NMR is gaining increasing interest in civil engineering for applications regarding microstructure characterization as e.g., to determine pore sizes or to monitor moisture transport in porous materials. This study reveals the capability of NMR as a tool for pore size characterization. Therefore, we measured floor screed and synthetic materials at partial and full saturation. For most examined materials, the pore size distribution was successfully determined using either a reference or a calibration method. Since diffusion effects were observed for some samples in single-sided NMR measurements, further tests employing an NMR core analyzer were carried out in a homogeneous magnetic field. The finally obtained surface relaxivity of floor screed (50 μm/s) resulted to be much higher than suggested by literature.

The topic of the Ph.D. thesis was focused on the process of sintering alumina and zirconia ceramic materials with the aim to compare kinetics of sintering sub-micro and nanoparticle systems. Zirconia ceramic powders stabilized by different amount of yttria addition in the concentration range of 0 – 8 mol% were used. The different crystal structure (secured by yttria stabilization) of zirconia, as found, did not play statistically proven role in the process of zirconia sintering. The possible influence was covered by other major factors as particle size and green body structure, which does affect sintering in general. According to the Herrings law, the formula predicting sintering temperature of materials with different particle size was defined. The predicted sintering temperatures were in good correlation with the experimental data for zirconia ceramic materials prepared from both, coarser submicrometer, and also nanometer powders. In case of alumina ceramics the predicted and experimentally observed sintering temperature values did not match very well. Mainly the nanoparticle alumina materials real sintering temperature values were markedly higher than predicted. The reason was, as shown in the work, strong agglomeration of the powders and strong irregularities of particle shape. The major role of green body microstructure in the sintering process was confirmed. The final density of ceramic materials was growing in spite of sintering temperature, which was decreasing together with pore - particle size ratio (materials with similar particle size were compared). Sintering temperature was increasing together with growing size of pores trapped in the green body structure. Clear message received from the above mentioned results was the importance of elimination of stable pores with high coordination number out off the green body microstructure during shaping ceramic green parts. Same sintering kinetics model was successfully applied on the sintering process of submicro- and also nanometer zirconia ceramics. Activation energy of nanometer zirconia was notably lower in comparison to submicrometer material. For the sintering of nanoparticle zirconia was typical so called “zero stage” of sintering, clearly visible on kinetic curves. It was found out, that processes running in zirconia “green” material during zero stage of sintering are heat activated and their activation energy was determined. Pores of submicrometer zirconia were growing in an open porosity stage of sintering just a slightly (1.3 times) compared to the nanoparticle zirconia, where the growth was much higher (5.5 times of the initial pore diameter). This difference was most probably caused by preferential sintering of agglomerates within the green bodies and by particle rearrangement processes which appears in the zero stage of sintering of nanoparticular ceramics. The technology of preparation of bulk dense ytria stabilized zirconia nanomaterial with high relative density of 99.6 % t.d. and average grain size 65nm was developed within the thesis research.

Mesoporous γ-alumina is the most extensively used catalysts support in a wide range of catalytic processes. The usefulness of γ-alumina relies on its favorable combination of physical, textural, thermal, and chemical properties. Pore structure properties are among the most important properties, since high surface area and large pore volume enable higher loading of active catalytic phases, while design of pore size and pore size distribution is critical to optimize pore diffusional transport and product selectivity. In addition, accurate determination of surface area (SA), pore volume (PV) and pore size distribution (PSD) of porous supports, catalysts, and nanomaterials is vital to successful design and optimization of these materials and to the development of robust models of pore diffusional resistance and catalyst deactivation.In this dissertation, we report a simple, one-pot, solvent-deficient process to synthesize mesoporous γ-alumina without using external templates or surfactants. XRD, TEM, TGA and N2 adsorption techniques are used to characterize the morphologies and structures of the prepared alumina nanomaterials. By varying the aluminum salts or the water to aluminum molar ratio in the hydrolysis of aluminum alkoxides, γ-alumina with different morphologies and pore structures are synthesized. The obtained alumina nanomaterials have surface areas ranging from 210 m2/g to 340 m2/g, pore volumes ranging from 0.4 cm3/g to 1.7 cm3/g, and average pore widths from 4 to 18 nm. By varying the alcohols used in the rinsing and gelation of boehmite/bayerite precursors derived from a controlled hydrolysis of aluminum alkoxides, the average pore width of the γ-aluminas can be tuned from 7 to 37 nm. We also report improved calculations of PSD based on the Kelvin equation and a proposed Slit Pore Geometry model for slit-shaped mesopores of relatively large pore size (>10 nm). Two structural factors, α and β, are introduced to correct for non-ideal pore geometries. The volume density function for a log normal distribution is used to calculate the geometric mean pore diameter and standard deviation of the PSD. The Comparative Adsorption (αs) Method is also employed to independently assess mesopore surface area and volume.

This cumulative dissertation is a compendium of five peer-reviewed and published scientific papers on developing an advanced NMR Cryoporometry toolbox for pore architecture characterization. The dissertation contains five chapters. The first introduces porous materials, their types and applications. Chapter two describes the fundamentals of fluid phase equilibria in mesoporous solids and how modifications of the well-known Laplace equation describe various fluid phase equilibria. The basic principles of the Gas Sorption and NMR Cryoporometry techniques are discussed. In chapter three, different characterization techniques are amalgamated onto a common framework which can be used to compare fluid phase coexistence in porous materials of different pore sizes. Chapter four explains a completely new NMR Cryoporometry characterization methodology developed for cylindrical and spherical pore shapes. Chapter five concludes and crowns the present work by discussing the complementary benefits of the advanced technique in characterizing random porous materials and accounting for pore connectivity effects. All materials synthesized for the work in this dissertation have been obtained through collaborations with the groups of Profs. Dr. Michael Fröba and Simone Mascotto of the Hamburg University and Prof. Dr. Dirk Enke of the Leipzig University.:Table of Contents Thesis Summary ........................................................................................................1 List of publications ......................................................................................................2 Acknowledgements ...................................................................................................4 CHAPTER 1:.............................................................................................................10 Introduction ..............................................................................................................10 CHAPTER 2:.............................................................................................................12 Fluid Phase Equilibria in Mesoporous Solids ..........................................................12 2.1 Gas Sorption................................................................................................... 13 2.1.1 Adsorption Isotherms................................................................................ 15 2.1.2 Adsorption Hysteresis............................................................................... 18 2.1.3 Scanning Behavior.................................................................................... 23 2.2 NMR Cryoporometry ....................................................................................... 25 2.2.1 Pore Size Distribution (PSD)....................................................................... 28 2.3 Serially-Connected Pore Model (SCPM)......................................................... 29 2.4 Problem Statement ......................................................................................... 30 CHAPTER 3:..............................................................................................................32 Analogy between Characterization Techniques ......................................................32 • Publication 3. On the Comparative Analysis of Different Phase Coexistences in Mesoporous Materials CHAPTER 4:.............................................................................................................42 An Advanced NMR Cryoporometry Approach.........................................................42 • Publication 4.1. Nuclear Magnetic Resonance Cryoporometry Study of Solid−Liquid Equilibria in Interconnected Spherical Nanocages • Publication 4.2. A novel approach for advanced thermoporometry characterization of mesoporous solids: Transition kernels and the serially connected pore model CHAPTER 5:.............................................................................................................65 Characterizing Random Porous Materials................................................................65 • Publication 5.1. Comparative Gas Sorption and Cryoporometry Study of Mesoporous Glass Structure: Application of the Serially Connected Pore Model • Publication 5.2. Impact of Geometrical Disorder on Phase Equilibria of Fluids and Solids Confined in Mesoporous Materials Appendix A:.............................................................................................................100 Porous Solid Characterization Techniques............................................................100 A.1: Mercury Intrusion Porosimetry (MIP) ........................................................... 100 A.1.1. Experimental Set-up.............................................................................. 101 A.2: Gas Sorption................................................................................................ 103 A.2.1. Experimental Set-Up ............................................................................. 103 A.2: NMR Cryoporometry.................................................................................... 106 A.2.2. Experimental Set-Up ............................................................................. 106 Appendix B:..............................................................................................................109 Supporting information ............................................................................................109 Appendix C:.............................................................................................................115 Author contributions ................................................................................................115 Bibliography ............................................................................................................117

Benefited from the efficiency of hydraulic fracturing and horizon drilling, the production of unconventional oil and gas resources, such as shale gas and tight oil, has grown quickly in 21th century and contributed to the North America oil and gas production. Although the new enhancing oil recover (EOR) technologies and strong demand spike the production of unconventional resources, there are still unknowns in recovery mechanisms and phase behavior in tight rock reservoirs. In such environment, the phase behavior is altered by high capillary pressure owing to the nanoscale pore throats of shale rocks and it may also influence minimum miscibility pressure (MMP), which is an important parameter controlling gas floods for CO2 injection EOR. To investigate this influence, flash calculation is modified with considering capillary pressure and this work implements three different method to calculate MMP: method of characteristics (MOC); multiple mixing cell (MMC); and slim-tube simulation. The results show that CO2 minimum miscibility pressure in nanopore size reservoirs are affected by gas-oil capillary pressure owing to the alternation of key tie lines in displacement. The values of CO2-MMP from three different methods match well. Moreover, in tight rock reservoirs, the heterogeneous pore size distribution, such as the ones seen in fractured reservoirs, may affect the recovery mechanisms and MMP. This work also investigates the effect of pore size heterogeneity on multicomponent multiphase hydrocarbon fluid composition distribution and its subsequent influence on mass transfer through shale nanopores. According to the simulation results, compositional gradient forms in heterogeneous nanopores of tight reservoirs because oil and gas phase compositions depend on the pore size. Considering that permeability is small in tight rocks and shales, we expect that mass transfer within heterogeneous pore size porous media to be diffusion-dominated. Our results imply that there can be a selective matrix-fracture component mass transfer during both primary production and gas injection secondary recovery in fractured shale rocks. Therefore, molecular diffusion should not be neglected from mass transfer equations for simulations of gas injection EOR or primary recovery of heterogeneous shale reservoirs with pore size distribution. / Master of Science / The new technologies to recover unconventional resources in oil and gas industry, such as fracturing and horizontal drilling, boosted the production of shale gas and tight oil in 21st century and contributed to the North America oil and gas production. Although the new technologies and strong demand spiked the production of tight oil resources, there are still unknowns of oil and gas flow mechanisms in tight rock reservoirs. As we know, the oil and gas resources are stored in the pores of reservoir formation rock. During production process, the oil and gas are pushed into production wells by formation pressure. However, the pore radius of shale rock is extremely small (around nanometers), which reduces the flow rate of oil and gas and raises capillary pressure in pores. The high capillary pressure will alter the oil and gas phase behavior and it may influence the value of minimum miscibility pressure (MMP), which is an important design parameter for CO2 injection (an important technology to raise production). To investigate this influence, we changed classical model with considering capillary pressure and this modified model is implemented in different methods to calculate MMP. The results show that CO2 -MMP in shale reservoirs are affected by capillary pressure and the results from different methods match well. Moreover, in tight rock reservoirs, the heterogeneous pore size distribution, such as fractures in reservoirs, may affect the flow of oil and gas and MMP value. So, this work also investigates the effect of pore size heterogeneity on oil and gas flow mechanisms. According to the simulation results, compositional gradient forms in heterogeneous nanopores of tight reservoirs and this gradient will cause diffusion which will dominate the other fluid flow mechanisms. Therefore, we always need to consider molecular diffusion in the simulation model for shale reservoirs.

Background: Separation science is heavily reliant on materials to fulfill ever more complicated demands raised by other areas of science, notably the rapidly expanding molecular biosciences and environmental monitoring. The key to successful separations lies in a combination of physical properties and surface chemistry of stationary phases used in liquid chromatographic separation, and this thesis address both aspects of novel separation materials. Methods: The thesis accounts for several approaches taken during the course of my graduate studies, and the main approaches have been i) to test a wild-grown variety of published methods for surface treatment of fused silica capillaries, to ascertain firm attachment of polymeric monoliths to the wall of microcolumns prepared in silica conduits; ii) developing a novel porogen scheme for organic monoliths including polymeric porogens and macromonomers; iii) evaluating a mesoporous styrenic monolith for characterization of telomers intended for use in surface modification schemes and; iv) to critically assess the validity of a common shortcut used for estimating the porosity of monoliths prepared in microconduits; and finally v) employing plasma chemistry for activating and subsequently modifying the surface of rigid, monodisperse particles prepared from divinylbenzene. Results: The efforts accounted for above have resulted in i) better knowledge of the etching and functionalization parameters that determine attachment of organic monoliths prepared by radical polymerization to the surface of silica; ii) polar methacrylic monoliths with a designed macroporosity that approaches the desired "connected rod" macropore morphology; iii) estab¬lishing the usefulness of monoliths prepared via nitroxide mediated polymerization in gradient polymer elution chromatography; iv) proving that scanning electron microscopy images are of limited value for assessing the macroporous properties of organic monoliths, and that pore measurements on externally polymerized monolith cocktails do not represent the porous properties of the same cocktail polymerized in narrow confinements; and v) showing that plasma bromination can be used as an activation step for rigid divinylbenzene particles to act as grafting handles for epoxy-containing telomers, that can be attached in a sufficiently dense layer and converted into carboxylate cation exchange layer that allows protein separations in fully aqueous eluents.

Deux approches pour caractériser les milieux poreux en terme de distribution de taille de pores (DTP) sont développées au sein de l'équipe ECPS. Ce travail a pour but de confirmer expérimentalement leurs validités. A l'instar des autres méthodes utilisant l'intrusion du mercure, l'adsorption isotherme ou la thermoporosimétrie, la première méthode consiste à utiliser un fluide à seuil d'écoulement. En effet, l'utilisation de l'écoulement d'un fluide à seuil de type Herschel-Bulkley, au travers d'un poreux, en fonction du gradient de pression permet (en utilisant les solutions analytique et numérique du problème inverse) de déterminer la fonction de distribution de la taille de pores. La seconde méthode utilise l'admittance complexe d'un milieu poreux, mesurée à partir de la réponse en débit à une sollicitation harmonique du gradient de pression. Comme la fréquence de la sollicitation est reliée aux rayons des pores par le biais de la profondeur de pénétration hydrodynamique, l'admittance permet de retrouver la distribution de taille de pores par la résolution numérique du problème inverse associé. Ces deux techniques sont basées sur le modèle de faisceaux de capillaires parallèles employé dans la plupart des autres études qui traitent du même problème. Nos expériences s'appuient sur des milieux poreux calibrés. L'application de ces techniques aux milieux poreux réels se fait actuellement en collaboration avec le TREFLE de Bordeaux. Les résultats expérimentaux obtenus affirment clairement la validité et l'applicabilité de ces deux méthodes pour la caractérisation de la DTP. Il est désormais envisageable de les transférer pour un usage industriel. / Two approaches to characterize porous media in terms of pore size distribution (PSD) are developed within our ECPS team. The aim of this study is to experimentally confirm their validity. Like the other methods using mercury intrusion, adsorption isotherm or thermoporometry, the first method consists in the use of a fluid flow threshold. Indeed, the use of flow of a yield-stress fluid like those of Herschel-Bulkley's, through a porous media, versus the pressure gradient, permits (using the analytical and numerical solutions of the inverse problem) to determine the distribution function of its PSD. The second method uses the complex admittance of a porous medium, measured from the flow rate response to a harmonic pressure gradient. As the frequency of the sollicitation is related to the pore radius through the hydrodynamic penetration depth, the admittance allows to determine the PSD using numerical solution of the associated inverse problem. Both techniques are based on the parallel capillaries bundle model, as used in most of similar studies. Our experiments use calibrated porous media. The application of these techniques to real porous media is currently lead in collaboration with the TREFLE (Bordeaux). Our experimental results clearly confirm the validity and the applicability of these methods for the characterization of the PSD. It is now possible to transfer them for an industrial use.

Les mousses à cellules ouvertes ont diverses applications industrielles, par exemple pour des échangeurs de chaleur, des réacteurs structurés, la filtration, la catalyse, récepteurs solaires volumétriques en raison de leurs propriétés uniques telles qu'une importante porosité et une surface spécifique élevée. Pour déterminer théoriquement la surface spécifique géométrique et les relations entre les paramètres géométriques de mousses, une corrélation mathématique généralisée a été développée. A cet effet, la géométrie de la tetrakaidecahedron a été utilisé et différentes formes de sections transversales de brins de structures en mousse ont été pris en compte de façon explicite. La corrélation dérivée pour prédire les propriétés géométriques peut facilement être étendue à des formes différentes. Des simulations numériques 3-D à l'échelle des pores ont été réalisées pour étudier la perte de charge et la conductivité effective thermique. L'écoulement du fluide à travers la mousse à cellule ouverte a été réalisé dans trois régimes différents: les régimes de Darcy, transitoire et inertiel. L'importance des propriétés géométriques sur les caractéristiques d'écoulement de fluide et leurs inclusions dans les corrélations proposées pour prédire la perte de charge est discutée. La question « Les paramètres d'Ergun peuvent-ils avoir des valeurs numériques constantes ou non ? » est discutée. Trois différentes corrélations étaient dérivées pour prédire la conductivité thermique effective à la fois isotrope et anisotrope des mousses. Les paramètres géométriques de la matrice de mousse étaient introduits dans les corrélations pour prédire la conductivité thermique effective. / Open cell foams have diverse industrial applications e.g. heat exchangers, structured reactors, filtration due to their unique properties such as high porosity and high specific surface area. In order to theoretically determine the geometric specific surface area and relationships between geometrical parameters of isotropic open cell foams, a generalized mathematical correlation was developed. For this purpose the tetrakaidecahedron geometry was used and different shapes of strut cross-sections of foam structures were taken explicitly into account. The derived correlation to predict geometrical properties can be easily extended to different strut shapes. 3-D numerical simulations at pore scale were performed to study the pressure drop characteristics and effective thermal conductivity. Fluid flow through open cell foam was performed in three different regimes: Darcy regime, transition regime and inertia regime. Importance of geometrical properties on fluid flow characteristics and their inclusion in the proposed correlations for predicting pressure drop is discussed. "Can Ergun parameters have constant numerical values or not" is also extensively discussed. Three different correlations were derived to predict the effective thermal conductivity for both, isotropic and anisotropic open cell foams. Geometrical parameters of foam matrix were introduced in the correlations to predict effective thermal conductivity.

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.

Made available in DSpace on 2017-07-21T19:26:10Z (GMT). No. of bitstreams: 1 Jocenei Antonio Oliveira.pdf: 2309316 bytes, checksum: 8527d62e93fbe03d332c4ffaa65aedda (MD5) Previous issue date: 2014-06-10 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Soil water retention properties can be described by so-called soil-water characteristic curve (SWCC) or retention curve (WRC). This curve expresses the relationship between matric potential and soil moisture based on weight or volume. Through the attainment and subsequent analytical interpolation of the WRC, it’s possible the indirect estimative of the pore-size distribution (PSD) curve of any porous system. Sometimes, obtaining the WRC may be a time-consuming process or involve the use of equipment not available in some laboratories. Thus the development of an alternative method to obtain the WRC and after the PSD becomes desirable, since these are properties of extreme importance to characterize porous media. The main objective of this study is to create and adapt methodology for obtaining PSD using computer simulation in tomographic images with micrometer resolution. In this study, there were used samples of sand and glass beads of different grain sizes for the generation of the PSD curve using a Haines’ funnel on balance. After WRC achievement, these were adjusted through an analytical model and then there were built experimental PSD curve. PSD were also determined by adaptation of a computer program using tomographic images of these samples. The results of obtained WRC associated with geometric models to predict the entry point of air have only revealed the idea about how may occur drying of the samples, showing only morphological considerations are not sufficient to describe this situation. The investigated porous systems homogeneity was able to be visualized by comparing the PSD curves in terms of their widths. / Propriedades de retenção da água no solo podem ser descritas pela chamada curva característica de água no solo ou curva de retenção (CR). Esta curva exprime a relação entre potencial mátrico e a umidade do solo à base de massa ou volume. Mediante o levantamento da CR e posterior interpolação analítica, pode-se estimar indiretamente a curva de distribuição de poros (CDP) de um sistema poroso qualquer. Algumas vezes, a obtenção da CR pode ser um processo demorado ou envolver a utilização de equipamentos não disponíveis em alguns laboratórios. Desta forma, o desenvolvimento de uma metodologia alternativa para a obtenção da CR e posteriormente da CDP se faz desejável, uma vez que se trata de propriedade de extrema importância para a caracterização de um meio poroso. O objetivo principal deste trabalho é criar e adaptar metodologia para a obtenção de CDPs utilizando simulação computacional em imagens tomográficas com resolução micrométrica. No presente estudo, foram utilizadas amostras de areias e esferas de vidro de diferentes granulometrias para o levantamento das CRs usando um funil de Haines adaptado. Depois de obtidas as CRs, essas foram ajustadas através do modelo de ajuste de van Genuchten e obtidas as CDPs (primeira derivada da CR). Também foram obtidas CDPs mediante a adaptação de um programa computacional que utiliza informações de imagens tomográficas dessas amostras. Os resultados das CDPs levantadas pelos dois métodos mostram alguma concordância. Verificou-se, no entanto, que apenas considerações sobre a morfologia dos poros não são suficientes para descrever a forma com que as amostras são drenadas.