This Dissertation is devoted to computational study of the solidification, dynamics and mechanics of model semiflexible polymers with variable chain flexibility as well as a computational investigation of the clogging phenomena observed in granular materials. Chain stiffness is an intrinsic factor that governs single-chain flexibility. It plays a critical role in the physics of polymeric materials. In this work, we employ a coarse-grained polymer model in which chain stiffness can be tuned by a single parameter (bending stiffness kb) that yields chain shape ranging from coil-like to rod-like in the flexible and very stiff limit respectively. In chapter 2, we focus on how chain stiffness affects how polymer melts solidify under thermal cooling. We observe a strong dependence of the solid-state morphology (formed after cooling) upon chain flexibility. In the flexible limit, we find that monomers possess crystalline order while chains retain random-walk like structure. In higher stiffness regime glass formation is obtained while nematic ordering typical of lamellar precursors coexists with close-packing in the rod-like limit. Surprisingly we observe various structures ranging from spiral, to multi-domain nematic phases in the intermediate values of kb. In chapter 3 we go a step further to relate the solidification behaviors of chains discussed in chapter 2 to their melt dynamics. We probe the microstructure and the dynamics of flexible, intermediate-stiffness and rod-like chains. We find that melts of flexible and stiff chains that crystallize under cooling show simple and fast dynamics with Arrhenius temperature dependence. Interestingly, the intermediate-stiffness chains exhibit Vogel-Fulcher dynamical relaxation typical of fragile glass-formers even though their ground states is a nematic-close-packed crystal. There is no compelling argument based on static micro-structure change explaining this dynamical arrest to be found. However, we find that the dynamics of intermediate-stiffness chains is dominated by the stringlike cooperative motion that correlates along their chain backbones. This cooperative rearrangement which is absent in other systems appears to be the main cause of the dynamical arrest observed for intermediate-stiffness chains. In chapter 4, we turn to another class of materials where the negligible contribution of thermal fluctuations gives rise to an interesting phenomenon, i.e. the clogging transition. Clogging is a probabilistic event that occurs through a transition from a homogeneous flowing state to a heterogeneous or phase separated jammed state. The granular system under study is an assemble of bidisperse disks externally driven through a two dimensional periodic substrate. We find that the probability for clogging strongly depend on particle packing, obstacle number and the driving direction. Surprisingly, under relevant conditions we observe a size-specific clogging transition in which the smaller species get trapped while the larger species keep flowing. Chapter 5 returns to discuss the polymer solidification in the context of isostaticity. Results from the simulations of semiflexible polymers described in chapter 2 allow us to derive a generalized isostaticity criterion that can be applied to finite-stiffness chains. The new criterion is based on the characteristic ratio C which characterizes the slow freezing out of configurational freedom of chains as chain stiffness increases. The results of the average coordination number at solidification Z(Ts) suggest a link between jamming in athermal systems and solidification in their thermal counterparts. Finally, in chapter 6 we study the effect of chain stiffness on the mechanical response of glassy polymers. We investigate shear deformation of three systems with a different degree of entanglement. We find that loosely entangled chains display strong shear banding and undergo fracture via chain pullout. In contrast, tightly entangled chains fail at high enough strain along a well-defined plane via chain scission shortly after chains are pulled taut. We explain these chain-stiffness-dependent behaviors qualitatively using the segmental packing efficiency argument and quantitatively using modern plasticity measures

Made available in DSpace on 2014-06-11T19:25:32Z (GMT). No. of bitstreams: 0 Previous issue date: 2003-12-18Bitstream added on 2014-06-13T20:33:13Z : No. of bitstreams: 1 delbianco_gab_me_rcla.pdf: 3365462 bytes, checksum: 094757b4ee8708afcd8c42a9657cb3e9 (MD5) / O encapsulamento de resíduos sólidos em vidros tem sido uma solução extremamente interessante porque permite a imobilização de resíduos tóxicos na estrutura do material produzido. O objetivo deste trabalho é estudar a aplicabilidade de resíduo galvânico das indústrias de bijuterias, como corante de vidrados cerâmicos. Este resíduo foi calcinado e micronizado, e adicionado ao esmalte cerâmico em diferentes concentrações. Este esmalte foi aplicado na superfície das peças cerâmicas retiradas da linha de produção de uma indústria e, em seguida, devolvidas à linha para serem submetidas ao processo de mono-queima. Os ensaios realizados nos vidrados das peças cerâmicas foram: (i) espectroscopia dispersiva de raios-X (EDS) para determinação semiquantitativa da composição química do resíduo, e fluorescência de raios-X para determinação da composição química da frita, (ii) ensaios de caracterização físico-químicas dos vidrados: microscopia óptica, microdureza Vickers, difração de raios-X, e espectroscopia de infravermelho. Foram também realizados ensaios de classificação dos vidrados das placas cerâmicas: resistência à abrasão superficial, resistência ao gretamento, manchamento, ataque químico e dureza Mohs. Adicionalmente foi efetuado um ensaio de lixiviação no produto que simula o desgaste da placa cerâmica como um todo, visando verificar o grau de inertização do resíduo. Todos os resultados foram comparados com resultados experimentais apresentadas na literatura, referentes a vitro-cerâmicas preparadas empregando resíduos diversos. Conclui-se, com base nos resultados obtidos, que a inertização deste resíduo foi altamente eficiente do ponto de vista físico-químico, pois as peças finais apresentaram propriedades iguais ou melhores que aquelas com vidrados equivalentes utilizados atualmente com corantes comerciais. / The encasing of solid waste in glass has been a solution extremely interesting because it allows the toxic waste immobilization at the produced material structure. this work goal is to study the galvanic waste applicability of the golden plated industries, as ceramic glassy coloring. This waste was calcined and micronized and added to the ceramic enamel in different concentrations. This enamel was applied on the surface of the ceramic pieces taken from the production line of an industry and, afterwards, given back to the line to be undertaken to the mono-burning process. The tests performed at the glass of ceramic pieces were: (i) x-ray disperse spectroscopy (EDS) for a semi-quantitative determination of chemical composition of the waste, and x-ray fluorescence for the frying chemical composition determination, (ii) tests of physic-chemical characterization of the glass, optic microscopy, Vickers micro-hardness, diffraction of x-ray and infrared spectroscopy. Tests of classification of ceramic plates glass also were performed: resistance to superficial abrasion; cracking to the resistance, spotting, and chemical aggression and Mohs hardness. Besides a lixiviation test at the product was performed at the product, in order to simulate a waste of the ceramic plate as a whole, searching to check the inertia degree of the waste. Every result was compared to the experimental results shown in the literature, referring to prepared ceramic-glass applying diverse waste. One notices, based on the gotten results that the inertia of this waste was highly efficient from the physic-chemical point-of-view. The final pieces showed similar or better proprieties that those ones with the same glassy ones applied nowadays with commercial coloring.

abstract: In the United States, 95% of the industrially produced hydrogen is from natural gas reforming. Membrane-based techniques offer great potential for energy efficient hydrogen separations. Pd77Ag23 is the bench-mark metallic membrane material for hydrogen separation at high temperatures. However, the high cost of palladium limits widespread application. Amorphous metals with lower cost elements are one alternative to replace palladium-based membranes. The overall aim of this thesis is to investigate the potential of binary and ternary amorphous metallic membranes for hydrogen separation. First, as a benchmark, the influence of surface state of Pd77Ag23 crystalline metallic membranes on the hydrogen permeability was investigated. Second, the hydrogen permeability, thermal stability and mechanical properties of Cu-Zr and Ni60Nb35M5 (M=Sn, Ti and Zr) amorphous metallic membranes was evaluated. Different heat treatments were applied to commercial Pd77Ag23 membranes to promote surface segregation. X-ray photoelectron spectroscopy (XPS) analysis indicates that the membrane surface composition changed after heat treatment. The surface area of all membranes increased after heat treatment. The higher the surface Pd/(Pd+Ag) ratio, the higher the hydrogen permeability. Surface carbon removal and surface area increase cannot explain the observed permeability differences. Previous computational modeling predicted that Cu54Zr46 would have high hydrogen permeability. Amorphous metallic Cu-Zr (Zr=37, 54, 60 at. %) membranes were synthesized and investigated. The surface oxides may result in the lower experimental hydrogen permeability lower than that predicted by the simulations. The permeability decrease indicates that the Cu-Zr alloys crystallized in less than two hours during the test (performed at 300 °C) at temperatures below the glass transition temperature. This original experimental results show that thermal stability of amorphous metallic membranes is critical for hydrogen separation applications. The hydrogen permeability of Ni60Nb35M5 (M=Sn, Ti and Zr) amorphous metallic membranes was investigated. Nanoindentation shows that the Young’s modulus and hardness increased after hydrogen permeability test. The structure is maintained amorphous after 24 hours of hydrogen permeability testing at 400°C. The maximum hydrogen permeability of three alloys is 10-10 mol m-1 s-1 Pa-0.5. Though these alloys exhibited a slight hydrogen permeability decreased during the test, the amorphous metallic membranes were thermally stable and did not crystalize. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2015

Orientador: Ervino Carlos Ziemath / Banca: Ana Paula Margarido Menegazzo / Banca: Gerson Antonio Santarine / Resumo: O encapsulamento de resíduos sólidos em vidros tem sido uma solução extremamente interessante porque permite a imobilização de resíduos tóxicos na estrutura do material produzido. O objetivo deste trabalho é estudar a aplicabilidade de resíduo galvânico das indústrias de bijuterias, como corante de vidrados cerâmicos. Este resíduo foi calcinado e micronizado, e adicionado ao esmalte cerâmico em diferentes concentrações. Este esmalte foi aplicado na superfície das peças cerâmicas retiradas da linha de produção de uma indústria e, em seguida, devolvidas à linha para serem submetidas ao processo de mono-queima. Os ensaios realizados nos vidrados das peças cerâmicas foram: (i) espectroscopia dispersiva de raios-X (EDS) para determinação semiquantitativa da composição química do resíduo, e fluorescência de raios-X para determinação da composição química da frita, (ii) ensaios de caracterização físico-químicas dos vidrados: microscopia óptica, microdureza Vickers, difração de raios-X, e espectroscopia de infravermelho. Foram também realizados ensaios de classificação dos vidrados das placas cerâmicas: resistência à abrasão superficial, resistência ao gretamento, manchamento, ataque químico e dureza Mohs. Adicionalmente foi efetuado um ensaio de lixiviação no produto que simula o desgaste da placa cerâmica como um todo, visando verificar o grau de inertização do resíduo. Todos os resultados foram comparados com resultados experimentais apresentadas na literatura, referentes a vitro-cerâmicas preparadas empregando resíduos diversos. Conclui-se, com base nos resultados obtidos, que a inertização deste resíduo foi altamente eficiente do ponto de vista físico-químico, pois as peças finais apresentaram propriedades iguais ou melhores que aquelas com vidrados equivalentes utilizados atualmente com corantes comerciais. / Abstract: The encasing of solid waste in glass has been a solution extremely interesting because it allows the toxic waste immobilization at the produced material structure. this work goal is to study the galvanic waste applicability of the golden plated industries, as ceramic glassy coloring. This waste was calcined and micronized and added to the ceramic enamel in different concentrations. This enamel was applied on the surface of the ceramic pieces taken from the production line of an industry and, afterwards, given back to the line to be undertaken to the mono-burning process. The tests performed at the glass of ceramic pieces were: (i) x-ray disperse spectroscopy (EDS) for a semi-quantitative determination of chemical composition of the waste, and x-ray fluorescence for the frying chemical composition determination, (ii) tests of physic-chemical characterization of the glass, optic microscopy, Vickers micro-hardness, diffraction of x-ray and infrared spectroscopy. Tests of classification of ceramic plates glass also were performed: resistance to superficial abrasion; cracking to the resistance, spotting, and chemical aggression and Mohs hardness. Besides a lixiviation test at the product was performed at the product, in order to simulate a waste of the ceramic plate as a whole, searching to check the inertia degree of the waste. Every result was compared to the experimental results shown in the literature, referring to prepared ceramic-glass applying diverse waste. One notices, based on the gotten results that the inertia of this waste was highly efficient from the physic-chemical point-of-view. The final pieces showed similar or better proprieties that those ones with the same glassy ones applied nowadays with commercial coloring. / Mestre

O presente trabalho relata a investigação de uma rota reprodutível de obtenção de materiais de carbono a partir do tratamento térmico de pré-polímero fenol formaldeído (resina fenólica) levando em consideração características morfológicas e estruturais.O controle da composição de resina bem como o estabelecimento cuidadoso da rampa de aquecimento foram fatores decisisvos para a obtenção de materiais análogos ao carbono vítreo de maneira reprodutível. Os materiais obtidos apresentaram reduzida presença de poros e condutividade térmica apreciável uma vez que foram testados como eletrodos de trabalho em ensaios eletroquímicos . A análise estrutural e morfológica dos compostos sintetizados demonstrou a presença de estrutura semelhante ao carbono vítreo relatado na literatura com presença de poucos poros superficiais da ordem de micrômetros até nanômetros. Já em relação aos materias de carbono porosos, buscou-se obter compostos com arranjo ordenado de mesoporos. Resultados preliminares demonstraram que os materiais apresentaram poros micrométricos superficiais organizados. / The present work reports on the investigation of reproducible route to synthesize carbon materials from phenolic resin take into account the structural and morphological features. The control or the resin composotion and the careful establinshing of the ramp heating were decisive for achievement the materials analogous to the glassy carbon (vitreous carbon) in a reproducicle way. The materials obtained materials revealed the glassy carbon structure with the presence of the superficial pores in the range of micrometers to nanometrers. In relation to the carbon materilas, they organized arrangement of the porous in the micrometric scale.

Pertencendo à família dos eletrodos de carbono, o carbono polimérico vítreo (CPV) apresenta condutividade elétrica, estabilidade térmica, resistência mecânica e grande intervalo de potencial. Dessa forma, se torna possível sua aplicação como eletrodo sólido para o monitoramento de processos de transferência de carga, suporte para polímeros eletroativos e modificadores de superfície. O processo de obtenção do CPV se baseia na carbonização em ambiente inerte de materiais precursores, dentre os quais, podem-se destacar as resinas fenólicas, como por exemplo, resol (C7H8O2). Neste contexto, este trabalho investiga a obtenção do CPV a partir da resina fenólica resol, bem como o efeito da incorporação de íons metálicos (crômio, ferro e cério) na estrutura cristalina e nas propriedades eletroquímicas. Os materiais foram caracterizados por análise térmica, microscopia eletrônica de varredura, difratometria de raio-X, espectrofotometria no infra-vermelho e por voltametria cíclica. O difratograma de raio-X confirmou a obtenção de um material com estrutura similar a do carbono vítreo e, através da microscopia eletrônica de varredura, ficou comprovada a baixa porosidade do CPV. Por espectrofotometria no infra-vermelho, ficou demonstrada a presença de grupos funcionais, como carbonilas e hidroxilas, na estrutura do material. Os resultados mostram que tanto o CPV quanto o CPV modificado por íons metálicos possuem boa estabilidade térmica, pois não houve nenhuma decomposição desses materiais abaixo de 400ºC. E, tanto o CPV quanto o CPV modificado por íons metálicos apresentam comportamento eletroquímico similar no sistema ferricianeto/ferrocianeto. Concluindo, o método desenvolvido para obtenção do CPV modificado por íons metálicos é satisfatório, reprodutivo além de proporcionar uma dispersão homogênea dos íons na fase do CPV. Desta forma, possibilita uma nova frente de estudos destes materiais eletródicos em eletrocatálise e eletroanalítica. / Belonging to the family of the carbon electrodes, the glassy polymeric carbon (GPC) presents electric conductivity, thermal stability, mechanical resistance mechanics and great potential interval. In this way, it is possible its application as solid electrode in order to follow electron transfer process, act as support of electroactive molecules and surface modifier. The glassy polymeric carbon production is based on carbonization of organic precursors in inert atmosphere such as phenolic resins (for example, resol - C7H8O2) In this context, this work investigates the production of GPC from phenolic resin, as well as the effect of incorporation of metallic ions (chromium, iron, and cerium) on crystalline structure and electrochemical properties. The materials were characterized by thermal analysis, scanning electron microscopy, X-ray diffraction, infrared spectrophotometry, and cyclic voltammetry. X-ray diffraction patterns had confirmed the presence of a material with similar structure of that found in conventional glassy carbon, and through SEM images it has shown a low porosity carbon material. From infrared spectrum, it can be observed carbonyl and hydroxide groups. The found results showed that both GPC and metallic ion modified GPC exhibit thermal stability, since no decomposition has occurred up to 450 oC. And, both carbon materials present similar electrochemical behavior in hexacyanoferrate system. In conclusion, the method developed for attainment of the GPC modified for ions metallic is satisfactory, and reproductive. Besides, it provides a homogeneous dispersion of ions in the bulk phase of the GPC. As a consequence, it makes possible a new front of studies of these materials in electrocatalysis and electroanalysis.

Esse trabalho descreve a caracterização térmica, estrutural e elétrica do sistema vítreo 50B203-(50-x)PbO-xLiF com x variando de 0,0 a 50,0. A técnica de calorimetria diferencial exploratória (DSC) foi utilizada na determinação das temperaturas características. A difratometria de raios x foi utilizada na detecção e identificação de fases cristalinas originadas durante a síntese ou durante o processo de aquecimento das amostras. As técnicas de espectroscopia Raman e Ressonância Magnética Nuclear (RMN) foram utilizadas na obtenção de informações estruturais da ordem a curto alcance em função da composição das amostras. A técnica de espectroscopia de impedância complexa foi utilizada na determinação das condutividades elétrica em função da quantidade de LiF e da temperatura. Amostras vítreas sem a presença de fases cristalinas foram obtidas para composições contendo no máximo 40moI % de LiF. Através da análise da medida de densidade, foi possível constatar que o aumento da quantidade de LiF leva a formação de uma estrutura mais aberta. A análise do espectro Raman das amostras vítreas mostrou que com o aumento da concentração de LiF, ocorre uma mudança significativa nas unidades estruturais borato presentes nas amostras. Na amostra vítrea contendo 40 mol% de LiF observou-se a existência de uma superunidade estrutural formada por diferentes unidades borato. Apesar dessa variação das unidades borato, as medidas de RMN do 11B mostraram que a razão entre as unidades trigonal B03 e tetraédrica B04 permanece praticamente constante em todo intervalo de composição analisada. A condutividade elétrica aumenta à medida que a concentração de LiF aumenta devido ao aumento do numero de portadores de carga. A 330°C uma condutividade de 3,55 x 10-5 S/cm foi medida para a amostra contendo 40 moI % de LiF. Utilizando as amostras contendo 40 e 45 mol% de LiF preparadas e caracterizadas durante a realização desse trabalho, foi possível construir um dispositivo para ser utilizado na demonstração do processo de condução elétrica em materiais vítreos condutores para alunos do ensino médio / This work describes the thermal, structural and electric characterization of 50B203-(50-x)PbO-xLiF glass system with x varying from 0,0 to 50,0. The differential scanning calorimetry (DSC) technique was used to determine the glass transition and the crystallization temperatures. The X-ray diffraction technique was used to detect and in the identification of the crystallized phases present on the glassy samples after the melt and during the heating. The Raman spectroscopy and the Nuclear Magnetic Resonance techniques were used in order to verify the structural changes induced by the substitution of PbO by LiF on the anionic borate units and on the B03/B04 species ratio. The impedance complex spectroscopy technique was used to evaluate the variation of the electrical conductivity and activation energy as a function of the LiF content. Homogenous glassy sample containing less than 45 mol % of LiF without any trace of crystallization were obtained. The analysis of the Raman spectra shows that as the amount of LiF increases the concentration of anionic borate species changes and that these changes are an indicative of the formation of B-F bonds. However, according to the 11B NMR data, these structural rearrangement should be of such nature that the ratio sup>[3]B/[4]B is near1y invariant. As expected, the electrical conduction increases as the amount of LiF increases because the number of carriers increases. At 330°C; , the conductivity varies from 3.93 x 10-10 (S/cm) for the sample without LiF to 3.55 x 10-5(S/cm) for the sample containing 40 mol % of LiF. The activation energy (Ea) varied respectively from 1.55 eV to 0.97 eV. Using the glassy samples with 40 and 45 mol% of LiF, we could built a set up that can be used to demonstrate the electrical conduction process on glass materials to high school students

Research in local fracture processes and micro-machining of polymers and polymer-based composites has attracted increasing attention, in development of composite materials and miniaturisation of polymer components. In this thesis, sectioning (machining) of a glassy polymer and a carbon nanotube based composite at the nanoscale was performed by an instrumented ultramicrotome. The yield stresses and fracture toughness of these materials were determined by analysing the sectioning forces. Fractographic analysis by atomic force microscopy was conducted to characterise the topographies and elastic properties of the sectioned surfaces to explore the deformation and fracture behaviour of the polymer during nanosectioning. The study reveals that a transition from homogenous to shear localised deformation occurred as the uncut chip thickness (depth of cut) or sectioning speed increased to a critical value. Analytical and finite element methods were used to model the nanosectioning process. The shear localised deformation was caused by thermal softening due to plastic dissipation. Although not considering sectioning, the tensile properties of a polymer nanocomposite were additionally investigated, where the degree of nanofibrillation and polyethylene glycol (PEG) content had significant effects.

Magister Scientiae - MSc / In this study multilayer graphene nanosheets was synthesize by oxidizing graphite to graphene oxide using H2SO4 and KMnO4 followed by reduction of graphene oxide to graphene using NaBH4. The graphene nanosheets were characterized by Fourier Transform Infrared (FTIR) and Raman spectroscopy, high resolution transmission electron microscopy (HRTEM), Scanning electron microscopy (SEM) and X-ray diffraction (XRD). HRTEM images showed that the multilayer graphene were obtained. The graphene was immobilized directly onto a glassy carbon electrode using the drop coating technique followed by the in situ deposition of mercury, bismuth or antimony thin films to afford graphene modified glassy carbon metal film electrodes (Gr-GC-MEs). The experimental parameters (deposition potential, deposition time, rotation speed, frequency and amplitude) were optimized, and the applicability of the modified electrode was investigated towards the individual and simultaneous determination of Zn2+, Cd2+ and Pb2+ at the low concentration levels (μg L-1) in 0.1 M acetate buffer (pH 4.6) using square wave anodic stripping voltammetry (SWASV). The detection limits values for the Gr-GC-HgE was 0.08, 0.05 and 0.14 μg L-1 for Zn2+, Cd2+ and Pb2+, respectively. The Gr-GC-BiE the detection limits for was 0.12, 0.22 and 0.28 μg L-1 for Zn2+, Cd2+ and Pb2+ while the detection limits for the Gr-GC-SbE was 0.1, 0.3 and 0.3 μg L-1 for Zn2+, Cd2+ and Pb2+, respectively. A Gr-GCE prepared without any binding agents or metal film had detection limits for Zn2+, Cd2+ and Pb2+ of 3.9, 0.8 and 0.2 μg L-1 for Zn2+, Cd2+ and Pb2+. Real sample analysis of which was laboratory tap water was performed using the Gr-GCMEs. Only Gr-GC-HgE was sensitive enough to detect metal ions in the tap water samples at the 3ppb level whereas, the GC-BiE and GC-SbE detected the metal ions at the 10 μg L-1 to 30 μg L-1 level.

In this thesis Moore and Yeo's proposed mapping of the structural glass to the Ising spin glass in a random field is presented. In contrast to Random First Order Theory and Mode Coupling Theory, this mapping predicts that there should be no glass transition at finite temperature. However, a growing correlation length is predicted from the size of rearranging regions in the supercooled liquid, and from this a growing structural relaxation time is predicted. Also presented is a study of the propensity of binary fluids (i.e. fluids containing particles of two sizes) to phase separate into regions dominated by one type of particle only. Binary fluids like this are commonly used as model glass formers and the study shows that this phase separation behaviour is something that must be taken into account.The mapping relies on the use of replica theory and is therefore very opaque. Here a model is presented that may be mapped directly to a system of spins, and also prevents the process of phase separation from occurring in binary fluids. The system of spins produced in the mapping is then analysed through the use of an effective Hamiltonian, which is in the universality class of the Ising spin glass in a random field. The behaviour of the correlation length depends on the spin-spin coupling J and the strength of the random field h. The variation of these with packing fraction and temperature T is studied for a simple model, and the results extended to the full system. Finally a prediction is made for the critical exponents governing the correlation length and structural relaxation time.