The synthesis, characterization and application of dendrimers on solid supports are described. Melamine-based dendrimers are incorporated on clay minerals and silica gel. The hybrid materials are characterized using a variety of analytical techniques including thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and mass spectrometry (MS). The first chapter gives an overview of the two main methods, convergent and divergent, for the synthesis of dendrimers. It also describes the synthesis of melamine-based dendrimers and their advantages over conventional dendrimers. Synthetic strategies and applications of dendrimers at surfaces are discussed. The preparation of organoclay materials containing dendritic surfactants is presented in the second chapter. The morphology of these organoclays is studied by X-ray powder diffraction (XPD). A new type of morphology is observed when large dendritic surfactants are incorporated onto the clay. This new morphology is described as frustrated intercalation. The ability of the dendritic organoclay composites to recognize small organic molecules in water is presented in the third chapter. Atrazine, a commonly used herbicide, is used as a model compound. Structure-activity relationship studies were conducted in order to gain some insight on the recognition and sequestration mechanisms. In the fourth chapter, reactive resins are evaluated for the covalent sequestration of monochlorotriazines from organic and aqueous solutions. The sequestration is monitored spectrophotometrically and using liquid chromatography coupled to a mass spectrometer (LC-MS). 1H NMR spectroscopy and MS are used to identify the covalent adducts formed between the monochlorotriazines and the resins. The efficiency of the resin is compared to several types of charcoal using aqueous solutions of atrazine. The final chapter describes the attachment of melamine-based dendrimers onto silica gels. Dendrimers are incorporated to the silica gel surface using two synthetic strategies, the stepwise growth strategy (SGS) and the "attach-to" strategy (ATS). These composites are also evaluated for their ability to remove atrazine from aqueous solutions.

In this thesis, firstly, the equilibrium adsorption capacity of water on a natural zeolite at several zeolite temperatures and water vapor pressures has been experimentally determined for adsorption and desorption processes. Additionally, the modified Dubinin-Astakhov adsorption equilibrium model has been fitted to experimental data and separate correlations are obtained for adsorption and desorption processes as well as a single correlation to model both processes. Experimental results show that the maximum adsorption capacity of natural zeolite is nearly 0.12 kgw/kgad for zeolite temperatures and water vapor pressures in the range 40-150 C and 0.87-7.38 kPa. Secondly, a thermally driven adsorption cooling prototype using natural zeolite-water as working pair has been built and its performance investigated experimentally at various evaporator temperatures. Under the experimental conditions of 45 C adsorption, 150 C desorption, 30 C condenser and 22:5 C, 15 C and 10 C evaporator temperatures, the COP of the adsorption cooling unit is approximately 0.25 and the maximum average volumetric specific cooling power density (SCPv) and mass specific cooling power density (SCP) of the cooling unit are 5.2 kWm-3 and 7 Wkg-1, respectively. Thirdly, in order to investigate the dynamic heat and mass transfer behavior of the adsorbent bed of an adsorption cooling unit, a transient local thermal non equilibrium model that accounts for both internal and external mass transfer resistances has been developed using the local volume averaging method. Finally, the influence of several design parameters on the transient distributions of temperature, pressure and amount adsorbed inside the cylindrical adsorbent bed of an adsorption cooling unit using silica-gel/water have been numerically investigated for the one and two dimensional computational domains. Moreover, validity of the thermal equilibrium model assumption has been shown under the given boundary and design conditions. Generally, for the conditions investigated, the validity of the local thermal equilibrium and spatially isobaric bed assumptions have been confirmed. To improve the performance of the bed considered, eorts should be focused on reducing heat transfer resistances and intra-particle mass transfer resistances but not inter-particle mass transfer resistances.

The synthesis, characterization and application of dendrimers on solid supports are described. Melamine-based dendrimers are incorporated on clay minerals and silica gel. The hybrid materials are characterized using a variety of analytical techniques including thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and mass spectrometry (MS). The first chapter gives an overview of the two main methods, convergent and divergent, for the synthesis of dendrimers. It also describes the synthesis of melamine-based dendrimers and their advantages over conventional dendrimers. Synthetic strategies and applications of dendrimers at surfaces are discussed. The preparation of organoclay materials containing dendritic surfactants is presented in the second chapter. The morphology of these organoclays is studied by X-ray powder diffraction (XPD). A new type of morphology is observed when large dendritic surfactants are incorporated onto the clay. This new morphology is described as frustrated intercalation. The ability of the dendritic organoclay composites to recognize small organic molecules in water is presented in the third chapter. Atrazine, a commonly used herbicide, is used as a model compound. Structure-activity relationship studies were conducted in order to gain some insight on the recognition and sequestration mechanisms. In the fourth chapter, reactive resins are evaluated for the covalent sequestration of monochlorotriazines from organic and aqueous solutions. The sequestration is monitored spectrophotometrically and using liquid chromatography coupled to a mass spectrometer (LC-MS). 1H NMR spectroscopy and MS are used to identify the covalent adducts formed between the monochlorotriazines and the resins. The efficiency of the resin is compared to several types of charcoal using aqueous solutions of atrazine. The final chapter describes the attachment of melamine-based dendrimers onto silica gels. Dendrimers are incorporated to the silica gel surface using two synthetic strategies, the stepwise growth strategy (SGS) and the "attach-to" strategy (ATS). These composites are also evaluated for their ability to remove atrazine from aqueous solutions.

Air-to-air energy recovery wheels are now widely used in industry and buildings; however, the effectiveness of water vapor exchange in these regenerative wheels appears to be much lower than may be economically feasible. The purpose of this research is to investigate the feasibility of using agglomerated desiccant particle coatings to improve the performance of regenerative wheels used in HVAC air-to-air heat and moisture exchange and energy recovery applications. Desiccant particles coated on wheels lose most of their water vapor sorption capacity due to the method of coating. Desiccant agglomerates can be made by mixing starch, fine silica gel particulate, and water within an agglomerating device. The desiccant particle agglomerating process improves the desiccant mass transfer properties by increasing the overall surface area of desiccant particles; and also by creating a much rougher surface that can increase the likelihood of turbulent flow, and therefore, increasing the overall mass transfer rates. The industrial desiccant coating process involves submerging the desiccant into a coating agent and then applying this mix to the substrate or the matrix of the energy wheel. This process was improved in this research by ensuring the particles are applied after the coating agent is applied to ensure that the agglomerates or desiccant particles are not submerged by the coating material. Because testing energy wheels under steady state operating conditions has proved to be difficult, time consuming and costly in the past, a small parallel flow test cell is used to measure the transient response of coated substrate aluminum sheets after a step change in the inlet air humidity or temperature. Using a previously developed theoretical model, the time constants for these inlet step change responses are then used to predict the sensible and latent effectiveness of a regenerative energy wheel coated with the same agglomerated particles, which is rotated at a known operating speed and wheel face velocity. When the new desiccant coatings are used, it is shown that the latent heat effectiveness for a typical wheel could be up to 85%. It is found that the steady state air flow pressure drop readings for the test cell shows that agglomerated particles coated on the surfaces within the test cell implies some transitional turbulent flow behavior compared to similar substrate surfaces coated in a conventional manner with desiccant particles (e.g. up to 60% higher pressure drop at a channel Reynolds number of 300) in the same test cell. This implied enhanced turbulence flow friction factor in the test cell suggests a somewhat similar enhancement for increased mass and heat transfer coefficients for the test cell or coated wheel matrices. The transient results for humidity step changes for air flow through the test cell reveals that the adsorption and desorption response time constants are much larger for the agglomerated coated substrate surfaces than the conventional industrial coated surfaces. These data imply much higher moisture or latent heat effectiveness values for wheels coated with agglomerated particles. When the new desiccant coatings are used, it is shown that the latent heat effectiveness for a typical wheel could be better than 80% or 20% higher than currently available typical energy wheels. With improvements to the desiccant particle agglomerating process, desiccant coating process and particle coating and testing methods, this thesis shows that significant improvements may be practical for the design, testing and operation of regenerative heat and moisture exchange wheels.

Thesis (M.S.) -- Mississippi State University. Department of Physics and Astronomy. / Title from title screen. Includes bibliographical references.

Orientador: Dimas Roberto Vollet / Banca: Antonio Tallarico Vicente Adorno / Banca: Fábio Simões de Vicente / Resumo: O presente trabalho estuda as características estruturais de géis de sílica preparados a partir da sonohidrólise do Tetraetilortosilicato (TEOS) em função de diferentes quantidades de álcool isopropílico (IPA), denominado conjunto de amostras A, e em função de diferentes quantidades de dimetilformamida (DMF), denominado conjunto de amostras B. Os géis são estudados desde o estágio saturado (gel úmido) até o estágio do gel seco (aerogel e xerogel) resultante da secagem a pressão ambiente. As caracterizações estruturais das amostras são realizadas através das técnicas de Termogravimetria (TG), densidade aparente, análise de distribuição de tamanho de poros e área superficial por adsorção de nitrogênio, e espalhamento de raios X a baixo ângulo (SAXS). A sonohidrólise foi realizada a partir de volumes constantes das misturas reagentes, mantendo-se a mesma razão molar água/TEOS para as diferentes adições de IPA do conjunto A e também a mesma razão molar água/TEOS para as diferentes adições de DMF do conjunto B. Géis úmidos produzidos a partir da estimulação ultrassônica do TEOS com aumento da quantidade de IPA (conjunto A) exibem uma estrutura de fractal de massa com dimensão fractal D em torno de 2,0 e com tamanho característico  do fractal de massa crescendo de 4,1 nm para 5,1 nm, quando a razão molar [IPA]/[TEOS] cresce de 0 para 10,8. Os géis do conjunto B exibem uma estrutura fractal de massa com dimensão fractal D em torno de 2,2 e com  decrescendo de 9,2 nm para 7,8 nm quando a razão molar R = [DMF]/[TEOS] cresce de 0 para 4. Aerogéis foram obtidos após lavagem dos géis úmidos de ambos os conjuntos com IPA, para remoção de resíduos provenientes da sonohidrólise, e depois imersos em solução de trimetilclorosilano (TMCS) em álcool isopropílico, para modificação... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The present work studies the structural characteristics of silica gels prepared from the sonohydrolysis of tetraetoxisilane (TEOS) as a function of different amounts of isopropyl alcohol (IPA), which will be called the set of samples A, and for different amounts of dimethylformamide (DMF) , which will be called set of samples B. The gels are studied from the saturated stage (wet gel) until the stage of dry gel (xerogel and aerogel) that results from a drying process at ambient pressure. The samples are characterized by Termogravimetry (TG), apparent density, surface area and pores size distribution by nitrogen adsorption, and small-angle X-ray scattering (SAXS). The sonohydrolysis was carried out from reagent mixtures with constant volumes, keeping the same water/TEOS molar ratio for different additions of IPA in the set A and also the same water/TEOS molar ratio for different additions of DMF in the set B. Wet gels produced from the ultrasonic stimulation of TEOS with increasing the quantity of IPA (set A) exhibit a structure of fractal mass with fractal dimension D around 2.0 and with characteristic size  growing from 4.1 nm to 5.1 nm, when the [IPA]/[TEOS] molar ratio increases from 0 to 10,8. The gels of the set B exhibit a structure of fractal mass with fractal dimension D around 2.2 and with  decreasing from 9.2 nm to 7.8 nm when increasing the molar ratio R =[DMF]/[TEOS] from 0 to 4. Aerogels were obtained after washing the wet gels from both sets with IPA, to remove wastes from the sonohydrolysis, and then immersing them in a solution of trimethylchlorosilane (TMCS) in isopropyl alcohol, for the silica surface modification (silylation), and finally in pure isopropyl alcohol. The drying process narrows the range of characteristic lengths  of the original structure of fractal mass of the wet gels, however, it does not change... (Complete abstract click electronic access below) / Mestre

Resumo: Sílica contendo crômio faz parte de uma classe importante de materiais devido às aplicações como catalisador de polimerização e de oxidação, fibras ópticas, laseres e preparação de pigmentos. Este trabalho está dividido em duas partes. A primeira refere-se ao gel úmido e seco de sílica contendo crômio. Os géis foram preparados fazendo-se a mistura das soluções de silicato de sódio solúvel (vidrolíquido) e de soluções aquosas de nitrato de crômio em pH 4 ou 9 previamente ajustado, ou em 4 após a mistura das soluções. O gel foi caracterizado por espectroscopia eletrônica de absorção no ultravioleta -visível e por microscopia eletrônica de transmissão. A morfologia dos géis de sílica e de sílica contendo crômio é dependente do valor de pH e da ordem de mistura dos reagentes. Este efeito é atribuído às espécies poliméricas do crômio diferenciadas presentes na solução que controlam a forma da partícula. Partículas esféricas podem ser obtidas pelo colapso de microgel com alto grau de ligação cruzada. A outra parte do trabalho consiste na preparação de sílica contendo crômio por dois métodos: aquecimento convencional e banho de ultra-som nas temperaturas de 50 e 80oC. O gel obtido foi tratado por extrações com soluções ácidas, extrações com água e diálise, e seco em forno de microondas. As amostras de sílica/crômio em pó foram submetidas ao tratamento térmico em temperaturas de 200 a 1400oC, com intervalos de 200oC, sob atmosfera...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Chromium-containing silica belongs to an important class of materials having technological applications such as polymerization and oxidation catalyses, lasers, pigments and optical fibers. The chromium-containing silica and pure silica gels were obtained by mixing solutions of soluble sodium silicate (water glass) and chromium nitrate with adjusted pH 4 or 9 previously. Other method to prepare the gels was carried out by mixing water glass and chromium nitrate solutions and then the pH 4. The gel was characterized by ultraviolet-visible spectroscopy and transmission electron microscopic. The gel morphology is dependent on the pH value and the order of mixture of reagents. This effect is due to the nature of polymeric shape of chromium species in solution. Spherical particles can be obtained from microgel collapsing with high degree of cross linking . The second part of this work deals with powders obtained from gels. The chromium-containing silica and silica powders were obtained from gel by two methods: i) conventional heating at temperatures of 80 and 50oC and ii) sonication and heating at 80 and 50oC. The resultant colloidal silica was treated by continuous extraction acid solution in followed by extraction in distilled water and then dialyzed against distilled water and dried in microwave oven. The samples were...(Complete abstract, click electronic access below) / Orientador: Marian Rosaly Davolos / Coorientador: Miguel Jafelicci Junior / Doutor

Tese (Doutorado) - Universidade Federal de Santa Catarina, Centro de Ciencias Fisicas e Matematicas / Made available in DSpace on 2012-10-17T00:08:25Z (GMT). No. of bitstreams: 0Bitstream added on 2016-01-08T21:52:01Z : No. of bitstreams: 1 148751.pdf: 3035857 bytes, checksum: 0113421a94fb1a46611db530535045ac (MD5) / O presente trabalho descreve a síntese de Cristais Líquidos não lineares, bem como as propriedades mesomórficas de séries homologas. Neste trabalho são informadas a síntese de moléculas contendo uma unidade de conexão central: enona a,b-insaturada, isoxazol 3,5-dissubstituídos e b-dicetonas. Os compostos sintetizados contendo a unidade de conexão central enona a,binsaturada, não apresentam a formação de mesofase. O comportamento é atribuído a existência de misturas de confôrmeros estruturais que desestabilizam a formação de mesofase. Os compostos sintetizados contendo a unidade de conexão central isoxazol 3,5dissubstituídos apresentam a formação de mesofases. Várias modificações a fim de minimizar o efeito do desvio da linearidade introduzidas pela conexão central, são apresentadas. Mesofases nemáticas e esméticas com maior faixa de estabilidade foram obtidas. Os compostos sintetizados contendo unidade central b-dicetonas não apresentam a formação de mesofase. O comportamento é atribuído ao grande número de possíveis ligação de hidrogênio intra e intermolecular. A estrutura do 1-(4-heptiloxifenii)-3carboxipropano-l,3-diona determinada por cristalografia de raios-X é apresentada. A natureza essencialmente coplanar do sistema é observada. Em todos os compostos a relação estrutura molecular e propriedade mesogênica são discutidas. Todos os compostos foram caracterizados por técnicas espectroscópicas e análise elementar.

Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro de Ciências Físicas e Matemáticas. Programa de Pós-graduação em Química. / Made available in DSpace on 2012-10-21T02:58:10Z (GMT). No. of bitstreams: 1 208827.pdf: 881087 bytes, checksum: 00ccc6b96173b4517e67fda31bb79d98 (MD5) / Este trabalho descreve o desenvolvimento de um sistema de pré-concentração em fluxo das espécies Cr (III) e Cr (VI), presentes em amostras de água, e detecção por espectrometria de absorção atômica em chama. O sistema é baseado na retenção de espécies catiônicas de Cr (III) e retenção de espécies aniônicas de Cr (VI) em mini-colunas preenchidas com sílica-gel modificada com fosfato de zircônio e sílica-gel zirconizada, respectivamente. Variáveis químicas e de fluxo foram otimizadas pelo método univariado. Os dados experimentais revelaram a importância da carga superficial dos sorventes e o pH do meio em relação à eficiência de adsorção. A faixa ótima de pH da amostra para Cr (III) foi de 4 a 9, e para Cr (VI) foi selecionado o pH 3. Para os dois sorventes em estudo a fração de 400 mL de eluato foi coletada após o descarte dos 100 mL iniciais. A eluição foi realizada simultaneamente e os eluatos coletados separadamente em pequenos frascos. A injeção discreta de 100 mL foi suficiente para que o sinal máximo fosse atingido. Os resultados das condições otimizadas, selecionados com o compromisso entre a sensibilidade e a velocidade analítica, foram vazão da amostra 4,0 mL min-1; vazão do eluente 0,53 mL min-1; concentração do eluente 0,1 mol L-1 de tris-(hidroximetil)aminometano (CrVI) e 0,1 mol L-1 de HNO3 (CrIII). A investigação do volume de amostra, para uma massa de analito constante, demonstrou que com o aumento do volume o sinal diminui. O volume máximo de 150 mL foi obtido para Cr(III) e de 200 mL para Cr(VI). O desvio padrão relativo (n=3) foi de 3,0% e 2,1% para Cr (III) e Cr (VI), respectivamente. O limite de detecção foi de 1,9 mg L-1 para Cr (III) e 2,3 mg L-1 para Cr (VI). A faixa linear de trabalho foi 25 a 350 mg L-1 para ambos metais. Para validar a metodologia proposta foi aplicada, nas amostras reais e amostras enriquecidas, a metodologia padrão descrita na literatura. O estudo efetuado demonstrou a viabilidade do uso dos sorventes sílica gel zirconizada e sílica gel modificada com fosfato de zircônio posicionados em série para a separação e a pré-concentração de espécies de cromo

Made available in DSpace on 2016-02-05T18:29:51Z (GMT). No. of bitstreams: 0 Previous issue date: 2015-05-22. Added 1 bitstream(s) on 2016-02-05T18:33:52Z : No. of bitstreams: 1 000856758_20170610.pdf: 92355 bytes, checksum: d68984beb418835cabad355cb1c998f2 (MD5) Bitstreams deleted on 2017-06-19T16:12:32Z: 000856758_20170610.pdf,. Added 1 bitstream(s) on 2017-06-19T16:13:17Z : No. of bitstreams: 1 000856758.pdf: 715358 bytes, checksum: c8ed7fae87732dccc9b310dd9be9df16 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Materiais híbridos de Sílica/Orgânico também conhecidos como Silicatos Modificados Organicamente (ORMOSIL) são muito estudados devido à variedade de alcóxidos de silício funcionalizados com moléculas orgânicas ligadas covalentemente ao silício (epóxi, vinil, amina, fenil, etc). Neste trabalho foram investigadas as propriedades elétricas de materiais híbridos de Sílica/orgânico à base de GPTS (3-glicidoxipropiltrimetoxisilano) e TEOS (tertraetilortosilicato), preparadas pelo processo sol-gel, a partir da hidrólise ácida. Os Materiais híbridos de Sílica/orgânico foram preparados por deposição do sol de GPTS/TEOS por dip-coating, em substratos de vidro. Eletrodos de ouro foram depositados paralelamente às faces da amostra para a realização de medidas de espectroscopia de impedância. O estudo foi realizado em amostras com diferentes composições de GPTS/TEOS e diferentes temperaturas de tratamentos térmicos de densificação, destas amostras em diferentes composições, foram realizadas medidas em diferentes temperaturas. Foi determinado que a condutividade aumenta com a concentração de GPTS na matriz híbrida, os valores foram de 8,04.10-9 S/cm e 8,74.10-10 S/cm, para os filmes GT(7:1) e GT(1:1), respectivamente. O mecanismo de transporte envolve íons H+ que transferem carga protônica ao oxigênio do epóxi proveniente do GPTS, esse mecanismo de transporte é descrito pelo mecanismo de Grotthuss. A energia de ativação diminuiu com a aumento da razão de GPTS, sendo 0,54 eV e 0,83 eV, para os filmes GT(7:1) e GT(3:1), respectivamente. Portanto, a concentração de GPTS, favorece a mobilidade de portadores na matriz, sendo também que o número de portadores de carga presentes na solução catalisadora aumenta proporcionalmente com a razão molar de GPTS. A temperatura de tratamento térmico de densificação favorece o processo de mobilidade dos portadores devido a eliminação de poros da matriz, aumentando a... / Organic/silica hybrid materials also known as Organically Modified Silicates (ORMOSIL) have been object of study due to the diversity of organically functionalized silicon alcoxides with organic groups covalently bonded to the silicon (epoxy, vinyl, amino, phenyl, etc). This work aims the study of the electrical properties of the organic/silica hybrid materials prepared by sol-gel technique derived from the acid hydrolysis of 3- glycidoxypropyltrimethoxysilane (GPTS) and tetraethylorthosilicate (TEOS). Organic/silica hybrid films were deposited on glass substrates by dip-coating technique and sandwiched between gold electrodes to allow the impedance spectroscopy measurements. The study was carried out on film samples with different GPTS/TEOS molar ratio and films submitted to different thermal treatments for densification. Also impedance spectroscopy measurements were performed at different temperatures for samples with different GPTS/TEOS molar ratio. It was determined regarding the increase of the GPTS concentration in the hybrid matrix that the conductivity increases from 8.74x10- 10 S/cm to 8.04x10-9 S/cm for films GT(1:1) and GT(7:1), respectively. The transport mechanism involves H+ ions transfer protonic charge to the oxygen of epoxy groups, and this transport mechanism is described by Grotthuss model. The activation energy decreases with the increase of the increase of the GPTS concentration, being 0.83 eV and 0.54 eV and for the GT (3: 1) and GT (7: 1), respectively. Therefore, the concentration of GPTS, promotes the mobility of carriers in the matrix, and also the number of charge carriers present in the catalyst solution increases proportionately with the increase in the molar ratio of GPTS. The thermal treatment for densification promotes elimination of pores in the hybrid matrix favoring the mobility of charge carriers increasing the conductivity of the hybrid material. Key-words: sol-gel; organic/silica hybrid; electrical ...