The coalburg seam coal is an example of difficult to float bituminous coal. Laboratory tests conducted on coalburg flotation feed sample revealed recovery values around 28% with 15% product ash when using fuel oil as collector under natural pH conditions. A detailed study showed that increasing pH from natural value of 5.6 to 7.5 provided a significant improvement in recovery of approximately 32 absolute percentage points. The improvement is believed to be result of the release of humic acids from the surface and the dispersion of clay particles thereby leaving a more hydrophobic surface. Based on the tests conducted with various commercially available collectors, oleic acid was selected as a model collector for oxidized coals. Conventional flotation tests found an increase in combustible recovery of 10 absolute percentage points above the pH improvement using 4:1 blend of fuel oil and oleic acid. The problem of higher ash in conventional cell product due to entrainment was minimized by the use of wash water in a flotation column. A flotation concentrate containing less than 7.5% ash was produced while recovering around 75% of the combustible material. Further testing using fatty acids-fuel oil blend also showed evidence of a near 200% increase in flotation rate.

Green chemistry principles served as a guide for three industrially-relevant projects. In the first project, silylamines were applied as reversible ionic liquids for carbon dioxide capture from post-combustion flue gas streams. The effect of silylamine structure was thoroughly researched to develop a comprehensive library of silylamines and an accompanying set of structure-property relationships. The proposed solvent systems have the potential to present significant energy savings, as design has focused on their use in a non-aqueous, solvent-free environment. The second project also dealt extensively with carbon dioxide capture, as a reversible, in-situ protecting group for amines. Three strategies for the reversible protection of amines using carbon dioxide were developed and evaluated. Further, a chemoselective reaction was performed using carbon dioxide to protect a reactive amine and consequentially direct reactivity elsewhere within the same molecule. The carbon dioxide-protection technology developed has significant impact in multi-step industrial syntheses, as reversible, in-situ protection with carbon dioxide could eliminate the need for separate protection and deprotection unit operations. Lastly, a study was performed on the thermal degradation and stabilization of PVC in the presence of both plasticizers and thermal stabilizers. The study combined both model compound experiments as well as work with bulk PVC blends to gain a holistic understanding of the processes that take place during the degradation and stabilization of PVC. A bio-based plasticizer was investigated as a replacement for petroleum-based phthalate plasticizers. Additionally, two novel thermal stabilizers for PVC were presented and evaluated.

Supramolecular polymer networks are prepared basing on two different supramolecular interactions, ionic interaction and hydrogen bonds interaction. Ionic interaction was introduced in P(BMA-co-MA) with CaCO3 as a filler. The presence of Ca2+ is confirmed with X-ray diffraction by the apperence of specific ionic peak. The hydrogen bond interaction was introduced by two approaches. One is to first prepare a supramolecular monomer bearing DA moiety then supramolecular polymer P(MAAM-co-St) and P(MAP-co-St) are prepared by polyaddition. In the other approach, the supramolecular polymer is synthesized by one-step PUU polycodensation from the reagent containing multiple-hydrogen-bond sequence. The presence of intermolecular hydrogen bonds is detected by FTIR qualitatively, and the strengh, quantified as Kass, is calculated by 1H-NMR for different moieties respectively. Solubility tests indicate that the introduction of supramolecular interaction in the traditional polymers leads to the crosslinking in different extents. Consequently, materials are strengthened showing better thermo-endurence property and higher modulus when the content of supramolecular moiety is increased. Furthermore, rheological analysis is performed to investigate the viscoelasticity and to track the thermo reversibility

This thesis primarily focuses on the systematic understanding of structure – reactivity relationships in two representative systems: bixbyite and related structures as well as indium doped CeO2. Topotactic reaction routes have gained significant attention over the past two decades due to their potential to access kinetically controlled metastable materials. This has contributed substantially to the understanding of solid state reaction pathways and provided first insights into mechanisms. Contrary to the widely used ex-situ methods, in – situ techniques including powder x-ray diffraction and thermogravimetric – differential thermal analysis have been employed extensively throughout this work in order to follow the reaction pathways in real time. Detailed analysis of the AVO3 (A = In, Sc) bixbyite reactivity under oxidative conditions has been carried out and a variety of novel metastable oxygen defect phases have been identified and characterized. The novel metastable materials have oxygen deficient fluorite structures and consequently are potential ion conductors. Structural aspects of the topotactic vs. reconstructive transformations are illustrated with this model system. The structure – reactivity study of AVO3 phases was extended to AVO3 perovskite family. Based on the research methodologies and results from AVO3 bixbyite reactivity studies a generalized mechanistic oxidation pathway has been established with a non-vanadium phase, ScTiO3 bixbyite. However, there is stark contrast in terms of structural stability and features beyond this stability limit during AVO3 and ScTiO3 bixbyite reaction pathways. A series of complex reaction sequences including phase separation and phase transitions were identified during the investigation of ScTiO3 reactivity. The two-step formation pathway for the fluorite – type oxide ion conductor Ce1-xInxO2-δ (0 ≤ x ≤ 0.3) is being reported. The formation of the BaCe1-xInxO3-δ perovskites and the subsequent CO2-capture reaction with the formation of Ce1-xInxO2-δ (0 ≤ x ≤ 0.3) has been investigated in detail. The two-step formation pathway is contrasted with the unsuccessful direct method. The stability and the extent of In – doping for the CeO2 fluorite phases that can be achieved through this CO2 – capture method are reported. The necessity and strategies for the selection of appropriate intermediate precursors for the preparation of doped CeO2 are also reported.

Šio darbo tikslas - ištirti polioksietilen(20) sorbitano monolaurato, sorbitano monopalmitato, polioksietilen(20) sorbitano tristearato ir sorbitano trioleato įtaką alkilakrilato krospolimero tiesioginės (a/v) emulsijos stabilumui. Tyrimo objektai - emulsija, pagaminta naudojant 0,6% koncentracijos alkilakrilato krospolimerą; nejonogeninės paviršinio aktyvumo medžiagos: polioksietilen(20) sorbitano monolauratas (Tween 20), sorbitano monopalmitatas (Span 40), polioksietile(20) tristearatas (Tween 65) ir sorbitano trioleatas (Span 85). Tyrimo uždaviniai: išanalizuoti literatūros duomenis apie nejonogenines paviršinio aktyvumo medžiagas ir jų įtaką alkilakrilato krospolimero emulsinėms savybėms; ištirti paviršinio aktyvumo medžiagų: polioksietilen(20) sorbitano monolaurato, sorbitano monopalmitato, polioksietilen(20) sorbitano tristearato ir sorbitano trioleato įtaką emulsinių lašelių dydžiui ir klampai; įvertinti paviršinio aktyvumo medžiagų įtaką emulsijos fiziniam stabilumui taikant diferencinio centrifugavimo testą ir šaldymo - šildymo ciklą; įvertinti laikymo sąlygų įtaką emulsinių lašelių dydžiui ir stabilumui. Literatūros analizė parodė, kad net maža alkilkrospolimero koncentracija (0,2-0,8%) pasižymi geromis emulsinėmis savybėmis ją derinant su nejonogeninėmis PAM. Rasta duomenų apie šio polimero sąveiką su polioksietilen(20) sorbitano trioleatu (Tween 85), tačiau šiame darbe tyrinėjami objektai iki šiol nebuvo tyrinėti, todėl yra aktualu ištirti nejonogeninių PAM... [toliau žr. visą tekstą] / Thesis goal - to explore impact of polyethylene glycol sorbitan monolaurate, sorbitan monopalmitate, polyethylene sorbitan tristearate and sorbitan trioleate to stability of direct (oil/water) emulsion of alkyl acrylate crosspolymer. Thesis object – emulsion, made with 0,6% concentration of Alkyl Crosspolymer; non-ionogenic surfactants: polyoxyethylene (20) sorbitan monolaurate, sorbitan monopalmitate, polyoxyethylene (20) sorbitan tristearate, sorbitan trioleate. Thesis objectives – To analyse sources of literary about the effects of non-iogenic surfactants on the stability of emulsion with alkyl acrylate crosspolymer; influence of non-ionogenic surfactants to size of emulsion droplets and viscosity; influence of non-ionogenic surfactants to physical stability of emulsion during centrifugation test and heating-cooling cycle; influence of conditional atmosphere to size of emulsion droplets and stability. The analysis of literary sources revealed that even a small concentration of Alkyl Crosspolymer (0.2–0.8%) has good emulsion properties, when combined with non-ionogenic surfactants. Data on the interaction of this polymer with polyoxyethylene (20) sorbitan trioleate (Tween 85) has been found; however, objects studied in this thesis have not been explored before, thus it is relevant to analyze the effects of non-iogenic surfactants on the stability of emulsion with alkyl acrylate crosspolymer. The obtained results showed that the analyzed non-ionogenic surfactants influence... [to full text]

In discussions of heterogeneous catalysis and other surface-related phenomena, the dynamical properties of the catalytic material are often neglected, even at elevated temperatures. An example is the three-way catalyst (TWC), used for treatment of exhaust gases from combustion engines operating at several hundred degrees Celsius. In the TWC, reduced ceria (CeO2-x) is one of the key components, where it functions as an oxygen buffer, storing and releasing oxygen to provide optimal conditions for the catalytic conversion of the pollutants. In this process it is evident that dynamics plays a crucial role, not only ionic vibrations, but also oxygen diffusion. In this thesis, the structure and dynamics of several ionic crystalline compounds and their surfaces have been studied by means of Molecular dynamics (MD) simulations and Lattice dynamics (LD) calculations. The main focus lies on CeO2-x, but also CeO2, MgO and CaF2 have been investigated. The presence of oxygen vacancies in ceria is found to lead to significant distortions of the oxygen framework around the defect (but not of the cerium framework). As a consequence, a new O-O distance emerges, as well as a significantly broadened Ce-O distance distribution. The presence of oxygen vacancies in ceria also leads to increased dynamics. The oxygen self-diffusion in reduced ceria was calculated from MD simulations in the temperature range 800-2000 K, and was found to follow an Arrhenius behaviour with a vacancy mechanism along the crystallographic <100> directions only. The cation and anion vibrational surface dynamics were investigated for MgO (001) using DFT-LD and for CaF2 (111) in a combined LEED and MD study. Specific surface modes were found for MgO and increased surface dynamics was found both experimentally and theoretically for CaF2, which is isostructural with CeO2. Many methodological aspects of modeling dynamics in ionic solids are also covered in this thesis. In many cases, the representation of the model system (slab thickness, simulation box-size and the choice of ensemble) was found to have a significant influence on the results.

This thesis deals with developing a thermodynamically consistent model to simulate the electromechanical response of ionic polymer-metal composites based on Euler-Bernoulli beam theory. Constitutive assumptions are made for the Helmholtz free energy and the rate of dissipation. The governing equations involving small deformations are formulated using the conservation laws, the power theorem, and the maximum rate of dissipation hypothesis. The model is extended to solve large deformation cantilever beams involving pure bending which could be used in the characterization of the material parameters. A linear finite element solution along with a staggered time stepping algorithm is provided to numerically solve the governing equations of the small deformations problem under generalized electromechanical loading and boundary conditions. The results are in qualitative and quantitative agreement with the experiments performed on both Nafion and Flemion based Ionic Polymer-Metal Composite strips.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24003号 / エネ博第439号 / 新制||エネ||83(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 萩原 理加, 教授 佐川 尚, 教授 野平 俊之 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Conventional glass ionomer cements (GICs), which continue to gain acceptance as superbly biocompatible dental materials, were first released in the early 1970s as a result of research into combining the advantages of silicate cements and polyalkenate cements. The chemistry of GICs is based upon the aqueous reaction between an ion-leachable fluoride glass and polyacid which yields the final cross-linked insoluble ionomer (ionic polymer). The significant advantages of GICs include direct adhesion to tooth structures, fluoride release, minimal dimensional change on curing, significant ease of use and superb biocompatibility, to the extent that affected proximal tooth structures may be retained, remineralised , and strengthened against further caries. GICs have, however, been unfavourably compared with other restorative materials in their mechanical properties and setting characteristics, in particular their relative weakness, the time limitations for the acid-base reaction to proceed to acceptable maturity, and the susceptibility of the immature cement to water sorption or desiccation.

Electrospinning is a method of producing nano structured material from a polymer solution or melt using high strength electric fields. It is a process that has yet to find extensive industrial application yet shows promise if obstacles such as low rate of production overcome perhaps by more complete theoretical modelling. This work examines the effects of adding an ionic salt to a solution of poly(vinyl alcohol) in water. The direct effect was an increase the charge density and electric current. It was found that an increase in charge density decreases the mass deposition rate and forms a thinner initial jet. When the sign of the charge on the polymer solution was changed from positive to negative the charge density increased and the initial jet diameter and mass deposition rate also decreased. It was proposed that a smaller radius of curvature is formed by the Taylor cone at higher charge densities resulting in a smaller “virtual orifice”. The extent of the bending instability was explored and it was found that adding ionic salt results in a decrease in the bending instability resulting in thicker fibres. Changing the sign of the charge on the polymer solution from positive to negative resulted in an increase in the bending instability and resulted in thinner fibres. The charge transfer mechanisms used in different electrospinning models are explored and some assumptions not explicitly stated are discussed. From this discussion a generalized equation describing the charge transport mechanisms is proposed.