Thesis--Helsingfors.

Thesis (Ph. D.)--Florida State University, 2003. / Advisor: Dr. John G. Dorsey, Florida State University, College of Arts and Sciences, Department of Chemistry and Biochemistry. Title and description from dissertation home page (viewed Aug. 23, 2004). Includes bibliographical references.

Thesis (M.S.)--University of Michigan, 1971.

Thesis (M.Sc.)--Memorial University of Newfoundland, 1999. / Restricted until November 2000. Bibliography: leaves 132-140.

Thesis (Ph.D.)--Cleveland State University, 2009. / Abstract. Title from PDF t.p. (viewed on Sept.8, 2009). Includes bibliographical references (p. 101-104). Available online via the OhioLINK ETD Center and also available in print.

Thesis (Ph. D.)--West Virginia University, 2006. / Title from document title page. Document formatted into pages; contains xiv, 152 p. : ill. (some col.). Includes abstract. Includes bibliographical references.

Orientador: Younés Messaddeq / Coorientador: Agnieszka Joanna Pawlicka Maule / Banca: Caio Eduardo de Campos Tambelli / Banca: Rogéria Rocha Gonçalves / Resumo: Esta dissertação apresenta a preparação e caracterização de membranas condutoras iônicas baseadas em celulose produzida pela bactéria Gluconacetobacter xylinus. Estas membranas foram preparadas a partir da imersão de membranas de celulose bacteriana (CB) em soluções aquosas de ácidos (ácido acético e ácido trifluoroacético) e/ou plastificantes (trietanolamina e glicerol). Estrutura e perfil térmico destas membranas condutoras foram investigados por difração de raios X (DRX), microscopia eletrônica de varredura (MEV), termogravimetria (TG), calorimetria exploratória diferencial (DSC), espectroscopia vibracional na região do infravermelho (FTIR) e espectroscopia de espalhamento Raman. As propriedades elétricas foram avaliadas utilizando-se espectroscopia de impedância eletroquímica (EIE). As análises de DRX mostram o aumento de plastificante diminui a cristalinidade das amostras, cujo recobrimento das microfibrilas pelo plastificante pode ser visualizado por análise de MEV, e os valores de condutividade iônica obtidos são maiores em comparação aos da CB seca. A condutividade na membrana é dependente do conteúdo de umidade e o plastificante age impedindo a desidratação da membrana. Foi observado também que combinações de ácido e plastificante resultaram em membranas com maiores condutividades do que aquelas em que houve apenas adição do plastificante, uma vez que a adição de ácidos pode aumentar a condutividade protônica / Abstract: This dissertation presents the preparation and characterization of ionic conducting membranes based on cellulose produced by bacteria Gluconacetobacter xylinus. These membranes have been prepared from bacterial cellulose membranes (BC) soaked in acids (acetic and trifluoroacetic acids) and/or plasticizer (triethanolamine and glycerol) aqueous solutions. The structure and thermal behavior of the conducting membranes were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry (TG), differential scanning calorymetry (DSC), infrared spectroscopy (FTIR) and Raman spectroscopy. Electrical properties were performed utilizing electrochemical impedance spectroscopy (EIS). From XRD analyses the amorphous phase becomes larger after increasing the amount of plasticizer that covers the cellulose microfibrils as revealed by SEM, and the obtained conductivity values were high in comparison to dried BC. The conductivity in the membrane is dependent on the moisture content and the plasticizer acts avoiding complete membrane dryness. It was also observed that the combination of acid and plasticizer resulted in membranes with higher ionic conductivity than plasticized ones, once the addition of acids may improve protonic conductivity / Mestre

The aim of this thesis was to research the new synthesis methodology of ionothermal synthesis, used for the synthesis of zeolite type materials, mainly aluminophosphates. An ionic liquid or eutectic mixture is to act as both the organic template and the solvent, hence eliminating the space filling effects in the reaction from the water. Initial reactions were carried out using the ionic liquid 1-ethyl-3-methylimidazolium bromide which acted as the solvent and template in the production of four three-dimensional structures and one layered structure. The addition of cobalt into the aluminophosphate framework was investigated and resulted in three different cobalt-aluminophosphates being synthesised, including one new zeolite framework. Experiments were carried out into the effect of altering the imidazolium cation alkyl chain. It appears likely that in the presence of fluoride, some of the imidazolium cations undergo a metathesis reaction forming 1,3-dimethylimidazolium which acts as a template in the formation of an aluminophosphate. Preliminary investigations have also been started into the effects of changing the ionic liquid anion from bromide to phosphorus hexafluoride and bis((trifluoromethyl)sulfonyl)amide. The use of these anions resulted in the production of several different one and two-dimensional structures. The use of eutectic mixtures as solvent and template was also investigated as a cheaper, more easily synthesised solvent than the ionic liquids. The results show a new methodology of eutectic mixtures acting as template delivery agents through the slow, in situ decomposition of the urea derivative of the eutectic mixture. This synthesis method resulted in the formation of nine one and two-dimensional aluminophosphates.

A series of hydrophobic ionic liquids (ILs) have been employed to extract acetic acid (AcOH) or formaldehyde (HCHO) from aqueous solutions at atmosphere pressure. The ILs, mainly trihexyl(tetradecyl)phosphonium ([P6,6,6,14]+) carboxylate based ILs, were tested as a function of the anion chain length, which ranges from isobutyrate ([IB]-) to dodecanoate ([D]-). Most of these ILs show a large two-phase region and high extraction efficiency. Furthermore, tetraoctylphosphonium ([P8,8,8,8]+) and trihexyl(tetradecyl)ammonium ([N6,6,6,14]+) based ILs were also investigated to study the effect of the cation on extraction performance. Besides pure IL extraction, the mixture of IL and other chemicals, such as matched carboxylic acid, alkane and ester, were also investigated on extraction. The matched carboxylic acid could enhance the extraction performance and thus could be called ‘enhancer’. A balance point could be found for the ratio IL/enhancer to obtain a better extraction in each {H2O + AcOH + IL/enhancer} system, compared with the corresponding pure IL liquid-liquid equilibrium (LLE). Several ILs, including [P6,6,6,14]+ based ILs and imidazolium based ILs, were investigated on extraction of HCHO. Among these ILs, the imidazolium based ILs performed better than the [P6,6,6,14]+ based ILs in terms of two-phase region, hydrophobicity of IL-rich phase and partition coefficient/relative selectivity. The UNIQUAC method was employed to correlate the LLE data for pure IL systems. Some physical property data, such as density and viscosity, of ILs were correlated. The Joback group contribution method was used to predict the heat capacities of some ILs in this work. These correlations with low deviations made it possible for ILs to be further studied in Aspen process modelling.

Understanding the fundamental chemistry of conjugated polymers and fullerenes has been the subject of intense research for the last three decades, with the last ten years seeing increased research toward the application of these materials into functional organic electronic devices such as organic photovoltaic devices (OPVs). This field has seen significant advances is cell efficiency in just the last few years (to >10%), in large part due to the development of new donor and acceptor materials, the fine tuning of fabrication parameters to control material nanostructure, as well as the introduction of new interfacial materials such as ionically functionalized conjugated polymers, also known as conjugated polyelectrolytes (CPEs). This dissertation aims to further understand the fundamental chemistry associated with charge injection processes in CPEs and ionically functionalized fullerenes. The role of ionic functionality on electrochemical, chemical, and interfacial charge injection processes is explored. The results presented demonstrate the use of ionic functionality to control the spatial doping profile of a bilayer structure of anionically and cationically functionalized CPEs to fabricate a p-n junction (Chapter II). The role of ionic functionality on chemical charge injection processes is explored via the reaction of polyacetylene and polythiophene based CPEs with molecular oxygen (Chapters III and IV). The results show the dramatic effect of ionic functionality, as well as the specific role of the counterion, on the photooxidative stability of CPEs. The control of reaction pathway via counterion charge density is also explored (Chapter IV) and shows a continuum of reaction pathways based on the charge density of the counter cation. Finally, the role of ionic functionality on interfacial charge injection processes in a functional OPV is explored using a cationically functionalized fullerene derivative (Chapters V and VI). Cell performance increases due to an increase in open-circuit voltage and substantial reduction in series resistance resulting from the high conductivity of the interfacial fullerene layer. The chemical origin of this high conductivity is explored in Chapter VI and shown to likely be the result of chemical reactions occurring between the counter anion and the fullerene core. This dissertation contains coauthored, previously published and unpublished work.