Submitted by JÚLIO HEBER SILVA (julioheber@yahoo.com.br) on 2017-04-07T20:19:45Z No. of bitstreams: 2 Dissertação - Letícia Gomes do Nascimento - 2017.pdf: 6868423 bytes, checksum: 7a54ea8b28095c4c81126f3998e87c13 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2017-04-10T11:16:14Z (GMT) No. of bitstreams: 2 Dissertação - Letícia Gomes do Nascimento - 2017.pdf: 6868423 bytes, checksum: 7a54ea8b28095c4c81126f3998e87c13 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-04-10T11:16:14Z (GMT). No. of bitstreams: 2 Dissertação - Letícia Gomes do Nascimento - 2017.pdf: 6868423 bytes, checksum: 7a54ea8b28095c4c81126f3998e87c13 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-03-07 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The Biginelli reaction involves the cyclocondensation of three reagents in the presence of an acid catalyst to obtain dihydropyrimidinones (DHPMs).This compound and its analogues are widely known to possess various pharmacological properties, such as antibacterial, antiinflammatory, antifungal, antiviral, anticancer and antihypertensive. This reaction is usually carried out via homogeneous catalysis, which presents, however, some difficulties, such as regeneration of the catalyst and difficult separation of the final product, thus becoming an obstacle for industrial use. In the present work, it was proposed the use of two classes of heterogeneous catalysts, which are: metal oxides and acid carbons in order to achieve attractive characteristics in the Biginelli reaction, as a reduction of reaction time and increase in yield. The acidic carbons were prepared by carbonization by impregnation of agroindustrial residues with sulfuric acid at a temperature of 200 °C in the mass ratio of 1:10 (precursor: H2SO4) for 6 h. The pure HY-340 and Nb2O5 were both tested and chemically treated with a solution of 30% sulfuric acid. The catalysts were characterized by X-ray diffraction (XRD), infrared spectroscopy (FTIR), thermogravimetric (TG), differential thermal analysis (DTA), textural adsorption/desorption analysis of N2 at -196 °C and desorption of ammonia at programmed temperature (DTP-NH3), scanning electron microscopy (SEM) and X-ray Dispersive Energy Spectrometry (EDS). The contents of C, N, O and S present on the surface of the coals were quantified by Elementary Analysis (CHNS-O). Exploratory catalytic tests were carried out to define the best experimental conditions of solvent, temperature, molar ratio and amount of catalyst. The results obtained allowed to establish the best experimental conditions for the realization of the Biginelli reaction. Thus, the following parameters were adopted to evaluate the performance of the different catalysts. These are: 5% catalyst content (by mass), molar ratio of 1 Benzaldehyde: 1,5 Methyl acetoacetate: 1,5 Urea, without solvent and temperature of 130 °C. The best catalyst was Nb2O5 treated with sulfuric acid, whereby a yield of 94% of dihydropyrimidinones (DHPMs). / A reação de Biginelli envolve a ciclocondensação de três reagentes na presença de um catalisador ácido para a obtenção de Dihidropirimidinonas (DHPMs). Este composto e seus derivados são amplamente conhecidos por possuir diversas propriedades farmacológicas e terapêuticas. Esta reação é geralmente realizada via catálise homogênea, que apresentam, no entanto, algumas dificuldades, como regeneração do catalisador e difícil separação do produto final, tornando-se dessa forma um obstáculo para utilização industrial. O presente trabalho teve como objetivo geral avaliar diferentes catalisadores ácidos heterogêneos na produção de dihidropirimidinonas, como óxidos de nióbio sulfonados e carvões sulfonados produzidos a partir de resíduos agroindustriais (casca de arroz e bagaço de tomate). Os carvões ácidos foram preparados por carbonização, por meio da impregnação de resíduos agroindustriais com ácido sulfúrico a uma temperatura de 200 °C na proporção mássica de 1:10 (precursor: H2SO4), por 6 h. Testou-se, também, o ácido nióbico (HY-340) e Nb2O5 ambos puros e tratados quimicamente com uma solução de 30% de ácido sulfúrico. Os catalisadores foram caracterizados por Difração de Raios X (DRX), Espectroscopia no Infravermelho (IV), Termogravimetria (TG), Análise Térmica Diferencial (DTA), Análise Textural por Adsorção/Dessorção de N2 a -196 °C, Dessorção de Amônia a Temperatura Programada (DTP-NH3), Microscopia Eletrônica de Varredura (MEV) e Espectrometria de Energia Dispersiva de Raios X (EDS). Os teores de C, N, O e S presentes na superfície dos carvões foram quantificados por Análise Elementar (CHNS-O). Foram realizados testes catalíticos exploratórios para definir melhores condições experimentais de solvente, temperatura, razão molar e quantidade de catalisador. Os resultados obtidos permitiram estabelecer as melhores condições experimentais para a realização da reação de Biginelli. Desse modo, adotaram-se os seguintes parâmetros para avaliar o desempenho dos diferentes catalisadores. São estes: teor de 5% de catalisador (em massa), razão molar de 1 Benzaldeído: 1,5 Acetoacetato de metila: 1,5 Ureia, sem solvente e temperatura de 130 °C. O melhor catalisador foi o Nb2O5 tratado com ácido sulfúrico, em que obteve-se um rendimento de 94% de dihidropirimidinonas (DHPMs).

Aramide and arylene ether multiblock copolymers of (AB)n-type with various degrees of sulfonation have been prepared for use in direct methanol fuel cells. / Aramid- und Arylethersulfon-Multiblockcopolymere vom Typ (AB)n mit unterschiedlichem Sulfonierungsgrad wurden hergestellt und hinsichtlich ihrer Eignung als Polymerelektrolyte in der Direkt-Methanol-Brennstoffzelle getestet.

This thesis reports on the synthesis and characterisation of various types of oxidised multiwalled carbon nanotubes (O-MWCNTs) modified polymeric membranes. These OMWCNT modified polymeric membranes were then assessed in terms of their remediation potential, in particular for the removal of estrogenic hormones, dissolved proteins and salts from brackish water sources. The fabricated O-MWCNT-based polyethersulfone (PES) membranes were applied as (i) adsorptive membranes, (ii) molecular-sieving membranes and (iii) as membrane substrates for thin-film composite nanofiltration (NF) membrane preparation. The research work commences with the preparation of MWCNTs via a facile catalytic chemical vapour deposition method and their chemical oxidation with strong acids in order to introduce hydrophilic carboxylic (–COOH) and hydroxyl (–OH) surface functional group moieties on the MWCNT outer walls. Intrinsically, MWCNTs are chemically inert and tend to form agglomerated nanoclusters (due to van der Waals interaction forces), which induce further difficulties in their homogenous dispersion in polar solvents (such as N-methyl-2- pyrrolidone and dimethylacetamide) employed to dissolve the polymers in the study. The introduction of these oxygen-containing moieties was therefore necessary to aid the dispersion of MWCNTs in organic solvents and for their enhanced interaction with PES and sulfonated polysulfone (SPSf). The PES/O-MWCNT ultrafiltration (UF) membranes were produced via a non-solvent induced phase separation (NIPS) method and employed in the adsorptive removal of natural hormone estrone (E1). The PES/O-MWCNT UF membranes thus prepared were characterised using SEM, AFM, zeta potential measurements and MWCO experiments. It was found that the adsorption of E1 initially increased with an increase in O-MWCNT content followed by a constant decline on further increments. Moreover, the inclusion of OMWCNTs (0.5 wt.%) in the PES membrane matrix resulted in an increase in the maximum adsorption capacity for E1 compared to pristine PES membrane, i.e., 31.25 mg/g adsorption capacity was achieved for PES/O-MWCNT compared to 23.81 mg/g for bare PES UF membrane. Based on the correlation coefficients, the Freundlich isotherm provided a better fit for the adsorption data and the adsorption kinetics followed the pseudo-second order kinetic model. Interestingly, after five regeneration cycles, the PES/O-MWCNT membranes were found to maintain similar adsorption efficiencies. The PES/O-MWCNT membranes thus prepared, present a viable approach for the removal of natural hormones and other endocrine disruptors present in water systems compared to the use of common adsorbents such as activated carbon, which end up generating large amounts of chemical sludge that require disposal in the environment. The third part of the study focused on the controlled formation of macrovoid-free polyethersulfone/sulfonated polysulfone (PES/SPSf) UF membranes with high water permeabilities, mechanical strength and antifouling properties, in the presence of O-MWCNTs. To date, the majority of polymeric nanocomposite membranes modified with O-MWCNTs as nanofillers, generally have finger-like structures and macrovoids in the membrane sublayer. While the presence of finger-like structures is favoured for the reduction in mass flow resistance, their presence induces mechanically weak points in the membrane and reduces the nanocomposite membranes’ mechanical strength properties and long-term performance stability. As such macrovoid-free PES/SPSf/O-MWCNT membranes were fabricated via the NIPS techniques, using H2O and polyethylene glycol (PEG 20 kDa) as non-solvent additives. The SEM cross-sectional images showed that a fully sponge-like morphology of the PES/SPSf membrane can be achieved in the presence of different loadings of O-MWCNTs. This was attributable to the formation of stronger hydrogen bonds between the SPSf polymer and non-solvent additives i.e., H2O, PEG 20kDa and OMWCNTs. The combination of the macrovoid-free morphology and homogenous distribution of high mechanical strength O-MWCNTs in the membrane matrix provided excellent mechanical strength enhancements for PES/SPSf/O-MWCNT membranes. Additionally, pure water flux initially increased from 598 L/m2 .h to 713 L/m2 .h followed by a decline to 578 L/m2 .h upon further increments in O-MWCNT contents, due to agglomeration of O-MWCNTs at higher loadings. The fabricated PES/SPSf/O-MWCNT membranes also displayed superior antifouling properties (FRR > 90%) and antibacterial properties (99% bacterial killing ratio) against E. coli bacteria. The fabricated support fabricfree PES/SPSf/O-MWCNT UF membranes with macrovoid-free sublayer morphologies displayed attractive features for use as UF membranes in the pre-treatment stages of water treatment and as support substrates for the preparation of TFC membranes. In general, sponge-like and macrovoid-free membrane structures are regarded as unfit for use as support membranes for TFC membrane preparation since they increase the membrane’s resistance to water flow, thereby reducing the overall TFC membrane permeability. This assumption has largely been based on sponge-like and macrovoid-free membranes structures achieved through the use of extremely high polymer concentrations, particularly using polysulfone (PSf) polymer. Hence, the sponge-like structures formed are very dense and less porous. Nevertheless, the macrovoid-free PES/SPSf/O-MWCNT membranes produced in this study, consisted of open cellular network microstructures within the membrane sublayer, which could be visualised at higher SEM magnifications. This part of the work therefore investigated the role of hydrophilic, macrovoid-free PES/SPSf and PES/SPSf/O-MWCNT as support membranes on the performance of TFC NF membranes. The TFC NF membranes were prepared via an efficient interfacial polymerization reaction between piperazine (PIP) and trimesoyl chloride (TMC). The deposition of the polyamide thin-film layer was confirmed by ATR-FTIR, SEM, AFM, contact angle and zeta potential measurements. Membrane performance results showed that TFC NF membranes fabricated on PES/SPSf/O-MWCNT support membranes displayed a 35% improvement in pure water flux with comparable salt rejections from those prepared on bare PES/SPSf support membranes. Salt rejection followed the order of Na2SO4 > MgSO4 > NaCl, which is typical for negatively charged NF membranes. It was established that the presence of hydrophilic O-MWCNTs in the support membrane allowed for the formation of a thin polyamide layer on the top surface of the support membrane, which gave rise to enhanced water permeability of the TFC NF membrane and the possibility of polyamide rejection layer within the support membrane pore channels. To further improve the performance of the TFC NF membranes, in particular, the monovalent/bivalent salt selectivity, a mixture of PIP and 2,4-diaminobenzene sulfonic acid (2,4-DABSA) at different weight ratios was prepared in the aqueous solution and reacted with TMC in the organic phase solution. It was found that the addition of low monomer weight ratio of 2,4-DABSA in the amine mixture, lead to the generation of a sulfonated TFC NF membrane with superior membrane performance in terms of pure water permeability (30.2 L/m2 .h), monovalent/bivalent salt selectivity (𝛼NaCl/Na2SO4 = 25.0) at low operating pressures (3 bar) and salt concentrations in the range of brackish waters. This was attributable to the combined presence of sulfonic acid groups on the membrane surface and the formation of the thin polyamide layer. Moreover, sulfonated TFC NF membranes exhibited good antifouling properties against bovine serum albumin (BSA), with FRR of 96.4% after three cycles of fouling and cleaning, with a fairly stable membrane performance over a 10-day period of pure water flux and Na2SO4 rejection testing. Indeed, the use of a macrovoid-free PES/SPSf/O-MWCNT support membrane did not only provide the mechanical strength for the deposition of TFC NF membrane, but also their open, cellular network microstructure, combined with high hydrophilicity and large surface pore sizes were beneficial in the reduction of polyamide layer thickness, and subsequently in the enhancement of TFC NF membrane performance. The study provided insightful information on lesser known aspects of O-MWCNT incorporated polymeric membranes, with regards to membrane structural configurations in relation to the membrane structure-performance relationships. It has been deduced that (i) the right combination of membrane surface characteristics and adsorbate solution chemistry is necessary for an open UF membrane to display reasonable removal efficiencies for low molecular-weight solutes, (ii) the combination of macrovoid-free membrane morphology with good dispersion of O-MWCNTs in the polymer matrix is necessary to realise significant enhancements in the mechanical properties of sulfonated membrane and (iii) formation of a thin sulfonated polyamide layer on top of the hydrophilic PES/SPSf/O-MWCNT support membrane is necessary to achieve high salt selectivity, and allow for the sulfonated TFC NF membrane to be operated at low pressures. / College of Engineering, Science and Technology

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M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / Fuel cell technology is a promising clean energy source compared to internal combustion engines and electricity generating plants which are associated with high emissions of greenhouse gases. The aim of this study was to modify chitosan into polymer electrolyte membranes suitable for use in PEMFC and DMFC fuel cells. Chitosan modification was done with 2-aminoethanesulfonic acid (2-AESA), dimethylformamide (DMF) and silica nanoparticles. The effect of the modification on the properties of the developed chitosan membranes was studied using FTIR, XRD, SEM-EDS and TGA. The performance of the membrane electrode assemblies was investigated. The formation of electrostatic interactions in the developed sulfonated chitosan membranes was confirmed via the Fourier transform infrared (FTIR) analysis, indicating a shift in the wavenumber of the N-H bonds from 1581 cm-1 on the chitosan spectrum to a lower wavenumber of 1532 cm-1 in the FTIR spectra of the membranes and by the new peak at the wavenumber of ~1260 cm-1 attributed to the asymmetric O=S=O stretching vibrations of the sulphate groups and sulfonic acid groups from the cross-linking sulphuric acid solution and 2-aminoethanesulfonic acid incorporated on the chitosan polymer chain during the modification. Notably, the FTIR spectra of the developed sulfonated chitosan membranes lacked the peak at the wavenumber of ~1153 cm-1 attributed to the stretching of C-O-C bonds of the polysaccharide ring of chitosan. A reaction mechanism was proposed in this study illustrating the possible conversion of the polysaccharide rings of chitosan into a poly (cyclohexene-oxide) thermoplastic rings in the developed membranes. The TGA/DTGA results of the developed sulfonated chitosan membranes showed three degradation stages. The initial weight loss occurred at temperatures ˂100 °C due to the evaporation of volatile components and water molecules inside the membranes. The second degradation phase of the membranes occurred at 208 ℃ with a loss in weight of >30% resulting from the decomposition of cross-linking networks. The third degradation stage was associated with the decomposition of the main polymer backbone of the membranes and occurred at 263°C for the chitosan membranes modified with 2-aminoethanesulfonic acid and at 266 °C for the chitosan membrane modified with silica nanofiller. The TGA/DTGA curves of Nafion 117 showed a small loss in weight of ~ 5% before a sharp decomposition that occurred between 346–505 °C. The XRD diffractograms of the developed sulfonated chitosan membranes showed amorphous phases, the crystal peaks of chitosan at 2theta of 10° and 20° were flattened on the membranes. The SEM images showed a homogenous surface morphology for the sulfonated chitosan membrane with a higher weight percentage of 2-aminoethanesulfonic acid (13,6 wt.%). The SEM images performed on the surface of the sulfonated chitosan membrane modified silica nanoparticles showed a slight agglomeration associated with the migration of the unbonded silica to the surface. The methanol permeability coefficient of the developed sulfonated chitosan membrane modified with 2-aminoethanesulfonic acid was calculated to be 2.29x10-6 cm2/s. This value was close to the methanol permeability coefficient of 2.33x10-6 cm2/s associated with unfavourable depolarisation at the cathode in direct methanol fuel cells when using Nafion 117. The proton diffusion coefficient of Nafion 117 was calculated to be 1.64x10-5 cm2/s and that of the developed sulfonated chitosan membrane modified with 2-aminoethanesulfonic acid was found to be 6.56x10-6 cm2/s, respectively. The fuel cell performance of the developed sulfonated chitosan membrane modified with 2AESA was investigated in a hydrogen fuel cell (PEMFC) supplied with H2 and O2 directly from the electrolyser. The sulfonated chitosan membrane modified with 2-aminoethanesulfonic acid (13.6 wt.%) achieved an open-circuit voltage of ~0.9 V and a maximum power output of 64.7 mW/cm2 at a maximum current of 70 mA. The current produced by the developed chitosan membrane was applied into the load and was able to turn (power) the electric fan. The sulfonated chitosan membrane modified with silica nanoparticles (2 wt.%) yielded an open-circuit voltage of ~0.9 V and attained a maximum power output of 58 mW/cm2 at a maximum current output of 60 mA/cm2. The current generated by the membrane was also able to turn the electric fan. The Nafion 117 membrane was also investigated under similar conditions and obtained an open-circuit voltage of 0.6 V and a maximum power output of 130 mW/cm2 at the maximum current output of 308 mA. The current produced by Nafion 117 was supplied into the load and was able to turn the electric fan.

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Poly(arylene ether sulfone)s are high-performance engineering thermoplastics that have been investigated extensively over the past several decades due to their outstanding mechanical properties, high glass transition temperatures (Tg), solvent resistance and exceptional thermal, oxidative and hydrolytic stability. Their thermal and mechanical properties are highly suited to a variety of applications including membrane applications such as reverse osmosis, ultrafiltration, and gas separation. This dissertation covers structure-property-performance relationships of poly(arylene ether sulfone) and poly(ethylene oxide)-containing random and segmented copolymers for reverse osmosis and gas separation membranes. The second chapter of this dissertation describes synthesis of disulfonated poly(arylene ether sulfone) random copolymers with oligomeric molecular weights that contain hydrophilic and hydrophobic segments for thin film composite (TFC) reverse osmosis membranes. These copolymers were synthesized and chemically modified to obtain novel crosslinkable poly(arylene ether sulfone) oligomers with acrylamide groups on both ends. The acrylamide-terminated oligomers were crosslinked with UV radiation in the presence of a multifunctional acrylate and a UV initiator. Transparent, dense films were obtained with high gel fractions. Mechanically robust TFC membranes were prepared from either aqueous or water-methanol solutions cast onto a commercial UDEL® foam support. This was the first example that utilized a water or alcohol solvent system and UV radiation to obtain reverse osmosis TFC membranes. The membranes were characterized with regard to composition, surface properties, and water uptake. Water and salt transport properties were elucidated at the department of chemical engineering at the University of Texas at Austin. The gas separation membranes presented in chapter three were poly(arylene ether sulfone) and poly(ethylene oxide) (PEO)-containing polyurethanes. Poly(arylene ether sulfone) copolymers with controlled molecular weights were synthesized and chemically modified to obtain poly(arylene ether sulfone) polyols with aliphatic hydroxyethyl terminal functionality. The hydroxyethyl-terminated oligomers and α-ω-hydroxy-terminated PEO were chain extended with a diisocyanate to obtain polyurethanes. Compositions with high poly(arylene ether sulfone) content relative to the hydrophilic PEO blocks were of interest due to their mechanical integrity. The membranes were characterized to analyze their compositions, thermal and mechanical properties, water uptake, and molecular weights. These membranes were also evaluated by collaborators at the University of Texas at Austin to explore single gas transport properties. The results showed that both polymer and transport properties closely related to PEO-content. The CO2/CH4 gas selectivities of our membranes were improved from 25 to 34 and the CO2/N2 gas selectivity nearly doubled from 25 to 46 by increasing PEO-content from 0 to 30 wt.% in polyurethanes. Chapter four also focuses on polymers for gas separation membranes. Disulfonated poly(arylene ether sulfone) and poly(ethylene oxide)-containing polyurethanes were synthesized for potential applications as gas separation membranes. Disulfonated polyols containing 20 and 40 mole percent of disulfonated repeat units with controlled molecular weights were synthesized. Poly(arylene ether sulfone) polyols and α,ω-hydroxy-terminated poly(ethylene oxide) were subsequently chain extended with a diisocyanate to obtain polyurethanes. Thermal and mechanical characterization revealed that the polyurethanes had a phase-mixed complex morphology. / Ph. D.