Nos últimos anos muita atenção tem sido dada a produtos que apresentam em sua composição, substâncias com uso restrito por seu risco potencial ao meio ambiente ou à saúde. A União Européia, inserida ativamente neste contexto, regulamenta requisitos que os fabricantes devem atender para, por exemplo, exportarem seus produtos à Europa. Em artefatos de borracha as maiores restrições são relativas ao uso de óleos plastificantes aromáticos e tipo ésteres ftálicos. Os óleos plastificantes são amplamente utilizados na aditivação de borrachas com o objetivo de melhorar processabilidade, reduzir custos e aperfeiçoar propriedades dos materiais visando suas aplicações. Neste âmbito alguns plastificantes reativos a base de ésteres, alguns óleos minerais e vegetais (renováveis) têm se demonstrado alternativas viáveis aos plastificantes restritos para borracha. Assim, o presente trabalho objetivou a avaliação desses plastificantes (de baixo impacto ambiental e sem restrições à saúde), explorando-se a capacidade reativa, compatibilidade e efeitos nas propriedades da borracha nitrílica hidrogenada, HNBR, e borracha de estireno-butadieno, SBR. As características das composições de HNBR contendo 10 phr e as de SBR contendo 15 phr de plastificante frente à vulcanização foram determinadas a partir das curvas reométricas. Igualmente, determinou-se a viscosidade e a relaxação de tensão destas composições. Os vulcanizados foram caracterizados quanto a sua dureza, resistência à tração, índice de dispersão da carga, densidade, resiliência, deformação permanente à compressão, flexibilidade a baixas temperaturas, comportamento frente ao envelhecimento térmico e inchamento em solvente e óleo IRM 903. Todas as composições contendo os plastificantes foram comparadas a composição sem plastificante (NTP). Nos estudos, verificou-se que o óleo vegetal de mamona in natura é capaz de substituir o plastificante éster de ftalato (DOP) na aplicação em HNBR, observando-se boa compatibilidade com este último. Na SBR os plastificantes Fluibrax Euro 40 (Petrobras), Nytex 4700 (Ninas), Flex NBS 100 (Quantiq) assim como os óleos vegetais de soja e linhaça mostraram-se em condições de substituir os óleos aromáticos restritos. Também, observou-se equivalência de desempenho entre os plastificantes, óleo vegetal de mamona e óleo éster reativo RP1020 (Hall Star) em HNBR curada com peróxido indicando que ambos plastificantes passam por um mecanismo de enxertia com a borracha. / In recent years much attention has been given to products that contain substances with restricted use because of its potential risks to the environment and health. The European Union regulates strongly the requirements that manufacturers must meet, for example, to export their products to Europe. In rubber products, the major constraints are related to the use of aromatic oils and phthalates ester plasticizers as additives. The plasticizers are widely used in rubber in order to improve processability, to reduce costs and to improve properties of materials to their applications. In this context some reactive ester plasticizers, some mineral and vegetable oils (renewable) have demonstrated viable alternatives to the restricted plasticizers for rubber. Thus, this study aimed to evaluate these plasticizers (low environmental impact and no restrictions on health), exploiting its reactive capacity, rubber compatibility and effects on the properties of hydrogenated nitrile rubber, HNBR, and on styrene-butadiene rubber, SBR. The characteristics of the compositions of the HNBR and SBR containing 10 phr and 15 phr of plasticizer, respectively, related to the vulcanization were determined by rheometric analysis. The influence of the plasticizer on the viscosity and stress relaxation were also determined. The cured material were characterized as the hardness, strength, dispersion of the filler, density, rebound, compression set, flexibility at low temperature, brittleness point, heat ageing and swelling behavior in solvent and in IRM 903 oil. All the compositions with plasticizer were compared to the composition without plasticizer (NTP). In this work it was found that the castor vegetable oil in natura has been able to replace the phthalate ester plasticizer (DOP) in HNBR, maintaining good compatibility with the elastomer. In SBR, the plasticizers Fluibrax Euro 40 (Petrobras), Nytex 4700 (Ninas), Flex NBS 100 (QuantiQ), and the vegetables oils soybean and linseed could be properly applied as alternatives to restricted aromatic oils. It was observed very similar behavior between the compounds with the plasticizers RP1020 (reactive) and castor oil. The results of rheometry, acetone extraction and toluene swelling support the hypothesis of the grafting mechanism/oligomers formation for the RP1020 and castor plasticizers in HNBR cured with peroxide, indicating that both plasticizers undergo a mechanism of grafting with the rubber.

Orientador: Helena Coutinho Franco de Oliveira / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-17T04:29:13Z (GMT). No. of bitstreams: 1 Patricio_PatriciaRiva_D.pdf: 4980020 bytes, checksum: e474966c1b7c224e3d8de5468871eefc (MD5) Previous issue date: 2010 / Resumo: A CETP é uma proteína plasmática que promove a transferência de lípides entre lipoproteínas, causando redução de HDL-colesterol e, portanto, aumento do risco de aterosclerose. Neste trabalho, investigamos o efeito da expressão desta proteína sobre a adiposidade e a expressão diferencial de genes em dois modelos animais. Inicialmente, comparamos camundongos transgênicos para a CETP humana (Tg) e controles irmãos não-transgênicos (NTg), que não expressam esta proteína. Verificamos que os camundongos CETP-Tg apresentaram redução do peso corporal, dos níveis plasmáticos de leptina, da massa dos depósitos de gordura perigonadal e subcutâneo e da área dos adipócitos. Também observamos que a expressão do RNAm da CETP é maior no tecido adiposo subcutâneo que no perigonadal. Quando comparados aos controles, os animais CETP-Tg tiveram as concentrações de RNAm no depósito perigonadal alteradas: apresentaram redução do fator de transcrição SREBP2 e da lipoproteína lipase e aumento da proteína quinase dependente de AMP (AMPK). Em relação ao tecido subcutâneo, houve diminuição do fator de transcrição PPAR_ e aumento da lipase hormônio sensível e da AMPK. Além disso, verificou-se também uma elevação de PPAR_ no fígado das fêmeas CETP-Tg, e uma elevação da lipase hepática no fígado de machos CETP-Tg. Em um segundo estudo, hamsters Golden Syrian, que expressam naturalmente a CETP, foram utilizados para confirmar se a inibição da CETP afetaria a adiposidade. Tratamento com anticorpo monoclonal neutralizante da CETP (TP2) durante um mês resultou em 70% de redução da atividade plasmática da proteína e em aumentos significativos de ganho de peso, massa de tecido adiposo visceral e área do adipócito, em comparação ao grupo controle (tratado com IgG irrelevante). Desta maneira, concluímos que a CETP induz a expressão diferencial de genes lipolíticos e lipogênicos no tecido adiposo, o que resulta em redução do conteúdo de gordura corporal. Esses resultados indicam, portanto, um novo papel antiadipogênico para a CETP. / Abstract: CETP is a plasma protein that promotes lipid transfer among plasma lipoproteins causing reduction of HDL-cholesterol and, thus, increases the risk of atherosclerosis. In this work we investigated the effect of CETP expression on differential gene expression and adiposity in two animal models. Human CETP expressing transgenic (Tg) mice and control CETP non-expressing littermates were compared. CETP-Tg mice had reduced body weight, plasma leptin levels, perigonadal and subcutaneous fat depots and adipocyte area. We also observed that CETP mRNA levels were higher in subcutaneous than in perigonadal adipose tissue. As compared to controls, CETP-Tg had altered tissue mRNA levels in the perigonadal adipose tissue: reduction of SREBP2 and lipoprotein lipase and elevation in AMPK. Regarding subcutaneous depot, there was a decrease in PPAR_ and marked elevation of hormone sensitive lipase and AMPK. In addition, an elevation in liver PPAR_ was found in female and hepatic lipase in male CETP Tg mice. Naturally CETP expressing Golden Syrian hamsters were used to confirm whether the inhibition of CETP would affect adiposity. Treatment with a neutralizing CETP monoclonal antibody (TP2) during one month resulted in 70% reduction in plasma CETP activity and significant increases in weight gain, visceral adipose tissue mass and adipocyte area, as compared to the control group (irrelevant IgG treated). In conclusion, CETP induces differential lipolitic and lipogenic gene expression in adipose tissue, resulting in reduction of body fat content. These findings disclose a novel anti-adipogenic role for CETP. / Doutorado / Fisiologia / Doutor em Biologia Funcional e Molecular

Orientador: Eliana Cotta de Faria / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Ciencias Medicas / Made available in DSpace on 2018-08-11T19:49:35Z (GMT). No. of bitstreams: 1 Urban_Aline_M.pdf: 815848 bytes, checksum: 55752c75065f47c7931dd73654d5a65d (MD5) Previous issue date: 2007 / Resumo: A resposta pós-prandial a uma sobrecarga de gordura apresenta efeitos pró-aterogênicos diretos por deposição de lipoproteínas remanescentes na parede arterial e, indiretos sobre o metabolismo de lipoproteínas ricas em triglicérides. Alterações durante a lipemia pósprandial podem estar relacionadas com as atividades das proteínas de transferência de ésteres de colesterol e da lipase hepática. Estas duas proteínas possuem papel ambíguo no desenvolvimento da aterosclerose e sua atuação sobre o metabolismo de lipoproteínas ricas em triglicérides pós-prandiais é muito pouco descrita na literatura. Estudamos as repercussões metabólicas em mulheres assintomáticas (n=28) após uma refeição oral única, líquida e rica em gordura em indivíduos apresentando deficiência primária de CETP e LH com coletas de sangue seriadas até 8h. A seleção dos casos foi feita através da determinação de valores de corte para CETP e LH, iguais ou menores aos percentis 10 ou iguais ou maiores que os percentis 90 de uma população normolipidêmica (n=129). Os indivíduos que possuem atividade das proteínas entre os percentis 10 e 90 foram selecionados como controles. A mulher que apresenta deficiência múltipla (CETP -79% e LH -88%) possui aumento da lipemia pós-prandial que foi atenuada após um ano de tratamento de reposição hormonal com Tibolona. Analisando um grupo de 6 indivíduos com um aumento médio de 33% de CETP, obtivemos curvas dos lipides pós-prandiais similares aos controles, em contraste com os relatos de casos com lipemia aumentada e deficiência de CETP. Este modelo demonstra uma ausência de um efeito de CETP na lipoproteína rica durante seu aumento moderado, provavelmente devido a falta das mudanças no transporte reverso do colesterol e igualmente a ausência dos triglicérides de um efeito direto da proteína de transferência no metabolismo lipoproteínas ricas em triglicérides. O estudo pós-prandial que usa modelos de roedores foram também realizados; observamos após uma sobrecarga oral da gordura que camundongos de ambos os sexos e ratos fêmeas apresentam lipemia pós-prandial com características similares aos seres humanos normolipidêmicos. Uma distinta resposta foi observada nos ratos machos que são mais sensíveis à dieta apresentando lipemia tardia. / Abstract: The postprandial response to a fat overload presents proatherogenic direct effects with remanescent lipoproteins deposition in arterial walls and indirect on the triglycerides-rich lipoprotein metabolism. Alterations during the postprandial lipemia are related with the activities of cholesteryl ester transfer protein and hepatic lipase. These two proteins possess ambiguous roles in the development of atherosclerosis and their performance on the triglycerides-rich lipoprotein metabolism is very scarcely described in the literature. We studied the metabolic repercussions in assimptomatics women (n=28) after a single liquid and rich in fat oral meal in individuals presenting primary deficiency of CETP and HL with serial collections of blood up to 8h. The selection of participants was made through cutoff values for CETP and HL either equal or lower or equal or higher than percentiles 10 and 90 of a normolipidemic population (n=129). The individuals that presented activities of proteins between percentiles 10 and 90 were selected as controls. In a a case-report here described a woman who presented multiple deficiencies (CETP= -79% and HL= -88%) had increased postprandial lipemia that was attenuated one year of hormonal treatment with Tibolona, a result not described yet in the literature. Analyzing a group of 6 individuals with an average CETP increase of 33%, we obtained postprandial lipids curves similar to controls, in a sharp contrast with the case report with increased lipemia and CETP deficiency. This model demonstrates an absence of a CETP effect on triglyceride rich lipoprotein during its moderate increase, probably due the lack of changes in the reverse cholesterol transport and also the absence of a direct effect of the transfer protein on triglyceride-rich lipoprotein metabolism. As well postprandial studies using rodent models were performed; we observed after an oral overload of fat that mice of both the sexes and female rats present postprandial lipemia with characteristics similar to normolipidemic humans. A distinguished response was observed in male rats that are more sensible to the diet with the presence of the delayed and late lipemia. / Mestrado / Ciencias Biomedicas / Mestre em Ciências Médicas

Orientador: Maria Isabel Felisberti / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-11T21:04:55Z (GMT). No. of bitstreams: 1 Alves_SabrinadeSousa_M.pdf: 1156094 bytes, checksum: 5b56bbbe834e47047d9d7c14d74333c1 (MD5) Previous issue date: 2008 / Resumo: Materiais poliméricos com propriedades como biodegradabilidade e biocompatibilidade, como o poli(hidroxibutirato) (PHB) e a poli(caprolactona), vêm sendo amplamente estudados para aplicações com alto valor agregado, como a área biomédica. A síntese de poliuretanas contendo blocos de PHB e PCL visa a obtenção de um material que mantenha as características de biodegradabilidade e biocompatibilidade e que possua propriedades mecânicas diferentes dos materiais de partida, o que viabiliza um aumento na gama de aplicações destes polímeros. Neste trabalho, polióis de PHB e PCL com massa molar inferior a 6000 g mol foram obtidos através de reações de glicólise. Diferentes rotas e condições experimentais, utilizando diferentes solventes, catalisadores, tempo e temperatura, foram testadas para esta reação. A caracterização destes oligômeros foi feita através de análise de RMN H e C, DSC, TGA, índice de hidroxila e GPC. Na segunda etapa do trabalho, foram realizadas reações dos oligômeros obtidos com hexametileno diisocianato (HDI), um isocianato de cadeia linear de baixo poder carcinogênico. As estruturas químicas das poliuretanas obtidas nesta reação foram caracterizadas por FTIR e RMN H e C, as propriedades térmicas caracterizadas por DSC, TGA e DMA, físicas através de GPC e teste de solubilidade para verificar existência de reticulação / Abstract:The synthesis of polyurethanes containing PHB and PCL blocks aims to obtain materials with controlled mechanical properties maintain biodegradable and biocompatible polymers such as poly(hidroxybutyrate) (PHB) and poly(caprolactone) (PCL) have been largely studied. The synthesis of polyurethanes containing blocks of PHB and PCL aims to obtain materials with controlled mechanical properties maintaing the biodegradability and biocompatibility. In this work, polyols of PHB and PCL with molar weight less than 6000 g mol were obtained from glicolise reactions with ethylene glycol. The polyols were characterizated by RMN H e C, DSC, TGA, hydroxyl index and GPC. Diferent routes and experimental conditions, using diferent solvents, catalysts, time and temperature were tested. In a second step of this research reactions between the polyols and hexamethylene diisocianate (HDI), an alifatic isocianate with low carcinogenic toxicity were conduced in order to obtin polyurethanes. The chemical structure of polyurethanes obtained was characterized by FTIR and RMN H e C, thermal properties were characterized by DSC, TGA and DMA em physical properties by GPC and solubility test / Mestrado / Físico-Química / Mestre em Química

As reações de adição aldólica entre a cetimina 1 e aldeídos aromáticos foram inicialmente efetuadas à temperatura ambiente, em sistema bifásico constituído por uma fase aquosa básica (KOH 10% ou NaOH 5% m/v) e por uma fase orgânica (aldeído), na ausência de solventes e de catalisadores, observando-se baixa conversão em produto. Porém, quando se utilizou o catalisador aliquat®-336, foi possível reduzir a concentração da base (NaOH 1%), com conversão total da imina em produto que, na maioria dos casos, era uma mistura de duas oxazolidinas isoméricas de estereoquímica cis e trans. Esses compostos puderam ser isolados e purificados por recristalização de etanol ou metanol. Em todas as reações efetuadas com benzaldeído, m-clorobenzaldeído e p-nitrobenzaldeído, não se observou excesso diastereomérico significativo. No entanto, as reações com p-clorobenzaldeído mostraram-se diastereosseletivas, conduzindo, à temperatura ambiente, quase que exclusivamente à oxazolidina de estereoquímica cis. A comparação entre o resultado de reações efetuadas a curto e longo tempo de reação, ou em diferentes temperaturas, permitiu concluir que o aldol de estereoquímica anti é o produto cinético, o qual se transforma lentamente na oxazolidina cis. O produto termodinâmico (aldol syn) cicliza rapidamente, não sendo observado nos espectros de RMN de H dos produtos brutos de reação, mas sim seu produto ciclizado, a oxazolidina trans. Tentativas de obter os produtos de reação com excesso enantiomérico, pelo emprego de catalisadores de transferência de fase assimétricos, não foram bem sucedidas. / The aldol addition reactions of ketimine 1 with four aromatic aldehydes could be performed at room temperature, in the presence of an alkaline aqueous solution (KOH 10% or NaOH 5% m/v), and in the absence of organic solvents or catalysts. Under this conditions, conversion to product was often incomplete. However, when the reaction was performed in the presence of aliquat®-336, the base concentration could be reduced (1% m/v), and the ketimine was completely converted into a mixture of diastereomeric oxazolidines, that could be isolated and purified by crystallization from ethanol or methanol. Although no significative diastereomeric excess was observed for the reactions of 1 with benzaldehyde, m-chlorobenzaldehyde or p-nitrobenzaldehyde, for reactions with p-chlorobenzaldehyde the cis oxazolidine was almost exclusively formed. The comparison of diastereomeric ratio at shorter or longer reaction times seems to indicate that the aldol anti adduct is the kinetic product and that cyclization to the corresponding cis oxazolidine is slower than the retro-aldol reaction. On the other hand, in lieu of the thermodynamic product (aldol syn), only the corresponding cyclized product (oxazolidine trans) could be visualized in the H NMR spectra of the crude product, as a result of a fast cyclization step. Attempts to produce enantiomeric enriched oxazolidines by performing the aldol reactions in the presence of chiral catalysts were unsuccessful.

Diels-Alder cycloaddition of methylcyclopentadienes to 2,5-dibromo-p-benzoquinone was performed. A single, isomerically pure cycloadduct was isolated, whose structure was assigned via analysis of its 1-D and 2-D NMR spectra. Diels-Alder cycloaddition of methylcyclopentadienes to 2 -methoxy-p-benzoquinone was performed. A single, isomerically pure cycloadduct was isolated, whose structure was assigned via analysis of the 1-D and 2-D NMR spectra of this cycloadduct and its reduction product obtained via stereo-specific reduction with sodium borohydride in the presence of cerous chloride. The structure of Thiele's ester was assigned via analysis of its 1-D and 2-D NMR spectra.

Philosophiae Doctor - PhD / The production of biodiesel (methyl esters) from vegetable oils represents analternative means of producing liquid fuels from biomass, and one which is growing rapidly in commercial importance and relevance due to increase in petroleum prices and the environmental advantages the process offers. Commercially, biodiesel is produced from vegetable oils, as well as from waste cooking oils and animal fats. These oils are typically composed of C14-C20 fatty acid triglycerides. In order to produce a fuel that is suitable for use in diesel engines, these triglycerides are usually converted into the respective mono alkyl esters by base-catalyzed transesterification with short chain alcohol, usually methanol. In the first part of this study, the transesterification reactions of three different vegetable oils; sunflower (SFO), soybean (SBO) and waste cooking oil (WCO) with methanol was studied using potassium hydroxide as catalyst in a conventional batch process. The production of biodiesel from waste cooking oil was also studied via continuous operation systems (employing the use of low frequency ultrasonic technology and the jet loop reactor). The characterisation of the feedstock used and the methyl ester products were determined by different analytical techniques such as gas chromatography (GC), high performance liquid chromatography (HPLC) and thin layer chromatography (TLC). The effects of different reaction parameters (catalyst amount, methanol to oil ratio, reaction temperature, reaction time) on methyl ester/FAME yield were studied and the optimum reaction conditions of the different process systems were determined. The optimum reaction conditions for production of methyl esters via the batch process with the fresh oil samples (SFO and SBO) were established as follows: a reaction time of 60 min at 60 ºC with a methanol: oil ratio of 6:1 and 1.0 KOH % wt/wt of oil; while the optimum reaction conditions for the used oil (WCO) was observed at a reaction time of 90 min at 60 ºC, methanol: oil ratio of 6:1 and 1.5% KOH wt/wt of oil. The optimum reaction conditions for the transesterification of the WCO via ultrasound technology applied in a continuous system in this study were: a reaction time of 30 min, 30 ºC, 6:1 methanol/oil ratio and a 0.75 wt% (KOH) catalyst concentration. The ultrasound assisted transesterification reactions performed at optimum conditions on the different oil samples led to higher yields of methyl esters (96.8, 98.32 and 97.65 % for WCO, SFO and SBO respectively) compared to methyl esters yields (90, 95 and 96 % for WCO, SFO and SBO respectively) obtained when using conventional batch procedures. A considerable increase in yields of the methyl esters in the ultrasound assisted reaction process were obtained at room temperature, in a remarkably short time span (completed in 30 min) and with a lower amount of catalyst (0.75 wt % KOH) while the results from the continuous jet loop process system showed even better results, at an optimum reaction condition of 25 min of reaction, a methanol: oil ratio of 4:1 and a catalyst amount of 0.5 wt%. This new jet loop process allowed an added advantage of intense agitation for an efficient separation and adequate purification of the methyl esters phase at a reduced time of 30 min. The use of homogeneous catalysts in conventional processes poses many disadvantages; heterogeneous catalysts on the other hand are attractive on the basis that their use could enable the biodiesel production to be more readily performed as a continuous process resulting in low production costs. Consequently, a solid base catalyst (KNO3/FA) prepared from fly ash (obtained from Arnot coal power station, South Africa) and a new zeolite, FA/Na-X synthesized from the same fly ash were used as solid base catalysts in the transesterification reactions in the conversion of a variety of oil feedstock with methanol to methyl esters. Since fly ash is a waste product generated from the combustion of coal for power generation, its utilization in this manner would allow for its beneficiation (as a catalytic support material and raw material for zeolite synthesis) in an environmentally friendly way aimed at making the transesterification process reasonably viable. Arnot fly ash (AFA) was loaded with potassium (using potassium nitrate as precursor) via a wet impregnation method while the synthesized zeolite FA/Na-X was ion exchanged with potassium (using potassium acetate as precursor) to obtain the KNO3/FA and FA/K-X catalysts respectively. Several analytical techniques were applied for characterization purposes. The results of the XRD and XRF showed that the AFA predominantly contained some mineral phases such as quartz, mullite, calcite and lime. The high concentration of CaO in AFA was apparent to be beneficial for the use of fresh fly ash as a support material in the heterogeneous catalysed transesterification reactions. XRD characterisation of KNO3/FA results indicated that the structure of KNO3/FA gradually changed with the increase in KNO3 loading. The catalyst function was retained until the loading of KNO3 was over 10 %. IR spectra showed that the KNO3 was decomposed to K2O on the fly ash support during preparation at a calcination temperature of 500 ºC. The CO2-TPD of the KNO3/FA catalysts showed that two basic catalytic sites were generated which were responsible for high catalytic abilities observed in the transesterification reactions of sunflower oil to methyl esters. On the other hand, XRD results for the as- received zeolite synthesized from AFA showed typical diffraction peaks of zeolite NaX. SEM images of the FA /NaX showed nano platelets unique morphology different from well known pyramidal octahedral shaped crystal formation of faujasite zeolites and the morphology of the FA /KX zeolite did not show any significant difference after ion exchange. The fly ash derived zeolite NaX (FA /NaX) exhibited a high surface area of 320 m2/g. The application of the KNO3/FA catalysts in the conversion reactions to produce methyl esters (biodiesel) via transesterification reactions revealed methyl ester yield of 87.5 % with 10 wt% KNO3 at optimum reaction conditions of methanol: oil ratio of 15:1, 5 h reaction time, catalyst amount of 15 g and reaction temperature 160 °C, while with the use of the zeolite FA/K-X catalyst, a FAME yield of 83.53 % was obtained for 8 h using the ion exchanged Arnot fly ash zeolite NaX catalyst (FA/KX) at reaction conditions of methanol: oil ratio of 6:1, catalyst amount of 3 % wt/wt of oil and reaction temperature of 65 ºC. Several studies have been carried out on the production of biodiesel using different heterogeneous catalysts but this study has been able to uniquely demonstrate the utilization of South African Class F AFA both as a catalyst support and as a raw material for zeolite synthesis; these catalyst materials subsequently applied sucessfully as solid base catalysts in the production of biodiesel. / South Africa

Water-in-oil (w/o) microemulsion systems, stabilised by either an anionic surfactant or a cationic surfactant were studied. The anionic system consisted of ethoxylated nonylphenol phosphate esters (Atpol), Shellsol oil and an alcohol. These microemulsions tolerated an increase in ionic strength of the water phase up to a point: Beyond this point no microemulsion could be obtained. However, adding amine salts, e.g. diethanolamine nitrite, improved the emulsification of the aqueous phase. Increasing the alcohol (cosurfactant) chain length up to octanol also increased the uptake of the aqueous phase. Thus octanol yielded the best results in terms of emulsifying large volumes of the water-phase, particularly at high salt concentrations. A key objective was to prepare stable microemulsions with high nitrite content. The maximum microemulsion nitrite contents (expressed as NaNO2equivalent by mass) achieved were: -- About 10% when a 30% NaNO2solution was emulsified -- 23% when neat diethyl ethanolamine nitrite (DEEAN) was solubilized, and -- 23% for mixtures of diethanolamine nitrite (DEtOHAN) and NaNO2 in water. The cationic microemulsion system was based on the double-chain cationic surfactant, didodecyldimethyl ammonium chloride (DDAC). In this case the solubilization of the following acetate salts were investigated: ammonium, sodium, magnesium, zinc and manganese. As with the Atpol system, it was found that increasing the ionic strength is detrimental to microemulsification of the aqueous phase. In the DDAC system, an increase in the alcohol chain length beyond butanol led to reduced aqueous phase uptake. Thus the natures and concentrations of the surfactant and the cosurfactant as well as the ionic strength of the aqueous phase determine the stability and the emulsification of large volumes of aqueous phase. In general there is an optimum ionic strength at which the salt content of the microemulsion formulation is maximised. / Dissertation (MSc (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

No description available.

Ester liquids including natural ester and synthetic ester are considered as potential substitutes for mineral oil, due to their good biodegradability and high fire points. Although these liquids have been widely used in distribution and traction transformers, research efforts are required for the purposes of design and manufacture of high voltage and large power transformers which are filled by esters. Indeed, it would be risky to apply esters in large power transformers without thorough understandings of their behaviours in large gaps and/or when combined with pressboard insulation. Therefore, investigations of creepage discharges along the surface of pressboard in esters are vitally important and their behaviours should be compared with those of mineral oils. This thesis is aimed to investigate the creepage discharges along pressboard in esters and mineral oil under ac divergent electric field. Apparent charges, current signals and images of streamer channels were obtained synchronously to identify whether and how the introduction of pressboard surface would influence the inception and propagation of discharges as compared to tests in open gap. When over-stressed by higher voltages, the surface tracking along the pressboard-ester interface, triggered by sustaining creepage discharges, was studied and the evolutions of accompanying creepage discharge patterns were investigated. In these experiments, both esters and mineral oil impregnated pressboards were comparatively studied. The test results indicated that at the inception stage, the presence of pressboard or any other solid types in different liquids under test do not influence the PD inception voltages; in the propagation stage, solid surface tends to promote the development of discharges, especially those occurring in negative half cycles, and shifts more discharges towards the zero-crossing phase angles. This discharge promotion effect is much more evident in esters than in mineral oil, probably because of higher discharge intensity in esters and higher viscosity of esters. The space charge effect and the residual low density channel effect are proved as the mechanisms best explaining the influences of solids on creepage discharges. Under higher voltages, it was found that the impregnated pressboard is susceptible to discharge erosion characterized by “white and carbonized tree-shaped marks”, due to intense discharges occurring on or near the pressboard surface. The “white mark” appears at a lower voltage and propagates more easily on ester impregnated pressboard. The gaseous “white mark” channels will attract the subsequent discharges to follow the same discharge routes; the accumulative energy dissipation in these channels will then result in the carbonization of the channels. Once formed, the surface tree-shaped mark can continue to grow even under reduced voltage levels until it bridges the gap and causes the final flashover.