rock mill for 5 hours at 2500 rpm in a 1,5% m/m suspension in water. The obtained gel was frozen for 48 hours at -20ºC for lyophilization at -40ºC for 50 hours. The aerogels obtained by lyophilization were treated with organosilane via vapor-phase deposition for 5 hours at 70ºC. The furniture industry residue was characterized as for its amounts of cellulose, hemicellulose, lignin, ashes, extractives and humidity. The process of steam explosion was characterized through the yields of individual components (cellulose and hemicellulose). Procedures like specific mass, contact angle, porosity, morphological characterization by scanning electron microscope with field emission gun, oil absorption tests and absorption kinetic in homogeneous and heterogeneous medium of petroleum and soy oil absorption were performed to characterize the aerogel. Kinetic models of pseudo-first, pseudo-second and pseudo-nth order were fitted to experimental data in their linear and non-linear forms. The absorption in homogeneous medium of petroleum was well fitted by pseudo-first linear kinetic model. Absorption of vegetable oil was well fitted by both pseudo-first and pseudo-second models. Models in non-linear form indicated a better fit for experimental data by the pseudo-nth order model (n=0,95) for petroleum and by pseudo-first order for vegetable oil. Kinetic adjusts showed that in heterogeneous medium CSME is maintained, but sorption rate is smaller.

Doctor of Philosophy / Department of Chemistry / Kenneth J. Klabunde / A new approach to synthesize nanosized strontium titanate (SrTiO3) and barium titanate (BaTiO3) has been developed. Nanocrystals of mixed metal oxide were synthesized by a modified aerogel procedure from alkoxides. The textural and surface characteristic properties were studied by nitrogen BET analysis, transmission electron microscopy, and powder XRD. The crystallite sizes of aerogel prepared powders can vary from 6 to 25 nm by the use of different solvents. A mixture of ethanol and toluene was found to be the best binary solvent for supercritical drying, which produced a SrTiO3 sample with a surface area of 159 m2/g and an average crystallite size of 8 nm, and a BaTiO3 sample with a surface area of 175 m2/g and an average crystallite size of 6 nm. These titanates have been studied for photocatalytic oxidation of volatile organic compounds and acetaldehyde (CH3CHO) in particular. The big band gaps of the bulk (3.2 eV for SrTiO3 and 3.1 eV for BaTiO3) limit their application to a UV light region only. The modification of titanates by doping with transition metal ions (partial substitution of Ti ions with metal ions) creates a valence band or electron donor level inside of the band gap, narrows it, and increases the visible light absorption. The enhanced adsorption of visible light was achieved by the synthesis of nanosized SrTiO3 and BaTiO3 by incorporating Cr ions during the modified aerogel procedure. Gaseous acetaldehyde photooxidation has been studied on pure SrTiO3 and BaTiO3, and on chromium doped Cr-SrTiO3 and Cr-BaTiO3 under UV and visible light irradiation, and compared with the photoactivity of P25 TiO2. SrTiO3 doped with antimony/chromium shows absorption in visible light and show photocatalytic activity for CH3CHO oxidation. The reason for the codoping of SrTiO3 with Sb/Cr was to maintain the charge balance and to suppress oxygen defects in the lattice. This photocatalyst shows high photoactivity under visible light irradiation even after several continuous runs. The photoactivity under visible and UV light irradiation was almost identical for the Sb/Cr-SrTiO3 photocatalyst. Dielectric properties of aerogel prepared barium titanate samples have being studied and the bulk resistance values of AP-BaTiO3 were significantly lower than that of commercial BaTiO3, by several orders of magnitude.

Amelioration of the building blocks is a plausible approach to graft aerogels with distinguished properties while preserving the aerogel superiority. However, the incorporation of designated properties into metallic aerogels, especially catalytically beneficial morphologies and transition metal doping, still remains a challenge. Here, we report on the first case of an aerogel electrocatalyst composed entirely of alloyed PdNi hollow nanospheres (HNSs) with controllable chemical composition and shell thickness. The synergy of the transition metal doping, combined with the hollow building blocks and the three dimensional network structure make the PdNi HNS aerogels promising electrocatalysts towards ethanol oxidation, among which the Pd83Ni17 HNS aerogel shows a 5.6-fold enhanced mass activity compared to commercial Pd/C. This work expands the exploitation approach of electrocatalytic properties of aerogels into morphology and composition control of its building blocks.