The aim of this project was to enhance the current state of knowledge of the void structure of paper, and pigments used to coat paper. The porosities and pore size distributions of consolidated pigments were measured using mercury porosimetry. Prior to this work, mercury porosimetry was rarely used in this field due to problems associated with the conventional interpretation of mercury porosimetry data. These problems were examined and two limitations of mercury porosimetry were addressed. Firstly, the shrinkage of compressible samples causes an apparent increase in void volume and secondly, large void spaces shielded by smaller ones are not intruded until anomalously high applied pressures of mercury are reached. The first limitation was overcome by means of a new correction procedure which, uniquely, also allows the measurement of the bulk modulus of the continuous solid phase of a porous sample. Shielding effects have been taken into account by means of a software package known as Pore-Cor, which generates a three dimensional structure which has both a mercury intrusion curve and porosity in close agreement with experiment. It has also been possible to calculate the permeabilities and tortuosity of the simulated structure and this provides realistic and useful values, which may not be measured experimentally. Mercury porosimetry and a range of specialised absorption techniques, including liquid porosimetry, were used to characterise the porous structures of a highly filled paper which had been calendered using a range of different conditions. A unique feature of this work is that for the first time it has been shown that two porosimetric techniques which measure overlapping pore size distributions may be combined to give a better indication of the total pore size distribution.

No description available.

Standard catalyst characterisation techniques such as gas adsorption porosimetry and mercury porosimetry only account for some of the physical heterogeneity of the catalyst surface. They completely ignore the chemical heterogeneity present and in most cases consider pores present in the medium to be independent of each other. Thus, most results of characterisation (pore space descriptors such as BET surface area, BJH pore size distribution, mercury porosimetry surface area, etc.) are not accurate. This has been a major issue that remains to be resolved during the characterisation of fresh and coked catalysts. In this thesis, the use of a multi-component adsorption system is recommended as a step-change solution to this limitation. Two approaches are adopted. Firstly, integrated nitrogen-waternitrogen gas adsorption experiments are performed on fresh and coked catalysts. This established the significance of pore coupling by showing the presence of advanced adsorption. The method also helped to determine the location of coke deposits within catalysts and indicated that water vapour adsorption was a good probe to understand the sites responsible for coking. Secondly, coadsorption of immiscible liquids – cyclohexane and water – was performed on fresh and coked catalysts following which the displacement of cyclohexane by water was studied using NMR relaxometry and diffusometry. This novel approach takes the wettability of the surface into consideration, unlike the former methods. It is therefore a method that accounts for the chemical heterogeneity of the surface. It also helped determine the location of coke within catalysts. The different approaches are presented in the context of combustion of heavy oil in bitumen reservoirs, and the use of supercritical conditions that help to dissolve coke precursors in the isomerisation of 1-hexene. Thus, the solutions provided in this thesis are directions in which catalyst characterisation, especially distinguishing fresh and coked catalysts, and other porous materials, must be carried out.

The glancing angle deposition (GLAD) technique is now used by over one hundred research groups, each requiring a fundamental understanding of and new techniques for modulating the properties of GLAD in order to optimize their results. In this thesis, the structural characteristics of nanostructured columnar films were therefore investigated and quantified using gas adsorption porosimetry, focused ion beam tomography, optical methods, scanning electron microscopy (SEM) image analysis. Questions such as ``What is their surface area?'', ``How porous are they?'', ``How do the films evolve as they grow?'', and ``Can the structural characteristics be manipulated?'' were answered. Surface areas, determined from krypton gas adsorption, were found to be high, making GLAD promising for applications requiring large and rough surface interfaces. Specifically, peak specific surface areas of 700 +/- 150 m^2g^{-1}, 325 +/- 40 m^2g^{-1}, 50 +/- 6 m^2g^{-1} were measured for silica (SiO_2), titania (TiO_2) and indium tin oxide (ITO), respectively. Broad pore distributions, with peaks in the low mesoporous regime of 2 nm to 5 nm, were also determined. The internal surface area may also be up to three times as high as that of the externally exposed surface. As well, despite the fact that GLAD column broaden as they grow, the surface area increases linearly with film thickness. Focused ion beam milling, with concurrent SEM imaging, was then employed to investigate and reconstruct the three-dimensional structure of GLAD films in the tens of nanometers regime not measurable by krypton gas adsorption porosimetry. The measured growth scaling trends agreed with previous findings, but were determined using only one sample, instead of multiple samples of increasing thickness. Mean column diameters, center-to-center spacings, void spacings, and column densities were found to scale with thickness as w = (9.4 +/- 3.0) t^{0.35 +/- 0.09} nm, c = (24.8 +/- 5.2) t^{0.31 +/- 0.08} nm, v = (15.2 +/- 3.8) t^{0.25 +/- 0.06} nm, and d = (3400 +/- 2500) t^{-0.65 +/- 0.15} columns um^{-2}, respectively. Finally, spatially graded nanostructures were demonstrated by extending the GLAD technique to include macroscopic shadowing. Optically transparent, graded thickness and pitch helical films were fabricated with polarization selectivity over a spatial range of 30 mm, concurrent with 70 nm spectral tunability. These structures will be useful for tunable frequency photonic devices. / Micro-Electrical-Mechanical Systems (MEMS) and Nanosystems

No description available.

In this work, a steady-state, one-dimensional model was developed for the cathode side of the PEM fuel cell. The model results compared well with available literature results. The effects of operating temperature, cathode gas pressure, cathode gas porosity, and membrane thickness were studied. Carbon materials used for the gas diffusion layer (GDL) were characterized. The materials were: untreated and Teflon-treated carbon paper and untreated and Teflon-treated carbon cloth. Physisorption data were analyzed using the BET and the BJH methods to determine surface area and pore size distribution. Capillary flow porometry measurements provided the bubble point, mean flow, and smallest pore diameters and pore size distribution. Gas permeability measurements were performed. Mercury/non-mercury intrusion porosimetry measurements were performed to obtain pore size distribution and cumulative pore volume. The microstructure structure of the materials was examined using Scanning Electron Microscopy. The elemental composition of the samples was measured using Energy Dispersive X-ray Spectroscopy.

Les méthodes expérimentales utilisées actuellement pour déterminer la distribution de taille des pores (DTP) dans les milieux poreux présentent des inconvénients, tels que par exemple, la toxicité des fluides employés (porosimétrie à mercure). La base théoriques d'une nouvelle méthode pour obtenir la DTP a été proposée dans la littérature. Celle-ci est fondée sur l'injection de fluides à seuil, caractérisés par une contrainte de cisaillement en deçà de laquelle ils ne s'écoulent pas. L'idée principale de ces travaux théoriques est que l'écoulement de fluides à seuil à travers un milieu poreux permet d'obtenir sa DTP à partir de la mesure des débits correspondant à différents gradients de pression Q(∇P). L'objectif du travail proposé ici est de présenter une nouvelle méthode d'exploitation des données expérimentales Q(∇P) permettant d'obtenir de façon simple, robuste et reproductible les DTPs des milieux poreux analysés. La démarche consiste à évaluer la contribution au débit total des nouveaux pores qui s'incorporent à l'écoulement entre deux valeurs de ∇P. Ces nouveaux pores sont caractérisés par un rayon représentatif qui est fonction de la contrainte seuil du fluide et de ∇P. L'importance de leur contribution au débit total par rapport à celle d'un seul pore donne le nombre de pores dans l'échantillon ayant ce rayon représentatif. Cette méthode est d'abord testée et validée avec des expériences générées numériquement. Ensuite, elle est utilisée pour exploiter des données provenant d'expériences de laboratoire réalisées avec de différents milieux poreux. Les résultats obtenus en termes de DTPs sont comparés avec ceux fournis par d'autres techniques: porosimétrie à mercure et microtomographie. / Current experimental methods used to determine pore size distributions (PSD)of porous media present several drawbacks such as toxicity of the employed fluids (e.g., mercury porosimetry). The theoretical basis of a new method to obtain the PSD by injecting yield stress fluids through porous media and measuring the flow rate Q at several pressure gradients ∇P was proposed in the literature. On the basis of these theoretical considerations,an intuitive approach to obtain PSD from Q(∇P) is presented in this work. It relies on considering the extra increment of Q when ∇P is increased, as a consequence of the pores of smaller radius newly incorporated to the flow. This procedure is first tested and validated on numerically generated experiments. Then, it is applied to exploit data coming from laboratory experiments and the obtained PSDs are compared to those deduced by mercury porosimetry and micro tomography.

Nanostructured, porous materials offer great promise for application in areas such as energy storage, photovoltaics, and catalysis. These materials are often difficult to characterize because they are structurally and compositionally inhomogeneous, and disordered with features to small to be resolved by scanning probe techniques such as atomic force microscopy (AFM) and scanning electron microscopy (SEM). These shortcomings require that new techniques be developed that can be applied to real world systems to elucidate how the interplay of material composition and structure alters their performance. Towards this end, the development of a hybrid quartz crystal microbalance/ ellipsometric porosimetry (QCM/EP) technique is being pursued to facilitate the determination of a number of material parameters such as porosity, pore size distribution, and surface area. Additionally, the use of adsorbate probe molecules of varying polarity gives further information about adsorbate-surface interactions and surface chemistry characteristics. Simultaneous acquisition of both mass-based and refractive index based adsorption isotherms fosters mechanistic understanding about the behavior of adsorbates confined in mesopores while at the same time reducing the uncertainty in the analysis of the optical parameters acquired via ellipsometry. To highlight the power of this approach, studies of TiO₂ and TiC, electrode materials as model systems will be presented that have helped us validate measurement and modeling protocols for extracting physical properties. / text

The objective of this thesis is to determine the mineralogy and petrography of 13 'opuka' stone samples taken out from different construction phases of the Church of the Beheading of St. John the Baptist in Dolní Chabry. The analysis of a mineralogical composition and structural properties of the extracted samples alongside with a comparison of their physical characteristics provided a basis for estimation of the samples' origin within the construction phase. Methodology used for the samples analysis has been inspired by the methods described in project NAKI (no. DF13P01OVV008 ) also known as "Materiálový rozbor přírodního kamene - opuky - exaktními laboratorními metodami jako nástroj ke stanovení zdrojové oblasti". These methods includes besides macro and microscopic analysis also X-ray powder diffraction and high pressure mercury porosimetry which together provided a complete set of data about the samples. For the purpose of obtaining the general characteristic of the rock and the initial estimate of the content of mineral phases within it the optical microscopy was used. The results made it possible to classify the samples into four groups depending on content of a silica matrix. This in turn allowed to link some of the samples conclusively with some of the older construction phases of the site....

O presente trabalho teve como objetivo a implementação de técnicas de Ressonância Magnética Nuclear (RMN) para o estudo de meios porosos em geral, com potenciais aplicações no estudo de rochas, ossos, polímeros e materiais cerâmicos porosos. Devido à heterogeneidade e à complexidade desses meios, torna-se importante correlacionar variados parâmetros físicos que contenham informações tanto sobre a dinâmica molecular quanto sobre a estrutura físico-química dos poros e dos fluidos que os permeiam. Utilizando técnicas de RMN, é possível investigar esses parâmetros através da medida dos coeficientes de difusão e dos tempos de relaxação longitudinal e transversal dos fluidos presentes nos poros, que apresentam diferentes estados dinâmicos, variando desde um líquido isotrópico até um líquido com alta viscosidade ou organizado devido à sua interação com a superfície dos poros ou com partículas presentes nos fluidos. Para isso, foram empregadas técnicas de RMN baseadas especialmente em medidas de tempos de relaxação transversal que, quando adequadamente combinadas, permitem a construção de mapas bidimensionais que correlacionam propriedades da dinâmica molecular de fluidos saturantes nessas amostras em instantes diferentes do experimento, provendo informações sobre as dimensões e escalas temporais envolvidas na dinâmica dos fluidos saturantes dos meios porosos. Esses mapas foram obtidos a partir de dados experimentais obtidos com rochas petrolíferas saturadas com água via algoritmos de inversão da transformada de Laplace bidimensional. Este trabalho foi realizado utilizando a infraestrutura existente nos laboratórios de RMN do IFSC, sendo grande parte do hardware e software desenvolvidos durante o projeto de doutorado. Foi desenvolvido um programa para processamento da transformada inversa de Laplace de dados unidimensionais, sendo este utilizado para o estudo de propriedades de adesão de pastilhas de gesso quando submetidas a diferentes pressões. Além disso, foram desenvolvidos modelos computacionais para simular essas propriedades relacionadas aos experimentos utilizados para o estudo dos meios porosos. Parte deste trabalho contou com a realização de dos estudos na Victoria University of Wellington em colaboração com o professor Paul T. Callaghan através do Programa de Doutorado e Estágio no Exterior (PDEE) da CAPES. / This study aimed to implement Nuclear Magnetic Resonance (NMR) for the study of porous media in general, with potential applications in the study of rocks, bones, porous polymers and ceramics. Due to the heterogeneity and complexity of these media, it becomes important to correlate various physical parameters that contain information about both the molecular dynamics on the structure and physical chemistry of pore fluid and the permeate. Using NMR techniques, it is possible to investigate these parameters by measuring diffusion coefficients, transverse and longitudinal relaxation times of fluids within the pores, which have different dynamical states, ranging from an isotropic liquid to a liquid with high viscosity or organized due to its interaction with the surface of the pores or particles suspended in fluid. For this, we employed NMR techniques based especially on measurements of transverse relaxation times, which when properly combined, allow the construction of two-dimensional maps that correlate properties of the molecular dynamics of fluids saturating these samples at different times of the experiment, providing information on dimensions and time scales involved in the dynamics of fluids saturating the porous media. These maps were obtained from experimental data on water-saturated oil rocks via inversion of two-dimensional Laplace transform. This work was performed using the existing infrastructure in the IFSC NMR laboratories and much of the hardware and software was developed during the doctoral project. We developed a program for processing the one-dimensional inverse Laplace transform data, which was used for studying the adhesion properties of gypsum pellets when subjected to different pressures. Additionally, we developed computational models to simulate physical-chemical properties related to the experiments used for the studies of fluids within porous media. Part of this work included studies performed in Victoria University of Wellington in collaboration with Professor Paul T. Callaghan through the Programa de Doutorado e Estágio no Exterior (PDEE) from CAPES.