Diffusion plays an important role in a number of processes like heterogeneous catalysis, corrosion, separation and purification of chemicals of industrial importance, steel hardening, fuel cells, and solid electrolytes for batteries. It also plays a vital role in several biological processes like transport across biomembranes, nerve impulse, flow of blood and permeation of ingested drug. The elementary process of diffusion in solids is quite different from those in liquids. Similarly, the mode of diffusion in porous solid where different regimes such Knudsen regime exists bears little similarity to those in a dense close-packed crystalline solid. Chapter 1 provides a brief introduction to basics of diffusion in different phases of condensed matter. Among the various phases discussed are liquids, close-packed crystalline solids (e.g., body-centered cubic solids), amorphous solids (e.g. glasses) and microporous crystalline solids (e.g., zeolites). Diffusion in these widely differing phases often bears no resemblance to each other; the rate of diffusion in these phases varies over many orders of magnitude and the elementary step and mechanism in the diffusion process are very different. Brief introduction to theories for diffusion in these phases is provided. Various experimental techniques to measure diffusivities are discussed. Different microscopic models to explain the Quasi Elastic Neutron Scattering (QENS) spectra of these phases yield an insight into the elementary step of the diffusion process. Notwithstanding the fact that completely different models are invoked to explain diffusion in different phases, there are certain underlying generic behaviour across these widely differing phases as the recent work on size dependence of diffusion in these phases demonstrate. Diffusion of a molecule or species (in the context of diffusion within condensed phases) without loss of generality may be said to occur in a medium. A universal behaviour observed is that self diffusivity exhibits a maximum as a function of the size of the diffusant when the diffusant is confined to a medium, as a result of what is known as the Levitation Effect. Such a maximum in self diffusivity has been seen in widely differing medium: microporous solids, dense liquids, ions in polar solvents, etc. The aim of the thesis is to investigate and further explore such universal behaviour and demonstrate for the first time the existence of common trends across different condensed phases in spite of difference in the detail at the microscopic level. In Chapter 2, we report a molecular dynamics study of diffusion of diatomic species AB within zeolite Y. The bond length of A-B as well as the interaction of A and B with the host zeolite atoms are varied. The results demonstrate that for the symmetric case (when A=B or AA), there exists a preferred bond length (determined by the bottleneck or window diameter) when the diffusivity is maximum. This is in agreement with previous results on monatomic species which also exhibit a similar diffusivity maximum. More importantly, no such maximum is seen when the interaction asymmetric is introduced in AB. Slight asymmetry in the interaction gives rise to a weak maximum while large asymmetry in interaction obliterates the diffusivity maximum. These results suggest that the importance of interaction between the diffusant and the medium in Levitation Effect or size-dependent diffusivity maximum. Further, it also demonstrates for the first time the close association between an inversion centre (in a statistical sense and not in the crystallographic sense) and the Levitation Effect. In Chapter 3, a study of size dependence of solutes in a Lennard-Jones liquid is reported. Einstein and others derived the reciprocal dependence of the self-diffusivity D on the solute radius ru for large solutes based on kinetic theory. We examine here (a) the range of ru over which Stokes-Einstein (SE) dependence is valid and (b) the precise dependence for small solutes outside of the SE regime. We show through molecular dynamics simulations that there are two distinct regimes for smaller solutes: (i) the interaction or Levitation Effect (LE) regime for solutes of intermediate sizes and (ii) the D 1/ru2 for still smaller solutes. We show that as the solute-solvent size ratio decreases, the breakdown in the Stokes-Einstein relationship leading to the LE regime has its origin in dispersion interaction between the solute and the solvent. These results explain reports of enhanced solute diffusion in solvents existing in the literature seen for small solutes for which no explanation exists. Several properties have been computed to understand the nature of solute motion in different regimes. We investigate in Chapter 4, the dependence of self diffusivity on the size of the diffusant in a disordered medium with the objective of understanding the experimentally observed correlation between self diffusivity and activation energy seen in a wide variety of glasses. Typically, it is found in many ionic glasses that a higher conductivity is associated with lower activation energy and vice versa. Our understanding of transport in glasses as provided by existing theories does not offer an explanation of this correlation. We have carried out molecular dynamics simulation as a function of the size of the impurity atom or diffusant (both neutral and charged) in a model host amorphous matrix. We find that there is a maximum in self diffusivity as a function of the size of the impurity atom suggesting that there is an appropriate size for which the diffusivity is maximum. The activation energy is found to be the lowest for this size of the impurity. A similar maximum has previously been found in other condensed phases such as confined fluids and dense liquids and has its origin in the Levitation Effect. The implications of this result for understanding ionic conductivity in glasses are discussed. Our result suggests that there is a relation between microscopic structure of the amorphous solid, diffusivity or conductivity and activation energy. The nature of this relationship is discussed in terms of the Levitation parameter showing that diffusivity is maximum when the size of the neck or doorway radius is comparable with the size of the diffusant. Our computational results here are in excellent agreement with independent experimental results which show that structural features of the glass are important in determining the ionic conductivity. In Chapter 5, we report results of molecular dynamics investigations into neutral impurity diffusing within an amorphous solid as a function of the size of the diffusant and density of the host amorphous matrix. We find that self diffusivity exhibits an anomalous maximum as a function of the size of the impurity species. An analysis of properties of the impurity atom with maximum diffusivity shows that it is associated with lower mean square force, reduced backscattering of velocity autocorrelation function, near-exponential decay of the intermediate scattering function (as compared to stretched-exponential decay for other sizes of the impurity species) and lower activation energy. These results demonstrate the existence of well known size-dependent diffusivity maximum in disordered solids. Further, we show that the diffusivity maximum is observed at lower impurity diameters with increase in density. This is explained in terms of the levitation parameter and the void structure of the amorphous solid. We demonstrate that these results imply contrasting dependence of self diffusivity (D) on the density of the amorphous matrix, . D increases with  for small sizes of the impurity but shows an increase followed by a decrease for intermediate sizes of the impurity atom. For large sizes of the impurity atom, D decreases with increase in . These contrasting dependence arises naturally from the existence of Levitation Effect. In Chapter 6, we discuss size dependence of impurity diffusion in an ordered system. We report molecular dynamics simulation studies to understand the role of impurity size and impurity-host interaction on impurity diffusivity in a body centered cubic solid. The simulation studies have been performed for a set of impurity-host interaction parameter ih (i=impurity, h=host atom) for a range of impurity sizes in rigid and flexible bcc solids. A double maximum is seen corresponding to two different sizes of the impurity species. Anomalous maximum is seen for a larger size of the impurity species in the case of the rigid host as compared to flexible host. The second anomalous diffusivity disappears with decrease in ih in flexible bcc solid. For one of the ih where double diffusivity maxima are observed, various properties are analysed to understand the anomalous diffusion behaviour. The impurity with anomalous diffusion has lower activation energy as compared to other impurities. Among the two anomalous impurities, the impurity with higher diffusivity has lower activation energy. The anomalous regime impurities as associated with velocity autocorrelation function with little or no backscattering, minimum average mean square force due to host atoms, lower activation energy. The self intermediate scattering function shows faster decay and a single relaxation time for anomalous regime impurity and two relaxation times for other impurity sizes. The wavenumber dependence of diffusivity of impurities shows oscillatory behaviour except for the anomalous regime impurities which show monotonic dependence on wavenumber. Chapter 7 discusses the influence of temperature induced solid-liquid phase transition on the size-dependent diffusivity. We report results for two distinct cases: (a) when the phase change is associated with corresponding changes in density and (b) when the phase change occurs at constant density. The latter is carried out so as to obtain the influence of disorder on the size-dependent diffusion or Levitation Effect. Studies with variable density are useful to understand the effect of disorder as well as change in density on size-dependent diffusivity. Two diffusivity maxima in the solid face-centred cubic phase is seen when the impurity-medium interaction is sufficiently large. One of these diffusivity maximum disappears with decrease in h. The impurities near the diffusivity maximum show velocity autocorrelation function with little backscattering, minimum in the average mean square force, lower activation energy, faster decay of self intermediate scattering function with a single relaxation time and a monotonic decay in wavevector dependence of diffusivity. Chapter 8 reports molecular dynamics simulations of a model guest tetrahedral molecule AX4 with differing bond lengths lAX have been carried out in a sphere with different surface roughness. The rotational-diffusion coefficient Dr shows a maximum for a particular value of lAX. This corresponds to the distance at which the interaction of the guest with the atoms of the host is most favourable. Although, the intensity of the maximum decreases with increase in the roughness of the confining surface, it is seen that the maximum exists even for a reasonably high degree of roughness. The observed maximum arises from the minimum in the torque on the tetrahedral molecule from its interaction with the confining medium due to mutual cancellation of forces. Activation energy for rotation is seen to be also a minimum for the bond length for which Dr is a maximum. These results suggest that there is a maximum in the rotational-diffusion coefficient when the rotating molecule is confined to a sphere of comparable size similar to the maximum in translational diffusion coefficient seen in porous solids and known as the Levitation Effect. On increase in the roughness of the sphere surface, the value of lAX at which the maximum in Dr is seen decreases. This is similar to the shift seen in the size of the diffusant corresponding to maximum diffusivity in the case of translational diffusivity. In Chapter 9 possible extensions to the work reported in the previous chapters and the directions to take are discussed. Symmetry plays an important role in size dependent diffusivity maximum in microporous crystalline solids; it would be interesting to investigate if similar role of symmetry exists in case of liquids and other disordered solids. Previous work from this laboratory on ions in water has shown the importance of electrostatic interactions. In the light of this, it would be interesting to see the influence of long-range interactions in breakdown of Stokes-Einstein relationship in liquids. Effect of density of the medium on impurity diffusion can be studied over a wide range of densities in case of supercritical fluids such as ions in water (where electrostatic interactions are present) and these can provide greater insight into dependence of diffusion on density. The origin of two diffusivity maxima in case of body-centered and face-centred cubic solids needs a detailed investigation to understand its origin. Quantification of disorder and its effect on size dependence of diffusion would be of interest. A detailed comparison with experimental data of matrix isolated molecules to understand and verify the dependence of rotational diffusivity on the size of the molecule as well as the cavity radius would be instructive.

Submitted by Emanuel Varela Cardoso (emanuel.varela@ufcg.edu.br) on 2018-06-05T19:47:03Z No. of bitstreams: 1 RENNAN PEREIRA DE GUSMÃO – TESE (PPGEP) 2015.pdf: 4781124 bytes, checksum: fd473ef9686e8dc699f6b0aa1da038e5 (MD5) / Made available in DSpace on 2018-06-05T19:47:03Z (GMT). No. of bitstreams: 1 RENNAN PEREIRA DE GUSMÃO – TESE (PPGEP) 2015.pdf: 4781124 bytes, checksum: fd473ef9686e8dc699f6b0aa1da038e5 (MD5) Previous issue date: 2015-03-25 / O segmento de biscoitos é de extrema importância para o Brasil, que se destaca como o 2º maior produtor mundial. A busca por matérias-primas alternativas ao trigo se torna cada vez mais necessária para desenvolvimento de produtos sem glúten, incremento no valor nutricional e redução de custos no setor de panificação. As vagens da algaroba apresentam alto valor nutritivo e podem ser utilizadas como matéria-prima para o desenvolvimento de novos produtos alimentícios. Com esses aspectos, o objetivo deste trabalho foi desenvolver biscoito enriquecido com farinha de algaroba com elevada qualidade nutricional e importância para o desenvolvimento econômico do semiárido nordestino; para tal, foi utilizada a algaroba madura, com teor de água de 20% (b.u) e realizados experimentos de secagem com temperaturas de 50, 60, 70 e 80°C; os modelos matemáticos de Fick, Page, Cavalcanti Mata, Exponencial de Dois Termos e Henderson & Pabis foram utilizados para ajuste aos dados experimentais; posteriormente, foram desenvolvidos biscoitos com farinha de algaroba e submetidos à análise sensorial. A farinha de algaroba utilizada na formulação do biscoito com maior aceitação, foi submetida à caracterização granulométrica, morfológica, reológica, físico -química, determinação dos minerais e utilizada para produção de biscoitos, mediante planejamento experimental. As cinco melhores formulações de biscoito foram submetidas ao teste de aceitação sensorial; a atividade de água, firmeza, fraturabilidade e cor das três formulações de biscoitos com maior aceitação foram analisadas durante 120 dias de armazenamento; a partir dos resultados obtidos pode-se afirmar que os modelos matemáticos de Fick, Page, Cavalcanti Mata, Exponencial de Dois Termos e Henderson & Pabis, representaram satisfatoriamente os dados experimentais da secagem de algaroba. A farinha de algaroba apresentou características reológicas adequadas à produção de biscoitos. A farinha de algaroba apresentou alta concentração de fibras (15,10.g.100g-1), proteínas (9,12.g.100g-1), cálcio (650,75.mg.100g-1) e fósforo (879,12.mg.100g-1). Os biscoitos elaborados com: 25% de farinha de algaroba, 30% de teor de açúcar e 45% de teor de gordura de palma (experimento 4), 5% de farinha de algaroba, 50% de teor de açúcar e 45% de teor de gordura de palma (experimento 7) e 15% de farinha de algaroba, 40% de teor de açúcar e 35% de teor de gordura de palma (experimento 9) foram os que tiveram maior aceitação e intenção de compra. Decorrido o período de 120 dias de armazenamento, os biscoitos elaborados com farinha de algaroba tiveram sua atividade de água, fraturabilidade e luminosidade aumentadas, e sua firmeza, intensidade de amarelo e vermelho, diminuídas. Conclui-se que os biscoitos elaborados com farinha de algaroba apresentaram nutrientes, como: cálcio, ferro e fósforo, boa aceitação sensorial e características de qualidade com comportamento similar ao de produtos já existentes no mercado, durante o armazenamento. / The segment of cookies is extremely important to Brazil, which stands as the 2nd largest producer. The search for alternative raw materials to wheat becomes increasingly necessary for the development of gluten-free products, increase the nutritional value and cost savings in the bakery sector. The mesquite pods have a high nutritional value and can be used as feedstock for the development of new food products. With these aspects, the objective of this study was to develop cookie enriched with mesquite flour which has high nutritional quality and importance to the economic development of the semi-arid northeast. In this work, the mature mesquite was used with a water content of 20% (wb). Drying experiments were performed at temperatures of 50, 60, 70 and 80 ° C. Mathematical models of Fick, Page, Cavalcanti Mata, Exponential Two Terms and Henderson & Pabis were used to fit the experimental data. Later, cookies were developed with mesquite flour and subjected to sensory analysis. The mesquite flour used in the cookie formulation with greater acceptance, was subjected to size grain, morphological, rheological, physico-chemical, determination of the chemical elements and was used for the production of cookies by using experimental design. The five best cookie formulations were subjected to sensory acceptance test. Water activity, firmness, fracture stress and color of all three formulations of cookies with greater acceptance were analyzed for 120 days of storage. From the results obtained, it can be said that the mathematical models Fick, Page, Cavalcanti Mata, Exponential Two Terms and Henderson & Pabis satisfactorily explained the experimental data of drying mesquite. The mesquite flour presented rheological characteristics suitable for production of cookies. The mesquite flour showed high concentration of fibers (15.10 g.100g-1), protein (9.12 g.100g-1), calcium (650.75.mg.100g-1) and phosphorous (879.12.mg.100g-1). The cookies made with 25% mesquite flour, 30% sugar and 45% palm fat content (experiment 4), 5% of mesquite flour, 50% sugar content and 45% content palm fat (experiment 7) and 15% of mesquite flour, 40% sugar and 35% palm fat content (experiment 9) were those who had greater acceptance and purchase intent. After the 120 days of storage, cookies of mesquite flour had their water activity and luminance increased, while its firmness, fracture stress, yellow and red intensity reduced. It is concluded that the cookies, of mesquite flour presented a high nutritional composition, high sensory acceptance, and similar quality characteristics to existing products on the market during storage.

Optically-transparent solids have a significant role in many emerging topics of fundamental and applied research, in areas related to Applied Optics and Photonics. In the functional devices based on them, the presence of ‘time-varying temperature fields’ critically limit their achievable performance, when used particularly for high power laser-related tasks such as light-generation, light-amplification, nonlinear-harmonic conversion etc. For optimization of these devices, accurate knowledge of the material thermal parameters is essential. Many optical and non-optical methods are currently in use, for the reliable estimation of the thermal parameters. The thermal diffusivity is a key parameter for dealing with ‘transient heat transport’ related problems. Although its importance in practical design for thermal management is well understood, its physical meaning however continues to be esoteric. The present effort concerns with a few investigations on the “Optical interrogation of ‘transient thermal conduction’ in dielectric solids”. In dielectric solids, the current understanding is that the conductive heat transport occurs only through phonons relevant to microscopic lattice vibrations. Introducing for the first time, a virtual linear translator motion as the basis for heat conduction in dielectric materials, the present investigation discusses an alternative physical mechanism and a new analytical model for the transient heat conduction in dielectric solids. The model brings into limelight a ‘new law of motion’ and a ‘new quantity’ which can be defined at every point in the material, through which time-varying heat flows resulting in time-varying temperature. Physically, this quantity is a measure for the linear translatory motion resulting from transient heat conduction. For step-temperature excitation it bears a simple algebraic relation to the thermal diffusivity of the material. This relationship helps to define the thermal diffusivity of a dielectric solid as the “translatory motion speed” measured at unit distance from the heat source. A novel two-beam interferometric technique is proposed and corroborated the proposed concept with significant advantages. Two new approaches are introduced to estimate thermal diffusivity of optically transparent dielectric solid; first of them involves measurement of the position dependent velocity of isothermal surface and second one depend on the measurement of position dependent instantaneous velocity of normalized moving intensity points. A ‘new mechanism’ is proposed and demonstrated to visualize, monitor and interrogate optically, the ‘linear translatory motion’ resulting from the transient heat flow due to step- temperature excitation. Two new approaches are introduced, first one is ‘mark’ and ‘track’ approach, it involves a new interaction between sample supporting unsteady heat flow with its ambient and produces optical mark. Thermal diffusivity is estimated by tracking the optical mark. Second one involves measurement of instantaneous velocity of optical mark for different step-temperature at a fixed location to estimate thermal diffusivity. A new inverse method is proposed to estimate thermal diffusivity and thermal conductivity from the volumetric specific heat capacity alone through thought experiment. A new method is proposed to predict volumetric specific heat capacity more accurately from thermal diffusivity.

Submitted by Emanuel Varela Cardoso (emanuel.varela@ufcg.edu.br) on 2018-08-17T17:30:45Z No. of bitstreams: 1 JOSÉ RICARDO FERREIRA OLIVEIRA – DISSERTAÇÃO (PPGEM) 2017.pdf: 2648257 bytes, checksum: 5e08d81aaa5973d7c6fd8bac23c313cc (MD5) / Made available in DSpace on 2018-08-17T17:30:45Z (GMT). No. of bitstreams: 1 JOSÉ RICARDO FERREIRA OLIVEIRA – DISSERTAÇÃO (PPGEM) 2017.pdf: 2648257 bytes, checksum: 5e08d81aaa5973d7c6fd8bac23c313cc (MD5) Previous issue date: 2017-11-30 / CNPq / A caracterização termofísica dos materiais utilizados na Engenharia é de grande importância para realização de projetos nas mais diversas áreas de conhecimento onde os fenômenos ligados aos processos de transferência de calor exercem um papel fundamental. A difusividade térmica é uma propriedade termofísica importantíssima na análise de problemas de difusão de energia térmica. Este trabalho teve como proposta a determinação desta propriedade utilizando um campo de temperatura periódico. Para isto, foi construído um dispositivo experimental com princípio de funcionamento no método de Angstrom, o qual faz uso de um fluxo de calor periódico de uma fonte controlada, gerando assim, um campo de temperatura periódico na amostra em teste. Termopares foram instalados nas amostras para captar os sinais de temperatura gerados pelo fluxo de calor periódico. A amplitude e a fase destes sinais foram obtidas por meio de um software de análise gráfica. O termopar mais próximo da fonte de calor foi adotado como referência, ao passo que a razão de amplitudes e a defasagem, entre os sinais térmicos registrados pelos demais termopares em relação ao registrado por àquele termopar , foram calculadas. Estes resultados foram utilizados em modelos matemáticos para determinar a difusividade térmica, que pode ser identificada ou atra vés da razão de amplitudes ou através da defasagem entre os perfis de temperatura. As amostras utilizadas neste trabalho foram de aço inox AISI 304, aço inox AISI 316 e de uma liga de memória de forma de níquel-titânio. Os valores de difusividade térmica identificados para estes materiais, quando foram comparados com valores disponíveis na literatura, obtiveram uma boa concordância, tendo em vista a faixa de incerteza apresentada. / Thermophysical characterization of materials used in engineering is very important for realization of projects in the most diverse areas of knowledge where the phenomena related to the process of heat transfer play an important role. Thermal diffusivity is a very important thermal property on the analysis of problems of diffusion of thermal energy. This work proposes the determination of this property using a periodic temperature field. For this, an experimental device was built with principle of operation in Angstrom’s method, which makes use of a periodic heat flow from a controlled source, thereby generating a periodic temperature field in the test sample. Thermocouples were installed on the samples for capture of signals generated by the periodic heat flow. Amplitude and phase of these signals were obtained by means of graphic analysis software. The thermocouple closest to the heat source was adopted as reference, and the ratio and phase lag, between the thermal signals registered by other thermocouples in relation to that registered by that thermocouple, were calculated. These results were utilized in mathematical models to determine the thermal diffusivity, whose identification can be performed either through the amplitude ratio or through the phase lag between the temperature profiles. Samples utilized in this work were stainless steel AISI 304, stainless steel AISI 316 and a shape memory alloy of nickel-titanium. Identified values of thermal diffusivity of these materials, when compared whit values available in literature obtained a good agreement, considering the range of uncertainty presented.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, desenvolveu-se um sistema de detecção fotoacústico para medidas simultâneas e independentes dos sinais fotoacústicos dianteiro e traseiro, utilizando dois microfones e um único feixe de excitação. Utiliza-se a diferença de fase entre estes sinais para a determinação da difusividade térmica de materiais, com base na abordagem teórica da técnica da Diferença de Fase dos Dois Feixes (T2F). Na metodologia apresentada não há a necessidade de se alternar o feixe de excitação entre as faces da amostra. Esta característica torna mais rápido o procedimento de medida e simplifica o monitoramento automatizado de processos dinâmicos que afetam a difusividade térmica do material, como a cura de resinas poliméricas. É apresentado o procedimento utilizado para determinar a diferença entre as fases intrínsecas dos microfones e o método empregado para compensar tal diferença e, assim, obter a defasagem entre os sinais fotoacústicos dianteiro e traseiro. O sistema de detecção desenvolvido é avaliado em medidas de difusividade térmica de amostras metálicas (aço inoxidável AISI 304 e aço SAE 1020) e poliméricas (polipropileno e polietileno de baixa densidade). Os resultados obtidos concordam de forma satisfatória com dados disponíveis na literatura. Finalmente, a aplicação do sistema proposto ao monitoramento de cura de amostras de resina epóxi indicou sua potencialidade de acompanhar, em tempo real, este tipo de processo dinâmico. / In this work, a photoacoustic detection system was developed for simultaneous and independent measurements of both front and rear photoacoustic signals, using two microphones and a single beam illumination mode. The phase-lag between these signals is used in the determination of thermal diffusivity of materials, based on the theoretical approach of the Two-Beam Phase-Lag technique. In the experimental setup presented in this work there is no need to alternate the light beam between the sample surfaces. This feature provides faster measurements and simplify the automated monitoring of dynamic processes that affect the material thermal diffusivity, as crosslinking processes. The procedure to determine the difference between the intrinsic phases of the microphones is presented, as well as the method to compensate this difference and to obtain the phase-lag between front and rear photoacoustic signals. The developed detection system is tested in thermal diffusivity measurements of metallic (AISI 304 stainless steel and SAE 1020 steel) and polymeric (polypropylene and low-density polyethylene) samples. The results are in good agreement with the available literature values. Finally, the system here proposed is applied in studies of epoxy resin curing, which shows its potentiality for real-time monitoring of dynamic process.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, desenvolveu-se um sistema de detecção fotoacústico para medidas simultâneas e independentes dos sinais fotoacústicos dianteiro e traseiro, utilizando dois microfones e um único feixe de excitação. Utiliza-se a diferença de fase entre estes sinais para a determinação da difusividade térmica de materiais, com base na abordagem teórica da técnica da Diferença de Fase dos Dois Feixes (T2F). Na metodologia apresentada não há a necessidade de se alternar o feixe de excitação entre as faces da amostra. Esta característica torna mais rápido o procedimento de medida e simplifica o monitoramento automatizado de processos dinâmicos que afetam a difusividade térmica do material, como a cura de resinas poliméricas. É apresentado o procedimento utilizado para determinar a diferença entre as fases intrínsecas dos microfones e o método empregado para compensar tal diferença e, assim, obter a defasagem entre os sinais fotoacústicos dianteiro e traseiro. O sistema de detecção desenvolvido é avaliado em medidas de difusividade térmica de amostras metálicas (aço inoxidável AISI 304 e aço SAE 1020) e poliméricas (polipropileno e polietileno de baixa densidade). Os resultados obtidos concordam de forma satisfatória com dados disponíveis na literatura. Finalmente, a aplicação do sistema proposto ao monitoramento de cura de amostras de resina epóxi indicou sua potencialidade de acompanhar, em tempo real, este tipo de processo dinâmico. / In this work, a photoacoustic detection system was developed for simultaneous and independent measurements of both front and rear photoacoustic signals, using two microphones and a single beam illumination mode. The phase-lag between these signals is used in the determination of thermal diffusivity of materials, based on the theoretical approach of the Two-Beam Phase-Lag technique. In the experimental setup presented in this work there is no need to alternate the light beam between the sample surfaces. This feature provides faster measurements and simplify the automated monitoring of dynamic processes that affect the material thermal diffusivity, as crosslinking processes. The procedure to determine the difference between the intrinsic phases of the microphones is presented, as well as the method to compensate this difference and to obtain the phase-lag between front and rear photoacoustic signals. The developed detection system is tested in thermal diffusivity measurements of metallic (AISI 304 stainless steel and SAE 1020 steel) and polymeric (polypropylene and low-density polyethylene) samples. The results are in good agreement with the available literature values. Finally, the system here proposed is applied in studies of epoxy resin curing, which shows its potentiality for real-time monitoring of dynamic process.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-06-08T12:29:33Z No. of bitstreams: 1 elaineaparecidacarvalho.pdf: 7755814 bytes, checksum: b31278b6963ad259e85e174cf59c5391 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-06-26T18:10:31Z (GMT) No. of bitstreams: 1 elaineaparecidacarvalho.pdf: 7755814 bytes, checksum: b31278b6963ad259e85e174cf59c5391 (MD5) / Made available in DSpace on 2017-06-26T18:10:31Z (GMT). No. of bitstreams: 1 elaineaparecidacarvalho.pdf: 7755814 bytes, checksum: b31278b6963ad259e85e174cf59c5391 (MD5) Previous issue date: 2013-03-18 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, três diferentes materiais (vidros, filmes finos e nanofluidos) foram analisados com o objetivo de verificar mudanças nas propriedades térmicas e ópticas devido a presença de nanopartículas de metais nobres. Nos vidros e filmes, o crescimento de nanopartículas foi induzido através do tratamento térmico das amostras enquanto que nos nanofluidos, a nucleação das nanopartículas foi obtida através de um procedimento químico de uma única etapa. A formação das nanopartículas metálicas nestes materiais foi confirmada pelas imagens de microscopia eletrônica e pelo pico de plasmon superficial presente nos espectros de absorção. Espectros Raman foram obtidos com a finalidade de verificar se ocorreu alguma mudança estrutural. Medidas de lente térmica foram realizadas em todas as amostras, fornecendo os valores da difusividade térmica. As matrizes vítreas estudadas foram germanato (Ge02 - PbO) e telurito (Te02 - PbO-Ge02), dopadas com nanopartículas de prata e com os íons terras raras Érbio, Ytérbio e Túlio na forma trivalente. Foi verificado que ocorreu um aumento de 20 % e 8 % na difusividade térmica dos vidros germanatos e teluritos, respectivamente, devido a adição de nanopartículas de prata e que o tratamento térmico provocou a quebra de anéis de tetraedros formados nos vidros germanato. Os filmes finos contendo nanopartículas de ouro e prata foram crescidos em um substrato através da técnica de co-sputtering utilizando a matriz vítrea de germanato (Ge02 - PbO) como alvo. Os resultados indicam a formação de estruturas diferentes daquelas detectadas no vidro, além de apresentar mudanças no comportamento térmico em relação a matriz vítrea. Nos nanofluidos de ouro e prata foram observados um aumento de 20% e 16%, respectivamente, na difusividade térmica em relação a difusividade térmica água pura. / In this work, three different materials (glasses, thin films and nanofluids) were analysed to check the changes in their thermal and optical properties due to the presence of noble metal nanoparticles. In the glasses and films, the nucleation of nanoparticles was induced by thermal treatment of the samples while in the nanofluids the nanoparticles were obtained through one-step chemical reaction. The presence of metallic nanoparticles was confirmed by electron microscopy images and by surface plasmon peaks detected via absorption technique in the ultraviolet and visible region of the electromagnetic spectrum. In addition, Raman spectra were obtained to check structural changes. Thermal lens measurements were performed in all samples to obtain the respective thermal diffusivity. Studied vitreous system were germanate (Ge02 - PbO) and tellurite (Te02 - PbO-Ge02) doped with silver nanoparticles, rare earth ions, erbium, thulium and ytterbium in the trivalent form. It was found an increase of 20% and 8% in the thermal diffusivity of germanate and tellurite glasses, respectively, due to the addition of silver nanoparticles. It also verified that the thermal treatment has caused the break of Ge04 tetrahedra rings. Thin films containing gold and silver nanoparticles were grown by the co-sputtering technique using the germanate vitreous matriz (Ge02 - PbO) as target. Raman results show structural differences between thin films and the corresponding glasses. This was reflected in a different thermal behavior. In gold and silver nanofluids were observed an increase of 20% and 16% in the thermal diffusivity in comparison with the thermal diffusivity of pure water, respectively.

Avec les récents développements obtenus grâce aux modèles globaux magnétohydrodynamiques en trois dimensions de la convection solaire, il est désormais possible de simuler des champs magnétiques structurés à grande échelle et présentant des inversions de polarité bien synchronisées dans chaque hémisphère. Ces modèles qui n'incluent, pour la plupart, aucune modélisation de la surface du Soleil génèrent donc leur dynamo avec l'action de la force électromotrice turbulente (FEM) et de la rotation différentielle uniquement. À partir de cette FEM, différentes techniques peuvent être utilisées pour extraire les coefficients de transport turbulent. Notamment, différents auteurs ont obtenu un tenseur alpha (coefficient du premier ordre) dont les 9 composantes présentent des amplitudes du même ordre, remettant en doute l'approximation faite dans le cas des modèles dynamo de type alphaOmega qui ne tient en compte qu’une de composante du tenseur. À partir d'un code d'analyse par décomposition en valeurs singulières pour évaluer les coefficients du tenseur alpha, nous avons généralisé la procédure pour extraire 18 des composantes du tenseur de deuxième ordre (tenseur beta). Les tenseurs alpha et beta obtenus par cette nouvelle procédure tel qu'appliquée aux sorties du modèle global EULAG-MHD, sont similaires aux tenseurs alpha et beta équivalant obtenus en utilisant l'approximation « Second Order Correlation Approximation ». À l'aide des coefficients de transport turbulent du premier ordre introduit dans un modèle dynamo en champ moyen, nous avons ensuite étudié certaines solutions magnétiques présentant des doubles dynamos. Cette analyse avait pour but de comparer les résultats obtenus par ce modèle simplifié caractérisé par la FEM provenant de EULAG-MHD aux résultats de EULAG-MHD directement. Cette preuve de concept nous a permis de démontrer que l'oscillation observée dans le champ magnétique en surface de EULAG-MHD pouvait provenir de l'action inductive d'une seconde dynamo. Une oscillation biennale est également observée dans plusieurs indices d'activité solaire dont l'origine n'est toujours pas établie. Il est évident que les deux modèles décrits ci-haut et le Soleil opèrent dans des régimes physiques différents. Toutefois, malgré leurs différences, le fait qu'il soit relativement facile de produire une seconde dynamo dans EULAG-MHD et dans le modèle en champ moyen indique que l'action inductive de la FEM peut facilement générer deux dynamos. Finalement, dans le but d'étudier les périodes de grands minima, phénomène encore non reproduit par les modèles globaux, nous avons ajouté une rétroaction magnétique sur l'écoulement azimutal au modèle dynamo cinématique en champ moyen décrit ci-haut. En analysant les solutions de ce modèle dynamo de type alpha2Omega non cinématique, nous avons pu reproduire la tendance observée jusqu'ici uniquement dans les modèles de type alphaOmega selon laquelle le nombre de nombre de Prandtl magnétique contrôle le rapport des périodes générées. De plus, en analysant une solution sur 50 000 ans présentant des périodes de grands minima et maxima non périodiques, nous avons obtenu une distribution de temps de séparation des grands minima presque exponentielle, caractéristique observée dans les reconstructions de l'activité solaire. La rotation différentielle associée à ces périodes de grands minima présente un niveau de fluctuation de 1% par rapport au profil moyen. Ce niveau de fluctuation est d'ailleurs comparable avec les reconstructions historiques de la rotation différentielle en surface obtenues lors du grand minimum de Maunder. / The recent developments achieved by tri-dimensionals magnetohydrodynamic (3D-MHD) global simulations of solar convection allow us to generate an organized large-scale magnetic fields with well-synchronized hemispheric polarity reversal. Because the vast majority of these simulations do not include a modelization of the Sun's surface layer, the generation of their dynamo is thus solely due to the action of the turbulent electromotive force (EMF) in conjunction with differential rotation. From this EMF, different methods can be used to extract the turbulent transport coefficients. In particular, various authors found a full 9 component alpha-tensor (first order coefficients) where all the components are of the same order of magnitude. This finding calls into question the alphaOmega approximation made by the vast majority of mean field dynamo models. We generalized a first order (alpha-tensor) singular value decomposition (SVD) analysis procedure to extract the 18 additional components of the second order tensor (beta-tensor). The alpha and beta tensors obtained by this new procedure as applied to the EULAG-MHD outputs, are similar to the equivalent alpha and beta tensors obtained using the second order correlation approximation (SOCA). By introducing the first order turbulent transport coefficients in a mean field dynamo model, we study the magnetic solutions where double dynamo modes were observed. This analysis allows us to compare the mean field dynamo solutions produced with the EMF, as extracted from EULAG-MHD, with the real magnetic output of EULAG-MHD. This proof of concept demonstrated that the quasi-biennal oscillation observed in the surface toroidal magnetic field in EULAG-MHD can be produced by the inductive action of a secondary dynamo. A similar quasi-biennal oscillation signal is also observed in multiple proxies of the solar activity whose origin is still not confirmed. Although the physical set of properties under which the two numerical models described above operate are different from the Sun, the fact that both models can reproduce a secondary dynamo shows us that the inductive action of the EMF can easily produce two dynamos. Finally, in order to study epochs of grand minima that still cannot be reproduced in global 3D-MHD simulations of convection, we added a magnetic feedback on the mean azimutal flow in our kinematic mean field model. This non-kinematic alpha2Omega model was able to reproduce the tendency of the Prandtl number (Pm) to control the ratio of the modulation period. More specifically, we found an inverse relation between Pm and the ratio of the main magnetic cycle period to the grand minima occurrence period. Moreover, by analyzing a simulation of a length of 50,000 years, where aperiodic periods of grand minima and maxima are observed, we found a waiting time distribution (WTD) of the grand minima close to an exponential, a characteristic also observed in the reconstruction of the solar activity. Finally, the level of fluctuation in the surface differential rotation associated with epochs of grand minima is ~1%. This level of fluctuation was also observed in historical reconstructions of the surface differential rotation during the Maunder minimum.

L’épithélium digestif est recouvert d’une couche protectrice de mucus, qui est un hydrogel perméable et viscoélastique. La couche de mucus est formée d'un réseau de fibres de mucines. Ces dernières sont des glycoprotéines de haut poids moléculaire avec un squelette protéique riche en sérine et thréonine, lié à une grande variété de O-glycanes qui représentent une source nutritionnelle pour les bactéries et/ou des ligands potentiels pour les adhésines bactériennes, contribuant ainsi probablement à la sélection et l'implantation d'un microbiote régio-spécifique. Nous nous sommes intéressés aux capacités muco-adhésives de L. lactis TIL448 par le couplage de (i) la microscopie à force atomique (AFM), à l'échelle de la cellule unique et en mode statique et (ii) la méthode hydrodynamique en chambre à écoulement cisaillé, à l'échelle de l’ensemble de la population bactérienne. Dans l'optique d'identifier la nature et le rôle fonctionnel des déterminants de surface mis en jeu, nous avons testé, outre la souche sauvage, la souche curée de plasmides TIL1230 et deux mutants TIL1289 et TIL1290, altérés dans la synthèse de pili et d'une protéine "mucus-binding", respectivement. Pour relier les propriétés muco-adhésives et diffusives de L. lactis, les capacités de migration de la souche TIL448 et de ses dérivés ont ensuite été évaluées dans des suspensions de PGM à concentration variable (0,5% et 5% (m/v)), en mettant en œuvre une nouvelle méthode "Diffusion Front Tracking" (DFT). Cette méthode consiste à suivre le front de diffusion de la suspension bactérienne au cours du temps au sein du réseau de PGM, dans une chambre de Hele-Shaw, couplée à une caméra CCD. Les bactéries L. lactis sont préalablement marquées avec la fuschine pour mieux visualiser le front de diffusion. Par ailleurs, nous avons démontré que les bactéries L. lactis ont tendance à être plus diffusives dans PGM 0,5% (m/v) que dans PGM 5% (m/v). La microstructure du réseau de mucines a donc été caractérisée par des approches de microrhéométrie 1 point (1P) et 2 points (2P) et de suivi de particules fluorescentes / The digestive epithelium is covered with a protective mucus layer, regarded as a viscoelastic and permeable hydrogel. Mucins are large glycoproteins with a serine and threonine-rich protein backbone, linked to a wide variety of O-linked oligosaccharide side chains arranged in a bottle-brush configuration. Such O-glycans are nutritive sources for bacteria and/or potential ligands for bacterial adhesins, probably contributing in this way to the selection of the species-specific microbiota. In this thesis, we focused on unraveling multi-scale interactions between a vegetal L. lactis subsp. lactis isolate, TIL448 and a model mucin, Pig Gastric Mucin (PGM). Our study, based on the combination of different biophysical approaches and tools, has allowed dissecting the muco-adhesive and diffusive phenotype of L. lactis TIL448, in relation with the nature of the bacterial surface determinants and the structural, mechanical and rheological properties of the PGM network. Firstly, the muco-adhesion of TIL448 were examined using the single-cell scale AFM measurements with dedicated lacto-probes and shear stress flow chamber experiments at the bacterial population level, under laminar flow conditions. We also tested the plasmid-cured strain and two mutants, obtained by disruption of the genes encoding the major pilin and the mucus-binding protein. Then, the diffusion ability of L. lactis was determined by implementing a novel method, named Diffusion Front Tracking (DFT). It consists of tracking the diffusion front of stained cell suspensions over time within the PGM network. In a second part, in order to have a more thorough understanding of the L. lactis muco-adhesive and diffusive ability, the microstructure and mechanical properties of PGM were determined. Gel microstructure for varying PGM concentration was probed by the analysis of diffusivities of 200-nm and 500-nm fluorescent nanoparticles with different surface properties (carboxyl-terminated, amine-terminated and neutral charged tracers), using fluorescence Multiple-Particle Tracking

This work deals with the study of diagnostic methods suitable for monitoring of the drying process of brick raw materials. Based on the extensive literature search, several parameters are selected, which are appropriate to monitoring during drying. In addition, a methodology for measuring these selected parameters is proposed. In the experimental part, the use of all described methods is gradually verified on the brick raw material with and without shortening additive (also known as grog). Was carried out: measurement of the surface temperature in the climatic chamber, determination of humidity distribution in the sample, determination of moisture diffusivity, determination of tensile strength, determination of ultrasonic wave velocity and determination of dynamic E-modulus of elasticity. Results of experiments and the gained experiences show, that at least two of the above-mentioned monitoring methods are very appropriate and beneficial – determination of moisture diffusivity and determination of tensile strength. In the work was described in detail the procedure of determination of moisture diffusivity of material. The dependence of moisture diffusivity on the moisture content of the dried material, has been described. Also, differences between raw material with grog and without grog has been described. As part of the practical verification of the experiment designed to determine the tensile strength at different humidity levels of test samples. A new shape of the test specimens and a new device were designed to allow them to be attached to a hydraulic press. The results of this work show that the tensile strength of the ceramic green bodies is primarily dependent on the moisture content of the material. The type of raw material almost does not affect the tensile strength.