Hydrophilic poly(2-hydroxyethyl methacrylate), PHEMA, and hydrophobic poly(dimethyl siloxane), PDMS, segments containing copolymers have been widely used as a biomaterial. These amphiphilic copolymers also used as an emulsifying agent in polymer solutions and compatibilizer in polymer blends. In this case, solution polymerizations of HEMA by radiation, ATRP and RAFT methods were studied. The thermal degradation mechanism of PHEMA, which was prepared in aqueous solution by gamma radiation technique, was studied in detail. The DSC, TGA and Mass Spectroscopy analyses revealed that the degradation is linkage and depolymerization with a combination of monomer fragmentation. The ATRP of HEMA was performed with ethyl-2-bromoisobutyrate (EBriB) initiator and CuCl/bipyridine catalyst in MEK/1-propanol solvent mixture. Cu(II) complexes and PHEMA obtained via ATRP were characterized by UV-vis, FTIR and 1H-NMR analysis. The RAFT polymerization of HEMA with different [RAFT]/[AIBN] ratios were also investigated in three solvents (methyl ethylketone, ethyl acetate and toluene). The controlled polymerization of HEMA with the ratio of [RAFT]/ [AIBN]=18 at 80 oC in MEK and ethyl acetate, shows the first-order kinetic up to the nearly 40 % conversion Macroazoinitiator PDMS-MAI was synthesized from bifunctional PDMS and then copolymerized with MMA, EMA, HEMA and TMS-HEMA monomers Different characterization methods such as FTIR, 1H-NMR, solid state NMR, GPC, XPS, SEM, DSC, etc. have been used for the characterization of block copolymers. P(DMS-b-TMSHEMA) was converted to the P(DMS-b-HEMA) block copolymer by deprotection of TMS groups. The phase separated morphology was observed for the P(DMS-b-HEMA) copolymer, which was different from P(DMS-b-MMA) and P(DMS-b-EMA) copolymers.

This thesis is aimed to understand the role of nanofiller type, nanofiller dispersion, nanofiller geometry, and, presence of reinforcing fibers in flame retardancy of polymer nanocomposites. For this purpose, montmorillonite nanoclays, multi-walled carbon nanotubes, halloysite clay nanotubes and silica nanoparticles were used as nanofillers in polymeric matrices of poly (methyl methacrylate) (PMMA), high-impact polystyrene (HIPS), polylactide (PLA) and polyamide-6 (PA6) containing certain conventional flame retardant additives. Furthermore, the influence of nanofiller and flame retardant additives on fiber/matrix interfacial interactions was studied. Materials were prepared by twin-screw extrusion melt-mixing and ultrasound-assisted solution-mixing techniques. Characterization of nanocomposite morphology was done by X-ray diffraction and transmission electron microscopy. Flame retardancy was investigated by mass loss cone calorimetry, limiting oxygen index measurements and UL94 standard tests. Flame retardancy mechanisms were revealed by characterization of solid fire residues by scanning electron microscopy, transmission electron microscopy, infrared spectroscopy and X-ray diffraction. Thermal degradation and stability was studied using thermogravimetric analysis. Mechanical properties were determined by tension tests and fracture surfaces were observed under scanning electron microscope. Influence of nanofiller type was investigated comparing the behavior of montmorillonite nanoclay and multi-walled carbon nanotube reinforced PMMA nanocomposites containing phosphorous/nitrogenous intumescent flame retardant. Carbon nanotubes hindered the formation of intumescent inorganic phosphate barrier which caused the samples to be exposed to larger effective heat fluxes during combustion. Contrarily, nanoclays physically reinforced the protective barrier without disrupting the intumescent character, thereby allowing for lower heat release and mass loss rates, and increased amounts of residue upon combustion. Influence of nanofiller dispersion was studied comparing nanocomposite and microcomposite morphologies in montmorillonite nanoclay reinforced HIPS containing aluminum hydroxide flame retardant. Relative to microcomposite morphology, reductions in peak heat release rates were doubled along with higher limiting oxygen index and lower burning rates with nanocomposite formation. Improved flame retardancy was attributed to increased amounts of char residue and lower mass loss rates. Nanocomposite formation allowed for the recovery of tensile strength reductions caused by high loading level of the conventional flame retardant additive in polymer matrix. Influence of nanofiller geometry was investigated for phosphorus based intumescent flame-retarded PLA nanocomposites. Fire performance was increased in the order of rod-like (1-D) &lt / spherical (0-D) &lt / &lt / plate-like (2-D) geometries which matched qualitatively with the effective surface area of nanoparticles in the nanocomposite. Well-dispersed plate-like nanoparticles rapidly migrated and accumulated on exposed sample surface resulting in the formation of strong aluminum phosphate/montmorillonite nanocomposite residue. Mechanical properties were increased in the order of 0-D &lt / 1-D &lt / 2-D nanofillers corresponding to the order of their effective aspect ratios in the nanocomposite. Influence of fiber reinforcement was studied for montmorillonite nanoclay containing short-glass fiber-reinforced, phosphorus/nitrogen based flame-retarded PA6 composites. Substitution of a certain fraction of conventional additive with nanofiller significantly reduced peak heat release rate, delayed ignition and improved limiting oxygen index along with maintained UL94 ratings. Improved flame retardancy was ascribed to the formation of a nanostructured carbonaceous boron/aluminum phosphate barrier reinforced by well-dispersed montmorillonite nanolayers. Fiber/matrix interfacial interactions in flame-retarded PA6 and HIPS containing nanoclays were investigated using a micromechanical approach, and it was found that the influence of nanoclay on the interface depends on crystallinity of polymer matrix. While the fiber/matrix interfacial strength is reduced with nanoclay incorporation into amorphous matrix composites, significant interfacial strengthening was imparted by large surface area, well-dispersed clay nanolayers acting as heterogeneous nucleation sites for the semi-crystalline matrix.

In the selection of candidates for CO2 absorption, solvent thermal degradation has become a general concern due to the significant impact on operational cost and the intention to use thermal compression from high temperature stripping to minimize the overall process energy. In this research, the impact of flue gas contaminants on Monoethanolamine (MEA) thermal degradation was investigated at elevated temperatures consistent with those in the CO2 stripper. Nitrite, fly ash, sulfate and thiosulfate were each added to 5.0 M MEA and the contaminant-containing MEA solutions were degraded at 125 °C, 135 °C and 145 °C. MEA degrades significantly more in the presence of nitrite (5000 ppm) than MEA alone at the same amine molar concentration for all three temperatures. MEA degradation activation energy of MEA-nitrite solution is approximately one-seventh of that of MEA solution without nitrite. Fly ash was observed to inhibit nitrite-induced MEA degradation and greatly increase the MEA degradation activation energy of MEA-nitrite solution. Fly ash, sodium sulfate and sodium thiosulfate by themselves were not shown to impact MEA thermal degradation rate. Sodium salts of glycine, sarcosine, alanine and ß-alanine were thermally degraded at 125 °C, 135 °C and 145 °C, respectively, to discover the structural reasons for their thermal stability. These four amino acids have enhanced thermal degradation rates compared to MEA. The stability order for amino acid salts tested to date is: sarcosinate > alaninate > ß-alaninate. Calculated activation energies for the degradation processes are lower than that of MEA. ß-Alaninate (ß-Ala) thermal degradation generates ß-Ala dimer (major degradation product), ß-Ala dimer carbamate and tetrahydro-1,3-oxazin-6-one. Functional groups, amine orders and steric effect were investigated for their impact on amine thermal degradation. Primary amines with chain structures showed a thermal stability trend as diamine > alkanolamine > amino acid salt. For alknolamine and diamine structural isomers, the primary amines are more stable than the secondary amines. Steric hindrance around the amine group plays a global positive role in protecting amines against thermal degradation.

Absorption-stripping with aqueous, concentrated piperazine (PZ) is a viable retrofit technology for post-combustion CO2 capture from coal-fired power plants. The rate of thermal degradation and oxidation of PZ was investigated over a range of temperature, CO2 loading, and PZ concentration. At 135 to 175 °C, degradation is first order in PZ with an activation energy of 183.5 kJ/mole. At 150 °C, the first order rate constant, k1, for thermal degradation of 8 m PZ with 0.3 mol CO2/mol alkalinity is 6.12 × 10-9 s-1. After 20 weeks of degradation at 165 °C, 74% and 63%, respectively, of the nitrogen and carbon lost in the form of PZ and CO2 was recovered in quantifiable degradation products. N-formylpiperazine, ammonium, and N-(2-aminoethyl) piperazine account for 57% and 45% of nitrogen and carbon lost, respectively. Thermal degradation of PZ likely proceeds through SN2 substitution reactions. In the suspected first step of the mechanism, 1-[2-[(2-aminoethyl) amino]ethyl] PZ is formed from a ring opening SN2 reaction of PZ with H+PZ. Formate was found to be generated during thermal degradation from CO2 or CO2-containing molecules. An analysis of k1 values was applied to a variety of amines screened for thermal stability in order to predict a maximum recommended stripper temperature. Morpholine, piperidine, PZ, and PZ derivatives were found to be the most stable with an allowable stripper temperature above 160 °C. Long-chain alkyl amines or alkanolamines such as N-(2-hydroxyethyl)ethylenediamine and diethanolamine were found to be the most unstable with an allowable stripper temperature below 120 °C. Iron (Fe2+) and stainless steel metals (Fe2+, Ni2+, and Cr3+) were found to be only weak catalysts for oxidation of PZ, while oxidation was rapidly catalyzed by copper (Cu2+). In a system with Fe2+ or SSM, 5 kPa O2 in the inlet flue gas, a 55 °C absorber, and one-third residence time with O2, the maximum loss rate of PZ is expected to 0.23 mol PZ/kg solvent in one year of operation. Under the same conditions but with Cu2+ present, the loss rate of PZ is predicted to be 1.23 mole PZ/kg solvent in one year of operation. Inhibitor A was found to be effective at decreasing PZ loss catalyzed by Cu2+. Ethylenediamine, carboxylate ions, and amides were the only identified oxidation products. Total organic carbon analysis and overall mass balances indicate a large concentration of unidentified oxidation products. / text

Piezoelectric materials have numerous applications like high temperature accelerometers, pressure, flow and NDT transducers, acoustic emission, ultrasonic cleaning, welding, high voltage generators, medical therapy etc. The commonly used piezoelectric material, PZT continues to dominate the commercial market for piezoelectric actuators applications. The primary limitations of PZT are the lower Curie temperature TC <390oC and rapid thermal degradation avobe 200oC. Continuing efforts are focused on the development of piezoelectric materials suitable for high temperature applications >200oC. These materials will be very useful for making sensors for space exploration, oil and geothermal well drilling tools, oil & gas pipeline health monitoring and automotive smart brakes. Recently material based on (1-x)Bi(Me)O3-xPbTiO3 developed with TC~460oC, and d33~500 pC/N compared to TC~390oC and d33~220 pC/N of pure PZT. Enhanced room temperature properties and higher transition temperature makes this material interesting for further investigation as a high temperature piezoelectric material. Reliability of technological piezoelectric devices is a major concern for their applications. Many piezoelectric materials undergo a process of aging, associated with a spontaneous decrease of electromechanical properties. In the current work thermal degradation and aging behavior of high temperature piezoelectric material BSPT was evaluated and compared with the commonly used PZT.

No description available.

ABSTRACT CHARACTERIZATION OF CONDUCTING POLYMERS OF ESTER LINKAGE CONTAINING THIOPHENE DERIVATIVES VIA MASS SPECTROSCOPY Aslan, Evren M.Sc., Department of Chemistry Supervisor: Prof. Dr. Levent Toppare Co-Supervisor: Prof.Dr. Jale Hacaloglu December 2004, 86 pages In order to investigate the thermal and structural characteristics of terepthalic acid bis-(2-thiophen-3-yl-ethyl)ester (TATE), decanedioic acid bis-(2-thiophen-3-yl- ethyl) ester (DATE) and octanoic acid 2-thiophen-3-yl-ethyl ester (OTE), their corresponding homopolymers, copolymers with thiophene and polythiophene, pyrolysis mass spectrometry technique was utilized. The results were discussed in detail considering the effects of spacer group in between ester linkages. Thermal Gravimetry Analysis was used to investigate the weight loss for polymers and monomers. Conductivities of samples were measured by four-probe technique. It was found that when the ester linkages contain hydrocarbon chains, the growth of polymer occurred through both 2 and 5 positions. On the other hand, when the ester linkages contain more rigid groups such as phenyl, steric hindrance inhibited the growth of the polymer through 2- position and polymerization proceeded via coupling of thiophene moieties mainly at 5-position yielding a polymer with lower conductivity. Though the structure of P(OTE) is inherently different than P(DATE) and P(TATE) extent of network structure is also quite low for this polymer compared to PTh. Similar thermal characterizations were recorded indicating that thermal units were not significantly affected by the presence of TATE, DATE or OTE for all copolymer samples.

Orientador: Lúcia Helena Innocentini Mei / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-16T13:24:11Z (GMT). No. of bitstreams: 1 Carvalho_JoseWilsonCamilher_D.pdf: 2648911 bytes, checksum: a24c06cac0abecd9825f4e073f262762 (MD5) Previous issue date: 2010 / Resumo: É apresentada a preparação e a caracterização de nanocompósitos, produzidos a partir da vermiculita e poliolefinas funcionalizadas como matriz polimérica. As poliolefinas foram representadas pelo polietileno de baixa densidade (PEBD) e o polietileno de baixa densidade linear (PEBDL), utilizadas com e sem o anidrido maleico. A vermiculita de origem nacional foi escolhida como fase inorgânica na preparação dos nanocompósitos, devido a sua abundância e o seu baixo custo associado. A interação das matrizes poliolefínicas com a vermiculita foi facilitada pela utilização de agentes de acoplamento, baseados em compostos de amônio, cujos efeitos sobre as propriedades de barreira, ao oxigênio, à umidade, e de retardância de chama dos compostos obtidos são relatados. Foi utilizada como ferramenta de análise a Espectroscopia de Infravermelho com transformada de Fourier (FTIR), para o acompanhamento e caracterização do processo de síntese das organo-vermiculitas. A Difração de Raio X (DRX) foi utilizada tanto para a análise do minério de vermiculita como recebido, quanto para a caracterização dos nanocompósitos utilizando as vermiculitas modificadas com os agentes de acoplamento. Os resultados foram confirmados com a utilização da Microscopia Eletrônica de Transmissão (MET) e a Microscopia Eletrônica de Varredura (MEV), com auxílio da técnica de feixe de íons (FIB). Essas técnicas confirmaram a obtenção de compostos esfoliados, evidenciando a eficiência dos agentes de acoplamento no processo de obtenção dos nanocompósitos, previamente analisados via DRX. A estrutura esfoliada dos compostos obtidos permitiu que fossem conduzidos testes sobre a sua capacidade de barreira ao oxigênio e a umidade, cujos resultados promissores mostraram a possibilidade de serem utilizados como materiais de embalagem. Da mesma forma, a característica esfoliada destes materiais possibilitou o desenvolvimento de testes para o atendimento da área de fios e cabos como isolamento e cobertura de cabos. Com este objetivo, foram analisados os requisitos de retardância de chama e ao aumento da temperatura de degradação, fundamental à preservação da integridade dos cabos durante o ataque das chamas. Este trabalho apresentou de maneira pioneira o processo de produção e utilização da vermiculita nacional, na obtenção de nanocompósitos, desde minério bruto até o produto final e a sua aplicação em casos reais / Abstract: The preparation and characterization of nanocomposites made from vermiculite and functionalized polyolefins as a polymeric matrix is presented. Polyolefins are represented by low-density polyethylene (LDPE) and linear low-density polyethylene (LLDPE), used with and without maleic anhydride. Vermiculite from a national origin was chosen as an inorganic phase in the nanocomposite preparation, due to its abundance and low cost. The interaction of the polyolefin matrixes with the vermiculite was facilitated using coupling agents. The coupling agents used were represented by the ammonium compounds and their effects were reported in the barrier properties to oxygen, humidity and in flame retardance in the produced compounds. As a nanocomposite analysis tool, Fourrier transformed infrared spectroscopy (FTIR) techniques were used, mainly in following and characterizing the organo-vermiculite process. X-ray diffraction (XRD) was used from the analysis of the vermiculite as received to the nanocomposite characterization using coupling agents. These results were confirmed using the transmission electronic microscopy (TEM) and scanning electronic microscopy (SEM), using focused ion beam (FIB), as well. These techniques confirmed the obtainment of exfoliated compounds that reinforced the coupling agents in the nanocomposite obtainment process, previously analyzed by XRD. The exfolied structure of the compounds obtained allowed for barrier-capacity tests. The nanocomposites tested as an oxygen and humidity barrier showed the possibility of being used as packaging materials due to the promising results presented. Likewise, the exfoliated characteristic of these materials enabled the development of tests to meet the needs of the wire and cable area as insulation and cable jacketing. Within this objective, there was the need to focus on the flame retardance requirements and the increase of the degradation temperature, crucial to preserve cable integrity during the flame attack. This work presents, in a pioneering manner, a revision of the production process and utilization of national vermiculite in obtaining the nanocomposite, from its ore to the final product and its application in real cases / Doutorado / Ciencia e Tecnologia de Materiais / Doutor em Engenharia Química

Orientador: Inés Joekes / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-19T10:48:43Z (GMT). No. of bitstreams: 1 Richena_Marina_M.pdf: 1581549 bytes, checksum: cea715827b6e69afa186bff163d1c821 (MD5) Previous issue date: 2011 / Resumo: O cabelo branco se torna amarelo com o tempo, apesar de não possuir melanina, o pigmento responsável pela coloração. Este amarelecimento gera insatisfação nas pessoas. Neste trabalho estudamos em profundidade as mudanças de cor e as propriedades mecânicas do cabelo branco após exposição ao UV, Vis e IV, e os fatores que afetam o amarelecimento, incluindo descoloração com H2O2 e a presença de umidade, e tentamos identificar os cromóforos amarelos. Usamos cabelos brancos de dois tipos: cabelo padrão (blenda de várias cabeças), mais amarelado (valor da coordenada de azul-amarelo, b* = 20), e cabelo comum (cabelo de uma cabeça), menos amarelo (b* = 10). Os resultados mostram que a coloração inicial interfere no comportamento frente à exposição ao UV - Vis: após exposição numa lâmpada de mercúrio por cerca de 200 h, o cabelo padrâo desamarela (Db* = - 6), e o cabelo comum amarela (Db* = 2). Entretanto, quando o cabelo padrâo é descolorido com H2O2 (b* = 8), amarela após poucas horas de irradiação (Db* = 3). Expondo apenas ao Vis ocorre desamarelecimento, independentemente da coloração inicial, tanto no cabelo padrão (Db* = - 9), quanto no cabelo comum (Db* = - 3). Os resultados de variação de cor do cabelo branco exposto ao sol concordam com os resultados de exposição à lâmpada de mercúrio. Já a radiação IV na temperatura de 81°C amarela tanto o cabelo branco comum (Db* = 9), quanto o cabelo branco padrão (Db* = 3). O cabelo padrão irradiado em 100% de umidade relativa não mostra variação de cor após 88 h de irradiação. Além disso, o cabelo que foi irradiado, mas lavado com solução de lauril sulfato de sódio após cada período de irradiação, manteve o valor de Db*. O cabelo não lavado continuou menos amarelo após a armazenagem; entretanto, um amarelecimento (Db* > 1,5) foi observado após 1 ano. A única alteração significativa observada nas propriedades mecânicas foi a redução da tensão máxima em 17% depois de 480 h de exposição ao Vis da lâmpada. Medidas de absorbância no UV - Vis de soluções de cabelo branco com diferentes tonalidades de amarelo mostram absorção em toda a faixa do visível, comportamento decorrente do amarelecimento. Há ainda a formação de uma banda forte em 320 nm após irradiação UV. Contrariamente ao mostrado na literatura de lã, que também é uma estrutura formada por queratina, esta banda não está relacionada com a formação dos cromóforos amarelos. Demonstramos que o amarelecimento inicial do cabelo é um fator determinante na sua variação de cor após irradiação UV e que este amarelecimento é decorrente da ação do calor. Ademais, após a irradiação são formados radicais livres responsáveis pelas reações de degradação no escuro, em que a água tem um papel importante na desativação destes radicais / Abstract: White hair turns yellow after time, but it has no melanin, the pigment responsible for hair color. This yellowing upsets people. In this work we study in depth the color changes and mechanical properties in white hair after exposure to UV, Vis and IR, and the factors that effect the yellowing, including bleaching with H2O2 and the presence of moisture, and try to identify the yellow chromophores. We use two types of white hair, blended hair (blend of several heads), initially yellowish (value of color coordinate blue-yellow, b* = 20), and single head hair (hair of one head), lesser yellow initially (b * = 10). The results show that the initial color affects the behavior by exposuring to UV - Vis: after exposure to a mercury lamp for 200 h, the blended hair turns less yellow (Db * = - 6), and the single head hair turns yellowier (Db * = 2). However, when the blended hair is bleached with H2O2 (b * = 8), turns yellowier after a few hours of irradiation (Db * = 3). By exposing only the Vis turns less yellow independently of initial color, both in blended hair (Db * = - 9) and in the single head hair (Db * = - 3). The results of color changes in white hair after sun irradiation agree with the results of exposure to mercury lamp. The IR radiation at 81°C turns hair yellowier both single head white hair (Db * = 9) and blended white hair (Db * = 3). The blended hair irradiated at 100% relative humidity shows no color variation after 88 h of irradiation. Still, the hair that has been irradiated, but washed with a sodium lauryl sulfate solution after each irradiation period, kept the Db* value. The without washings hair continued less yellow after storage, however, a yellowing (Db* > 1.5) was observed after 1 year. The only significant change in mechanical properties was observed in the reduction of maximum stress by 17% after 480 h of exposure to Vis lamp. UV - Vis absorbance measurements in the white hair solutions with different shades of yellow show absorption in the visible range, these behavior is due to the yellowing, and the formation of a strong band at 320 nm after UV irradiation. Unlike shown in the wool literature, which is also a structure formed by keratin, this band is not related to the formation of yellow chromophores. We demonstrate that the initial hair yellowing is a determining factor in their color variation after UV radiation, and this yellowing is caused by heat action. Still, after irradiations are formed free radicals responsible for the degradation reactions in the dark, in which water plays an important role in the deactivation of these radicals / Mestrado / Físico-Química / Mestre em Química

Thermal oil oxidation is an important reason for the engine oil degradation in trucks. Having a comprehensive model that includes all the influential factors while it is feasible for being implemented in the ECUs, was aimed for this work. Therefore, the chemical investigating of the problem leaded to propose a first kinetic model and its thermal analysis caused modelling the oil thermal behaviour. The latter was developed for four compartments: Bearings, turbocharger, piston cooling and oil sump in the oil path through the lubrication system, because the highest oil temperature happens due to friction, combustion of fuels and exhaust gas transportation. Independency from the design parameters of the compartments and simplicity of models for the ECU implementation caused to investigate two various modelling hybrid approach: physical modelling and control theory approach. The first one was done for the bearings and piston cooling, and showed a high level of complexity leading to switch to the second approach. The latter was applied for all compartments while it satisfied requested requirements. To adjust and evaluate the models, an experimental campaign was devoted to acquiring the needed parameters with consideration of the project budget. Also using the previous simulation and experimental efforts at the company provided a possibility to develop flow rate sub-models used in the thermal modelling. The proposed model for all compartments, well predicted the oil thermal behaviour for both stationary and dynamic operating conditions. A comparison between the experimental data for the oil in the oil sump and turbo charger was done to show the reliability of the related models in both stationary and transient statuses. For the bearings, the simulation data for stationary condition were applied as a reference. The modelled oil temperature after piston cooling was compared to a set of experimental data that presented the probable temperature in some conditions close to stationary operating points.