Zugl.: Stuttgart, Univ., Diss., 2006.

Stuttgart, Univ., Diss., 2002.

The goal of this work is to improve the understanding of adsorption-induced deformation in nanoporous (and in particular microporous) materials in order to explore its potential for material characterization and provide guidelines for related technical applications such as adsorption-driven actuation. For this purpose this work combines in-situ dilatometry measurements with in-depth modeling of the obtained adsorption-induced strains. A major advantage with respect to previous studies is the combination of the dilatometric setup and a commercial sorption instrument resulting in high quality adsorption and strain isotherms. The considered model materials are (activated and thermally annealed) carbon xerogels, a sintered silica aerogel, a sintered hierarchical structured porous silica and binderless zeolites of type LTA and FAU; this selection covers micro-, meso- and macroporous as well as ordered and disordered model materials. All sample materials were characterized by scanning electron microscopy, gas adsorption and sound velocity measurements. In-situ dilatometry measurements on mesoporous model materials were performed for the adsorption of N2 at 77 K, while microporous model materials were also investigated for CO2 adsorption at 273 K, Ar adsorption at 77 K and H2O adsorption at 298 K. Within this work the available in-situ dilatometry setup was revised to improve resolution and reproducibility of measurements of small strains at low relative pressures, which are of particular relevance for microporous materials. The obtained experimental adsorption and strain isotherms of the hierarchical structured porous silica and a micro-macroporous carbon xerogel were quantitatively analyzed based on the adsorption stress model; this approach, originally proposed by Ravikovitch and Neimark, was extended for anisotropic pore geometries within this work. While the adsorption in silica mesopores could be well described by the classical and analytical theory of Derjaguin, Broekhoff and de Boer, the adsorption in carbon micropores required for comprehensive nonlocal density functional theory calculations. To connect adsorption-induced stresses and strains, furthermore mechanical models for the respective model materials were derived. The resulting theoretical framework of adsorption, adsorption stress and mechanical model was applied to the experimental data yielding structural and mechanical information about the model materials investigated, i.e., pore size or pore size distribution, respectively, and mechanical moduli of the porous matrix and the nonporous solid skeleton. The derived structural and mechanical properties of the model materials were found to be consistent with independent measurements and/or literature values. Noteworthy, the proposed extension of the adsorption stress model proved to be crucial for the correct description of the experimental data. Furthermore, it could be shown that the adsorption-induced deformation of disordered mesoporous aero-/xerogel structures follows qualitatively the same mechanisms obtained for the ordered hierarchical structured porous silica. However, respective quantitative modeling proved to be challenging due to the ill-shaped pore geometry of aero-/xerogels; good agreement between model and experiment could only be achieved for the filled pore regime of the adsorption isotherm and the relative pressure range of monolayer formation. In the intermediate regime of multilayer formation a more complex model than the one proposed here is required to correctly describe stress related to the curved adsorbate-adsorptive interface. Notably, for micro-mesoporous carbon xerogels it could be shown that micro- and mesopore related strain mechanisms superimpose one another. The strain isotherms of the zeolites were only qualitatively evaluated. The result for the FAU type zeolite is in good agreement with other experiments reported in literature and the theoretical understanding derived from the adsorption stress model. On the contrary, the strain isotherm of the LTA type zeolite is rather exceptional as it shows monotonic expansion over the whole relative pressure range. Qualitatively this type of strain isotherm can also be explained by the adsorption stress model, but a respective quantitative analysis is beyond the scope of this work. In summary, the analysis of the model materials' adsorption-induced strains proved to be a suitable tool to obtain information on their structural and mechanical properties including the stiffness of the nonporous solid skeleton. Investigations on the carbon xerogels modified by activation and thermal annealing revealed that adsorption-induced deformation is particularly suited to analyze even small changes of carbon micropore structures. / Ziel dieser Arbeit ist es, dass Verständnis der adsorptionsinduzierter Deformation von nanoporösen (insbesondere mikroporösen) Materialien zu erweitern, um ihr Potenzial für die Materialcharakterisierung zu erforschen. Zusätzlich sollen Orientierungshilfen für technische Anwendungen, wie z.B. adsorptionsgetriebene Aktuatoren, bereitgestellt werden. Hierfür kombiniert diese Arbeit in-situ Dilatometriemessungen und detaillierte Modellierung der gemessenen adsorptionsinduzierten Dehnungen. Der wesentliche Vorteil dieser Arbeit gegenüber vorherigen Studien ist die Kombination des dilatometrischen Messaufbaus mit einer kommerziellen Gasadsorptionsanlage, was die Messung qualitativ hochwertiger Adsorptions- und Dehnungsisothermen erlaubt. Die betrachteten Materialsysteme sind (aktivierte und geglühte) Kohlenstoffxerogele, ein gesintertes Silica-Aerogel, ein gesintertes, hierarchisch strukturiertes, poröses Silica und binderlose Zeolithe der Typen LTA und FAU. Diese Auswahl umfasst mikro-, meso- und makroporöse ebenso wie geordnete und ungeordnete Modellmaterialien. Alle Modellmaterialien wurden mit Rasterelektronenmikroskopie, Gasadsorption und Schallgeschwindigkeitsmessungen charakterisiert. In-situ Dilatometriemessungen an mesoporösen Modellsystemen wurden für N2-Adsorption bei 77 K durchgeführt, während alle mikroporösen Modellsysteme zusätzlich bei CO2-Adsorption (273 K), Ar-Adsorption (77 K) und H2O-Adsorption (298 K) untersucht wurden. Der verfügbare Messaufbau für in-situ Dilatometrie wurde im Rahmen dieser Arbeit weiterentwickelt, um Auflösung und Reproduzierbarkeit der Messungen von kleinen Dehnungen zu verbessern, was insbesondere für mikroporöse Materialien von Bedeutung ist. Die experimentellen Adsorptions- und Dehnungsisothermen des hierarchisch strukturierten, porösen Silicas und des mikro-makroporösen Kohlenstoff-Xerogels wurden mit dem adsorption-stress-Modell quantitativ ausgewertet. Hierfür wurde das adsorption-stress-Modell, ursprünglich eingeführt von Ravikovitch et al., für die Verwendung von anisotropen Porengeometrien erweitert. Während die der Deformation zu Grunde liegende Adsorption im Fall des mesoporösen Silicas gut mit der klassischen und analytischen Theorie von Derjaguin, Broekhoff und de Boer beschrieben werden konnte, erforderte die Adsorption in den Kohlenstoffmikroporen umfassende Berechnungen mittels nichtlokaler Dichtefunktionaltheorie. Um die adsorptionsinduzierten Spannungen mit entsprechenden Dehnungen zu korrelieren, wurden zusätzlich mechanische Modelle für die untersuchten Materialien entworfen. Das resultierende theoretische Konstrukt aus Adsorptions-, adsorption-stress- und mechanischem Modell wurde auf die ermittelten experimentellen Daten angewandt und strukturelle und mechanische Eigenschaften der Modellmaterialien bestimmt, d.h. Porengröße bzw. Porengrößenverteilung sowie die mechanischen Module der porösen Matrix und des unporösen Festkörperskeletts. Es konnte gezeigt werden, dass die ermittelten Materialeigenschaften konsistent mit unabhängigen Messungen und/oder Literaturwerten sind. Hierbei ist zu beachten, dass sich die Erweiterung des adsorption-stress-Modells für eine korrekte Auswertung der experimentellen Daten als zwingend erforderlich erwies. Des Weiteren konnte gezeigt werden, dass die adsorptionsinduzierte Deformation von ungeordneten mesoporösen Aero-/Xerogelstrukturen qualitativ denselben Mechanismen folgt, die für das geordnete, hierarchisch strukturierte, poröse Silica identifiziert wurden. Die entsprechende quantitative Modellierung erwies sich allerdings als schwierig, da die Poren in Aero-/Xerogelstrukturen geometrisch schlecht zu fassen sind. Gute Übereinstimmung zwischen Modell und Experiment konnte nur für das Stadium gefüllter Poren und den relativen Druckbereich der Monolagenbildung erzielt werden. Der Zwischenbereich der Multilagenadsorption erfordert ein komplexeres Modell, um die Spannung quantitativ korrekt zu beschreiben, die sich auf Grund der gekrümmten Adsorbat-Adsorptiv-Grenzfläche im Material ausbildet. Mit Hinblick auf mikro-mesoporöse Kohlenstoffxerogele konnte gezeigt werden, dass sich dort Deformationsmechanismen von Mikro- und Mesoporen überlagern. Die Dehnungsisothermen der Zeolithe wurden nur qualitativ ausgewertet. Das Ergebnis für den Zeolithen vom Typ FAU stimmt gut mit anderen in der Literatur beschriebenen Experimenten und dem theoretischen Verständnis überein, das sich aus dem adsorption-stress-Modell ergibt. Im Gegensatz dazu ist die gemessene Dehnungsisotherme des Zeolithen vom Typ LTA eher ungewöhnlich, da sie monotone Expansion des LTA-Zeolithen über den gesamten Druckbereich zeigt. Qualitativ kann dieses Ergebnis ebenfals mit dem adsorption-stress-Modell erklärt werden, aber eine detaillierte, quantitative Analyse übersteigt den Rahmen dieser Arbeit. Insgesamt erweist sich die Analyse der adsorptionsinduzierten Dehnungen der Modellmaterialien als geeignetes Mittel, um Informationen über deren strukturelle und mechanische Eigenschaften zu erlangen, was auch die Steifigkeit des unporösen Festkörperskeletts miteinschließt. Desweiteren zeigen Untersuchungen an aktivierten und geglühten Kohlenstoffxerogelen, dass adsorptionsinduzierte Deformation insbesondere geeignet ist, um kleine Änderungen an Mikroporenstrukturen zu analysieren.

Zugl.: Stuttgart, Univ., Diss., 2003.

This diploma work is focused on exploitation of high-temperature dilatometry in sintering of advanced ceramic materials. Newly developed software is presented in this diploma work. This software is able to calculate activation energy of sintering process via concept of Master Sintering Curve. In the second part of diploma work the software was verified by evaluation of sintering of four different ceramics materials. The following activation energies of sintering were calculated: 990kJ/mol for tetragonal ZrO2 (3mol% Y2O3), 620kJ/mol for cubic ZrO2 (8mol% Y2O3) and 640kJ/mol resp. 720kJ for Al2O3 with two different particle size.

This diploma thesis deals with the preparation of doped piezoceramic materials based on BaTiO3 using electrophoretic deposition. Five rare earth oxides, i.e. Er2O3, Dy2O3, Eu2O3, Tb407 and CeO2, were used as dopants in amounts of 1, 3, and 5 wt. %. The prepared deposits were evaluated in terms of preparation methodology, high temperature dilatometry, X-ray diffraction analysis, relative density, mean grain size, hardness and fractographic analysis. The study of dilatometric curves described the sintering behavior and its changes at different material compositions. X-ray diffraction analysis revealed a tetragonal phase in all samples; the tetragonality of the BaTiO3 crystalline cell decreased with dopant content. By a suitable choice of dopant, it was possible to significantly increase the relative density of sintered samples, their hardness and at the same time prevent the samples from coarsening of the microstructure during heat treatment. A relative density up to 98 %, a mean grain size below 1 m and a hardness of over 10 GPa were achieved. Analysis of the fracture surfaces revealed that the fracture mode was transcrystalline for the most of studied materials; only the samples doped with cerium dioxide had fracture surfaces with both transcrystalline and intercrystalline fracture modes. Based on the obtained results, a suitable composition of the material for the intended use in a layered piezoceramic harvester was identified, which, in addition to the BaTiO3 layers, consists of functionally-protective Al2O3 and ZrO2 layers.

Sintering is a one of the key step in a processing of bulk ceramic materials. New sintering methods were invented in the last years. These new sintering methods, according to their authors, can be used for obtaining finer final microstructure of ceramics only by modifying the heating schedule. This work is focused on an influence of the Two Step Sintering method on the final microstructure for oxide ceramics. Obtained experimental results have shown that the effectivity of the Two Step Sintering method is rising with crystallographic symmetry of used material. Thesis is also focused on a high-temperature dilatometry and concept of the Master Sintering Curve. This concept was used for calculation of the activation energy of sintering and finding different sintering mechanisms acting in the intermediate and final stage of sintering. Activation energy of sintering was compared with activation energy of grain growth with target to find the kinetic window. Kinetic window can allow a sintering without a grain growth. Master Sintering Curve method was also used in a pressure assisted unconventional sintering technique Spark Plasma Sintering. Master Sintering Curve applied to a Spark Plasma Sintering technique reveals and quantified different sintering mechanisms acting in Spark Plasma Sintering. These findings led to preparation of transparent tetragonal ZrO2.

Alkali compounds were added to a South African coal with a high swelling propensity and the behaviour of the blends were investigated. A vitrinite-rich bituminous coal from the Tshikondeni coal mine in the Limpopo province of South Africa was used. To reduce the influence of the minerals in the coal, the coal was partially demineralized by leaching with HCl and HF. The ash content of the coal sample was successfully reduced from 17.7% to 0.6%. KOH, KCl, K2CO3 and KCH3CO2 were then added to the demineralized coal in mass percentages of 1%, 4%, 5% and 10%. The free swelling indices (FSI) of the blends were determined and the samples were subjected to acquisition of TMA and TG-MS data. Addition of these potassium compounds to the demineralized coal reduced the swelling of the vitrinite-rich coal. From the free swelling indices of the various mixtures, it was concluded that the potassium compounds reduce the swelling of the coal in the following order of decreasing impact: KCH3CO2 > KOH > K2CO3 > KCl. From dilatometry experiments done on the blends with the 10% addition of potassium compounds, it was seen that with the addition of potassium compounds to the demineralized coal, a reduction in dilatation volume was obtained. The influence of the potassium compound in decreasing order: K2CO3> KOH> KCH3CO2> KCl. An increase in the softening temperature was observed for the demineralized coal-alkali blends. Thermogravimetric analyses were performed on the demineralized coal-potassium blended samples (<75 μm). These samples were pyrolyzed under a nitrogen atmosphere to a maximum temperature of 1200 °C using a heating rate of 10 °C/min. The relative reactivity for each of the blends with the different wt% addition was determined. From these results it was seen that KCH3CO2 increased the relative reactivity, whereas the KOH, KCl and K2CO3 showed an inhibiting influence. The attached mass spectrometer provided information on the low molecular mass gaseous products formed in the various temperature ranges as the thermal treatment proceeded. From the mass spectroscopy results, it was found that the potassium compounds decreased the temperature at which maximum evolution of H2 takes place. Thermomechanical analyses were performed on the 10 wt% addition of the potassium compounds to the demineralized coal. During TMA analyses, the sample was heated to 1000 °C using a heating rate of 10 °C/min. From the TMA result obtained it was clear that the addition of KCl did not have an influence on the swelling of the demineralized coal. All results are discussed. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

Alkali compounds were added to a South African coal with a high swelling propensity and the behaviour of the blends were investigated. A vitrinite-rich bituminous coal from the Tshikondeni coal mine in the Limpopo province of South Africa was used. To reduce the influence of the minerals in the coal, the coal was partially demineralized by leaching with HCl and HF. The ash content of the coal sample was successfully reduced from 17.7% to 0.6%. KOH, KCl, K2CO3 and KCH3CO2 were then added to the demineralized coal in mass percentages of 1%, 4%, 5% and 10%. The free swelling indices (FSI) of the blends were determined and the samples were subjected to acquisition of TMA and TG-MS data. Addition of these potassium compounds to the demineralized coal reduced the swelling of the vitrinite-rich coal. From the free swelling indices of the various mixtures, it was concluded that the potassium compounds reduce the swelling of the coal in the following order of decreasing impact: KCH3CO2 > KOH > K2CO3 > KCl. From dilatometry experiments done on the blends with the 10% addition of potassium compounds, it was seen that with the addition of potassium compounds to the demineralized coal, a reduction in dilatation volume was obtained. The influence of the potassium compound in decreasing order: K2CO3> KOH> KCH3CO2> KCl. An increase in the softening temperature was observed for the demineralized coal-alkali blends. Thermogravimetric analyses were performed on the demineralized coal-potassium blended samples (<75 μm). These samples were pyrolyzed under a nitrogen atmosphere to a maximum temperature of 1200 °C using a heating rate of 10 °C/min. The relative reactivity for each of the blends with the different wt% addition was determined. From these results it was seen that KCH3CO2 increased the relative reactivity, whereas the KOH, KCl and K2CO3 showed an inhibiting influence. The attached mass spectrometer provided information on the low molecular mass gaseous products formed in the various temperature ranges as the thermal treatment proceeded. From the mass spectroscopy results, it was found that the potassium compounds decreased the temperature at which maximum evolution of H2 takes place. Thermomechanical analyses were performed on the 10 wt% addition of the potassium compounds to the demineralized coal. During TMA analyses, the sample was heated to 1000 °C using a heating rate of 10 °C/min. From the TMA result obtained it was clear that the addition of KCl did not have an influence on the swelling of the demineralized coal. All results are discussed. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

Dresden, Techn. Univ., Diss., 2000.