221 |
Light Scattering in Complex Mesoscale Systems: Modelling Optical Trapping and MicromachinesVincent Loke Unknown Date (has links)
Optical tweezers using highly focussed laser beams can be used to exert forces and torques and thus drive micromachines. This opens up a new field of microengineering, whose potential has yet to be fully realized. Until now, methods that have been used for modelling optical tweezers are limited to scatterers that are homogeneous or that have simple geometry. To aid in designing more general micromachines, I developed and implemented two main methods for modelling the micromachines that we use. These methods can be used for further proposed structures to be fabricated. The first is a FDFD/T-matrix hybrid method that incorporates the finite difference frequency domain (FDFD) method, which is used for inhomogeneous and anisotropic media, with vector spherical wave functions (VSWF) to formulate the T-matrix. The T-matrix is then used to calculate the torque of the trapped vaterite sphere, which is apparently composed of birefringent unit crystals but the bulk structure appears to be arranged in a sheaf-of-wheat fashion. The second method is formulating the T-matrix via discrete dipole approximation (DDA) of complex arbitrarily shaped mesoscale objects and implementing symmetry optimizations to allow calculations to be performed on high-end desktop PCs that are otherwise impractical due to memory requirements and calculation time. This method was applied to modelling microrotors. The T-matrix represents the scattering properties of an object for a given wavelength. Once it is calculated, subsequent calculations with different illumination conditions can be performed rapidly. This thesis also deals with studies of other light scattering phenomena including the modelling of scattered fields from protein molecules subsequently used to model FRET resonance, determining the limits of trappability, interferometric Brownian motion and the comparison between integral transforms by direct numerical integration and overdetermined point-matching.
|
222 |
Light Scattering in Complex Mesoscale Systems: Modelling Optical Trapping and MicromachinesVincent Loke Unknown Date (has links)
Optical tweezers using highly focussed laser beams can be used to exert forces and torques and thus drive micromachines. This opens up a new field of microengineering, whose potential has yet to be fully realized. Until now, methods that have been used for modelling optical tweezers are limited to scatterers that are homogeneous or that have simple geometry. To aid in designing more general micromachines, I developed and implemented two main methods for modelling the micromachines that we use. These methods can be used for further proposed structures to be fabricated. The first is a FDFD/T-matrix hybrid method that incorporates the finite difference frequency domain (FDFD) method, which is used for inhomogeneous and anisotropic media, with vector spherical wave functions (VSWF) to formulate the T-matrix. The T-matrix is then used to calculate the torque of the trapped vaterite sphere, which is apparently composed of birefringent unit crystals but the bulk structure appears to be arranged in a sheaf-of-wheat fashion. The second method is formulating the T-matrix via discrete dipole approximation (DDA) of complex arbitrarily shaped mesoscale objects and implementing symmetry optimizations to allow calculations to be performed on high-end desktop PCs that are otherwise impractical due to memory requirements and calculation time. This method was applied to modelling microrotors. The T-matrix represents the scattering properties of an object for a given wavelength. Once it is calculated, subsequent calculations with different illumination conditions can be performed rapidly. This thesis also deals with studies of other light scattering phenomena including the modelling of scattered fields from protein molecules subsequently used to model FRET resonance, determining the limits of trappability, interferometric Brownian motion and the comparison between integral transforms by direct numerical integration and overdetermined point-matching.
|
223 |
New Insights into the Mechanisms of Crystallisation and Vitrification - a Dynamic Light Scattering Study of Colloidal Hard SpheresMartinez, Vincent Arnaud, vincent.martinez@student.rmit.edu.au January 2009 (has links)
This thesis reports on a comprehensive experimental study of the collective dynamics of colloidal hard sphere suspensions. The main quantity measured is the coherent Intermediate Scattering Function (ISF) using a range of techniques based on Dynamic Light Scattering (DLS). The collective dynamics are measured as a function of scattering vector for volume fractions spanning from dilute samples, through the fluid phase and the metastable region, up until deep in the glass region. This work describes two major explorations: (i) the effect of volume of fraction on the q-dependency of the collective dynamics; and (ii) a study of the ageing processes in colloidal glasses. The present work is unique in the application of several advanced experimental techniques, and in the level of averaging that has been carried out, enabling a more sophisticated analysis than has previously been possible. This includes the characterization of non-Fickian processes and the determinatio n of the current-current correlation function (CCCF) in the metastable fluid, and the quantitative characterization of the ageing process in the hard sphere glass. In addition, by combining aspects of the coherent and incoherent ISFs, this work also allows the expression of the collective dynamics in terms of the single particle displacement. The results show a dynamical change at the freezing point (f), which exposes the incapacity of the system to dissipate thermal energy via diffusing momentum currents, i.e. viscous flow. The structural impediments responsible for this, associated with dynamical heterogeneities, begin at the structure factor peak, and spread to other spatial modes as the volume fraction increases. Above the glass transition (g), structural relaxation becomes arrested at all spatial modes probed, i.e. flow is arrested. It is found that, following the quench, samples above the glass volume fraction approach some final
|
224 |
Intensity auto- and cross-correlations and other properties of a 85Rb atom coupled to a driven, damped two-mode optical cavityHemphill, Patrick A. January 2009 (has links)
Thesis (M.S.)--Miami University, Dept. of Physics, 2009. / Title from first page of PDF document. Includes bibliographical references (p. Xx-Xx).
|
225 |
Dynamic failure precursors in soft matter / Précurseurs dynamiques de la défaillance dans la matière molleAime, Stefano 14 September 2017 (has links)
La fracture des matériaux, omniprésente aussi bien en science des matériaux qu’en géologie, implique souvent des événements soudains et imprévisibles, sans précurseurs détectables macroscopiquement. Une compréhension approfondie des mécanismes microscopiques conduisant in fine à la rupture est requise, mais les expériences restent rares. La détection de la dynamique microscopique dans les échantillons cisaillés est expérimentalement très difficile, car elle nécessite de combiner sensibilité mécanique, qualité optique et exigences strictes sur l’encombrement. Dans ce travail, nous présentons l'une des premières tentatives réussies de mesure des précurseurs microscopiques de fracture dans des matériaux mous modèles, grâce à des mesures de la plasticité microscopique à l'aide d'un nouvel instrument, couplant une cellule de cisaillement à contrainte contrôlée à un appareil de diffusion de lumière statique et dynamique (DLS) à petits angles. Dans un premier temps, nous montrons théoriquement, numériquement et expérimentalement comment la DLS, une technique très puissante difficile à utiliser pour un échantillon sous cisaillement, peut être utilisée comme outil de mesure de la dynamique microscopique dans les systèmes mous sous cisaillement. Pour un solide parfait et un fluide visqueux simple, le champ de déplacement résultant d'une déformation de cisaillement est purement affine. Nous montrons comment les déplacements affines et non affines, qui sont présents dans de nombreuses situations d’intérêt (matériaux élastiquement hétérogènes ou en raison de réarrangements plastiques) peuvent être évalués séparément par DLS et discutons de l'effet des non-idéalités dans des expériences typiques.Ce travail est centré sur un gel colloïdal fractal modèle, dont nous caractérisons la rhéologie linéaire en loi de puissance. Nous montrons que celle-ci est décrite par un modèle phénoménologique Fractional Maxwell (FMM), et discutons la relation possible entre FMM et la structure microscopique du gel.Sous une contrainte de cisaillement constante (expérience de fluage), le gel colloïdal présente une déformation rapide élastique suivie d'un fluage lent en loi de puissance, puis, après plusieurs heures par une accélération du taux de cisaillement, entraînant la rupture retardée du gel. Nos expériences montrent que le premier régime en loi de puissance, bien décrit par la viscoélasticité linéaire, correspond à l'échelle microscopique à une dynamique partiellement nonaffine, mais entièrement réversible. Lorsque la viscoélasticité dévie de la linéarité, une accélération nette, localisée dans le temps de la dynamique non-affine, est observée. Ces réarrangements rapides précèdent la fracture macroscopique du gel de plusieurs heures: ce sont des précurseurs dynamiques de la fracture qui permettent de prédire l’évolution du gel bien avant toute mesure rhéologique.Pour obtenir une image plus complète de la fracture, nous étudions l'apparition de l'irréversibilité lors d’une perturbation cyclique répétée plusieurs fois (expérience de fatigue). En suivant l'évolution stroboscopique du système en fonction de la déformation cumulée, on constate que, au-delà du régime linéaire, le taux de relaxation augmente brusquement, signature de plasticité. Si la contrainte appliquée est suffisamment grande, le gel à long terme montre une rupture retardée, en analogie avec celle observée en fluage. Les différences et similitudes entre les deux mécanismes de fracture sont discutées.Enfin, la généralité des résultats obtenus sur les gels colloïdaux est vérifiée en étudiant comme second système modèle un verre colloïdal, dont la mise en écoulement sous contrainte oscillante est un processus progressif, pour lequel deux modes de relaxation contribuent à la dynamique observée. Les analogies qualitatives trouvées avec des systèmes similaires (par ex. des émulsions concentrées) suggèrent qu'une image unifiée pourrait être obtenue, motivant des recherches futures. / Material failure is ubiquitous, with implications from geology to everyday life and material science. It often involves sudden, unpredictable events, with little or no macroscopically detectable precursors. A deeper understanding of the microscopic mechanisms eventually leading to failure is clearly required, but experiments remain scarce. The detection of microscopic dynamics in samples under shear is experimentally very challenging, because it requires to combine the highest mechanical sensitivity to strict requirements on the geometry of the whole setup and on the quality of the optical interfaces. In this work we present one of the first successful attempts to measure microscopic failure precursors in model soft solids. Here, microscopic plasticity under shear is observed using a novel setup, coupling a custom-made stress controlled shear cell to small angle static and dynamic light scattering (DLS).DLS is a very powerful technique, but its application to materials under shear is not trivial. In a first step we show a theoretical, numerical and experimental investigation of how DLS may be used as a tool to measure the microscopic dynamics in soft systems under shear. In ideal solids and simple viscous fluids, the displacement field resulting from an applied shear deformation is purely affine. Additional non-affine displacements arise in many situations of great interest, for example in elastically heterogeneous materials or due to plastic rearrangements. We show how affine and non-affine displacements can be separately resolved by DLS, and discuss the effect of several non-idealities in typical experiments.As a model system, this work mainly focuses on a fractal colloidal gel. We thoroughly characterize the linear power-law rheology of the gel, we show that it is very accurately described by the phenomenological Fractional Maxwell (FM) model, and we discuss the possible relationship between the FM model and the microscopic structure of the gel.Under a constant shear stress (creep experiment), the colloidal gel exhibits a fast, elastic deformation followed by a slow sublinear power-law creep, which is eventually interrupted after several hours by an upturn in the shear rate, leading to the delayed failure of the material. Our experiments show that the first power-law regime, nicely described by linear viscoelasticity, corresponds at the microscopic scale to partially nonaffine, yet fully reversible dynamics. Upon deviation from the linear viscoelasticity, a sharp acceleration, localized in time of the nonaffine dynamics is observed. These faster rearrangements precede the macroscopic failure of the gel by thousands of seconds: they thus are dynamic precursors of failure that allow one to predict the fate of the gel well before any rheological measurement.To obtain a more comprehensive picture of material failure, we next address the onset of irreversibility under a cyclic perturbation repeated many times (fatigue experiment). By following the stroboscopic evolution of the system as a function of the cumulated deformation, we observe that as soon as the shear amplitude is increased beyond the linear regime the relaxation rate increases abruptly, indicating that irreversible plasticity is at play. If a large enough stress amplitude is applied, the system on the long run displays delayed fatigue failure, with reminiscences of the one observed in creep. Differences and similarities between the two failure mechanisms are discussed.Finally, the generality of the results obtained on colloidal gels is checked by investigating as second model system a soft colloidal glass. In this case, our experiments indicate that oscillatory yielding is a gradual process, where two relaxation modes contribute to the observed dynamics. Qualitative analogies found with similar systems (e.g. concentrated emulsions) suggest that a general picture might be obtained with our study, which motivates ongoing and future investigations.
|
226 |
Advanced Characterization of Aqueous Inorganic Nanoscale ClustersJackson Jr, Milton 18 August 2015 (has links)
Inorganic nanoscale clusters have garnered significant interest for many practical applications within the fields of materials chemistry, inorganic chemistry, geochemistry, and environmental chemistry. However, the fundamental inner workings of how these materials interact in the solid state and solution continues to be a very elusive problem for scientists. My dissertation focuses on taking non-traditional approaches and characterization techniques to further understand the dynamic interactions of some of the aforementioned clusters. Chapter I is a comprehensive survey and perspective on selected characterization techniques used to study Group 13 aqueous nanoscale clusters and other polyoxometalates in solution. Chapter II focuses on utilizing Raman spectroscopy, infrared spectroscopy, and quantum mechanical computations to unambiguously identify Group 13 tridecameric species in the solid state and aqueous solution. Chapter III discusses the first instance of transmetalation of aqueous aluminum clusters via salt addition of In(NO3)3 in aqueous or methanol. Chapters IV and V explore the effects that aprotic and protic solvents can have on the solution speciation of the flat aluminum tridecamer. Chapter VI discusses the utility of using electrochemically synthesized gallium tridecamer and its functional use as a thin film semiconductor. Chapter VII describes a unique graduate level chemistry course designed to allow students to conduct and generate publication-worthy research within the timeframe of the course. Chapter VIII ventures out beyond the group 13 cluster and introduces techniques used to study the formation and stability of aqueous hafnium clusters. Chapter IX details the synthesis and characterization of rhombic structured copper clusters in the solid state. Finally, chapter X highlights my unfinished projects that can propel future research within the lab.
This dissertation includes previously published and unpublished co-authored material.
|
227 |
Produção de sistemas supramoleculares nanoestruturados a partir da complexação de DNA e copolímeros catiônicos com potencial aplicação em terapia gênicaAlbuquerque, Lindomar Jose Calumby January 2016 (has links)
Orientador: Prof. Dr. Fernando Carlos Giacomelli / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Biotecnociência, 2016. / A internalização celular de acidos nucleicos requer um agente de transfeccao, uma vez que o DNA isolado nao e capaz de atravessar membranas lipidicas. Embora diversos agentes polimericos de transfeccao tenham sido estudados, nenhum dos veiculos de entrega de gene propostos preenche todos os requisitos necessarios para uma terapia eficaz (capacidade de condensar e compactar o DNA, estabilidade em ambiente plasmatico, baixa toxicidade, eficiencia de internalizacao, escape endossomal e liberacao intracelular de material genetico). Nesta direcao, foram produzidos poliplexos a partir da complexacao entre copolimeros cationicos e DNA. Os poliplexos foram preparados a partir de DNA de timo de bezerro (ctDNA) dissolvido em tampao fosfato. Medidas de espectroscopia de correlacao de fluorescencia (FLCS), potencial-¿ê e eletroforese em gel de agarose indicaram complexacao eficiente entre as cadeias de DNA e os copolimeros em bloco PEO113-b-PDEA50 e POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47). Os copolimeros em bloco foram capazes de condensar as cadeias de DNA em particulas com tamanho desejado para absorcao celular por meio das vias de endocitose (RH ~ 65-85 nm). Os resultados obtidos por AFM, SAXS e SLS sugerem que as estruturas supramoleculares sao esfericas, porem de elevado grau de hidratacao. Os dados de ITC revelaram que a ligacao polimero/DNA e endotermica, e consequentemente o processo e governado por efeitos entropicos. A combinacao dos resultados sugerem que POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47) condensa as cadeias de DNA de forma mais eficiente do que PEO113-b-PDEA50. Mostrou-se tambem por medidas de espectroscopia de dicroismo circular que a conformacao do DNA permaneceu estavel, mesmo apos a complexacao e os poliplexos se mostraram estaveis em meio plasmatico. Os resultados obtidos de viabilidade celular mostram que ambos os sistemas apresentam baixa citotoxicidade, entretanto ensaios de microscopia e citometria de fluxo mostram que os sistemas nao sao funcionais do ponto de vista de expressao de GFP. Porem, quando estes sistemas sao avaliados na presenca de cadeias polimericas livres de polietilenoimina (PEI) se obtem sucesso nas etapas da internalizacao e transfeccao genica indicando que a presenca de cadeias livres de PEI tem papel fundamental nos processos. / PThe intracellular delivery of nucleic acids requires a vector system as they cannot diffuse across lipid membranes. Although polymeric transfecting agents have been extensively investigated, none of the proposed gene delivery vehicles fulfills all the requirements needed for an effective therapy namely ability to bind and compact DNA into polyplexes, stability in serum environment, endosome-disrupting capacity, efficient intracellular DNA release and low toxicity. Accordingly, investigations aiming at safe and efficient therapies are still essential to achieve clinical success of gene therapies. Polyplexes based on the complexation between DNA and cationic copolymers have been produced. The polyplexes were prepared by previously dissolving DNA from calf thymus (ctDNA) in phosphate buffer saline. Measurements of FCS, ¿ê-potential and agarose gel electrophoresis indicated the complexation of DNA and some of block copolymer systems, namely PEO113-b-PDEA50 and POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47). The block copolymers were evidenced to properly condense DNA into particles with desirable size for cellular uptake via endocytic pathways (RH ~ 65-85 nm). The shape and surface morphology of the polyplexes were investigated using SLS, SAXS and AFM and the data suggest that the supramolecular structures are spherical, however, highly swollen by water. The ITC data revealed that the polymer/DNA binding is endothermic and therefore the process in entropically driven. The combo of results supports that POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47) condenses DNA more efficiently and with higher thermodynamic outputs as compared to PEO113-b-PDEA50. Finally, circular dichroism spectroscopy indicated that the conformation of DNA remained the same after complexation and that the polyplexes are highly stable in serum environment. The cell viability results show that both systems have low cytotoxicity, however microscopy and flow cytometry assays showed that the polymers are poor tranfecting agents themselves. Nevertheless, in the presence of PEI chains, cellular uptake and transfection efficiency are subtantially enhances point out the fundamental importance of positive charges in the processes.
|
228 |
Light scattering studies of irregularly shaped particlesHeinson, Yuli Wang January 1900 (has links)
Doctor of Philosophy / Physics / Christopher M. Sorensen / We present light scattering studies of irregularly shaped particles which significantly affect the climate. We built and calibrated our apparatus which was able to measure all six independent scattering matrix elements. Our apparatus detects light from 0.32° to 157° simultaneously. We studied all six scattering matrix elements of irregularly shaped Arizona Road Dust which behave differently than those of spheres. We strongly focused on the most important scattering matrix element – the phase function, scattered intensity vs. the scattering angle, which we applied Q-space analysis to. Q-space analysis involves plotting the scattering intensity vs. the magnitude of the scattering wave vector q or qR with R the radius of a particle, on a double logarithmic scale. We measured and studied the phase functions of Al₂O₃ abrasives; compared the scattering from the abrasives with the scattering of spheres.
To generalize the study, we collected a large amount of experimental and theoretical data from our group and others and applied Q-space analysis. They all displayed a common scattering pattern. The power law exponents showed a quasi-universal functionality with the internal coupling parameter ρ'. In situ studies of the soot fractal aggregates produced from a burner were also conducted. A power law exponent -1.85 is seen to imply the aggregates have fractal dimension of D[subscript f]=1.85.
The overall work presented shows Q-space analysis uncovers patterns common to all particles: a q-independent forward scattering regime is followed by a Guinier regime, a power law regime, and sometimes an enhanced back scattering regime. The description of the patterns applies to spheres as well, except the power law regime has more than a single power law. These simple patterns give a unified description for all particle shapes. Moreover, the power law exponents have a quasi-universal functionality with ρ' for non-fractal aggregates. The absolute value of the exponents start from 4 when ρ' is small. As ρ' increases, the exponents decrease until the trend levels off at ρ'≳10 where the exponents reach a constant 1.75±0.25. All the non-fractal particles fall on the same trend regardless of the detail of their structure.
|
229 |
Modification et dégradation enzymatique de polysaccharides : investigation par imagerie et diffusion de rayonnement / modification and enzymatic degradation of polysaccharides : Imaging and light scattering studyMkedder, Ilham 15 November 2012 (has links)
Le travail présenté dans se manuscrit s'inscrit dans le domaine de la chimie et physico-chimie des polysaccharides. Une étude des propriétés physico-chimiques du xyloglucane en fonction de différentes conditions est d'abords réalisée, elle montre la difficulté d'obtenir des solutions stables à l'échelle moléculaire ainsi que la possibilité d'obtenir des nanoparticules à base de xyloglucanes. Le suivi de l'hydrolyse enzymatique du xyloglucane en solution par la diffusion de la lumière a mis en évidence l'agrégation des produits obtenus en solution. L'imagerie par la microscopie à force atomique a révélé l'importance de la surface dans le phénomène de dégradation. Enfin des dérivés de xyloglucane ont été obtenus par oxydation par le système TEMPO/NaOCl/NaBr, et des essais de préparation de conjugués xyloglucane-cytarabine ont été effectués. / The work presented in this manuscript is in the field of chemistry and physical chemistry of polysaccharides. A study of the physicochemical properties of xyloglucan under different conditions is carried around and showing the difficulty to obtaining stable solutions at the molecular level. The study also evidenced the possibility of obtaining nanoparticles based on xyloglucan. Monitoring of the enzymatic hydrolysis of xyloglucan in solution by light scattering indicated the aggregation of the degradation products. Imaging by atomic force microscopy revealed the importance of the surface in the degradation phenomenon. Finally xyloglucan derivatives were obtained by oxidation system TEMPO / NaOCl / NaBr, and test on the coupling of xyloglucan and cytarabine conjugates were made.
|
230 |
Preparação e caracterização de aerogéis por adsorção de nitrogênio e espalhamento de luz visível / Preparation and characterization of aerogels by nitrogen adsorption and visible light scatteringLima, Bruna Patrocinio [UNESP] 15 March 2017 (has links)
Submitted by Bruna Patrocinio Lima null (brunapatrocinio@globo.com) on 2017-05-12T15:11:12Z
No. of bitstreams: 1
Bruna_ dissertação final.pdf: 13918588 bytes, checksum: 30ea5c3dcd5492e9be4f34c07ae6e137 (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-05-12T16:51:27Z (GMT) No. of bitstreams: 1
lima_bp_me_rcla.pdf: 13918588 bytes, checksum: 30ea5c3dcd5492e9be4f34c07ae6e137 (MD5) / Made available in DSpace on 2017-05-12T16:51:27Z (GMT). No. of bitstreams: 1
lima_bp_me_rcla.pdf: 13918588 bytes, checksum: 30ea5c3dcd5492e9be4f34c07ae6e137 (MD5)
Previous issue date: 2017-03-15 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O Processo Sol-Gel tem sido utilizado para a preparação de materiais vítreos ou vítreo-cerâmicos a partir das reações de hidrólise e policondensação de alcoóxidos metálicos. A reação global do processo envolve a reação de hidrólise e policondensação dos siloxanos, seguido de gelificação, envelhecimento e secagem dos géis. Para preservar as propriedades estruturais dos géis úmidos, a secagem pode ser realizada por processos hipercríticos, ou pela introdução de agentes hidrofóbicos, ou até mesmo por sublimação dos solventes remanescentes das reações de hidrólise e policondensação. Quando a secagem é realizada por processo hipercrítico, o material obtido é conhecido como Aerogel. O método consiste em fazer a troca dos solventes remanescentes das reações de hidrólise e policondensação por um solvente que possa ser extraído por processo hipercrítico. No nosso caso, as amostras híbridas de sílica foram preparadas via Processo Sol-Gel utilizando os alcoóxidos 3-Glicidoxipropiltrimetoxisilano e Tetraethoxisilano na relação molar de 4:1. A hidrólise do sistema foi promovida em meio ácido pela adição de 3 diferentes ácidos Clorídrico, ou Nítrico, ou Bromídrico. Após o término da reação de hidrólise, as soluções, que recebem o nome de Sol, foram acondicionadas em recipientes e mantidas em estufa a 40 °C para gelificação e envelhecimento. A troca dos solventes foi realizada por Etanol, seguida de CO2 líquido em autoclave especialmente desenvolvida para o processo e sua extração realizada em temperatura e pressão superiores a 31° C e 74 atm, respectivamente. As características estruturais dos aerogéis de silica foram estudadas através dos métodos de adsorção de nitrogênio e espalhamento de luz visível (λ= 405 nm, 543 nm e 612 nm). A técnica de adsorção de nitrogênio permitiu determinar a distribuição de tamanho dos poros que apresentou um pico relativamente estreito na região de mesoporos , a superfície específica em torno de 600 m²/g, o tamanho médio dos poros em torno de 10 nm e o tamanho médio das partículas em torno de 3 nm. A técnica de espalhamento de luz visível permitiu determinar a dimensão do fractal dentro do intervalo de 1 < D < 3 que caracteriza uma estrutura que pode ser descrita como fractal de massa, o tamanho médio dos poros entre 1000 nm e 4000 nm, e o tamanho médio das partículas entre 300 nm e 800 nm. Os resultados obtidos para o tamanho de poros e tamanho de partícula obtido através das duas técnicas apresentarem grande discrepância, e a razão entre esses parâmetros são equivalentes mesmo quando vistas em diferentes escalas. / The Sol-Gel Process has been used for the preparation of vitreous or vitreous-ceramic materials from the hydrolysis and polycondensation reactions of metal alkoxides. The overall reaction of the process involves the hydrolysis reaction and the polycondensation reaction of the siloxanes, followed by gelling, aging and drying of the gels. To preserve the structural properties of wet gels, the drying can be carried out by hypercritical processes, by the introduction of hydrophobic agents, or even by sublimation of the remaining solvents of the hydrolysis and polycondensation reactions. When the drying is performed by hypercritical process, the material obtained is known as Aerogel. The method consists of making the exchange of remaining solvent hydrolysis and polycondensation reactions by a solvent that can be extracted by hypercritical process. In our case, the hybrid silica samples were prepared by Sol-Gel Process using the alkoxides 3-glycidoxypropyltrimethoxysilane and Tetraethoxisilano in molar ratio of 4:1. Hydrolysis of the system was promoted in acidic medium due to the addition of the 3 different hydrochloric, or nitric, or hydrobromic acids. After completion of the hydrolysis reaction, the solutions, which are called Sol, were packed in containers and kept in an oven at 40° C for gelling and aging. Solvent exchange was carried out by Ethanol, followed by liquid CO2 in an autoclave specially developed for the process and its extraction performed at higher temperature and pressure at 31 ° C and 74 atm, respectively. The structural characteristics of silica aerogels were studied through the methods of nitrogen adsorption and scattering of visible light (λ= 405 nm, 543 nm e 612 nm). The nitrogen adsorption technique made it possible to determine the pore size distribution which presented A relatively narrow peak in the mesoporous region, the specific surface around 600 m²/g, The average size of the pores around 10 nm and the average size of the particle around 3 nm.. The visible light scattering technique allowed to determine the Dimension of the fractal within the range of 1 <D <3 which features a structure that can be described as mass fractal, the average size of the pores between 1000 nm and 4000 nm and the average size of the particle between 300 nm and 800 nm. The results obtained for the size of pore and particle size obtained by the two techniques present greater discrepancy and the ratio between these parameters are equivalent.
|
Page generated in 0.0927 seconds