Abstract This work investigates the kinetics of the emulsion polymerization of vinyl acetate. Several aspects of this system have been clarified, including the induced decomposition of persulfate, retardation by oxygen and entry by, and analysis of, the aqueous phase oligomeric radicals. It has been shown that the retardation period observed in the emulsion polymerization of VAc can be explained by the effect of traces of oxygen (< 10-6 M) on the entry efficiency of the initiator-derived aqueous-phase oligomeric radicals. Comparison of rates of polymerization in V and persulfate -initiated polymerizations together with electrospray mass spectrometry of aqueous phase oligomers, has shown that the mechanism for the induced decomposition of persulfate by vinyl acetate is chain transfer to initiator from aqueous-phase oligomeric radicals. A value has been determined for the rate coefficient for transfer to initiator, by fitting literature data to a model based on this mechanism. The reported independence of the rate of polymerization from the monomer concentration in the emulsion polymerization of vinyl acetate has been investigated. Possible explanations for this behaviour have been proposed and tested in this work, by measuring radical-loss rates directly with y-relaxation techniques. Although the Y relaxations were found to be affected by experimental artefacts, it has been demonstrated that rapid exit is not responsible for the high radical-loss rates in this system. The major artefact identified in the y relaxations was the significant effect of relatively small exotherms on relaxation behaviour, Methodologies were developed for correcting affected data and for avoiding exotherms under certain conditions. Arrhenius parameters were determined for the rate coefficient for chain transfer to monomer using the In^M method, which utilises the whole MWD. This section of the work is incomplete, for reasons detailed in chapter 5. However, as a preliminary indication it was found that the frequency factor was 106.38 M-1 s-1 and the activation energy was 38.8 kJ mol-1.

Abstract This work investigates the kinetics of the emulsion polymerization of vinyl acetate. Several aspects of this system have been clarified, including the induced decomposition of persulfate, retardation by oxygen and entry by, and analysis of, the aqueous phase oligomeric radicals. It has been shown that the retardation period observed in the emulsion polymerization of VAc can be explained by the effect of traces of oxygen (< 10-6 M) on the entry efficiency of the initiator-derived aqueous-phase oligomeric radicals. Comparison of rates of polymerization in V and persulfate -initiated polymerizations together with electrospray mass spectrometry of aqueous phase oligomers, has shown that the mechanism for the induced decomposition of persulfate by vinyl acetate is chain transfer to initiator from aqueous-phase oligomeric radicals. A value has been determined for the rate coefficient for transfer to initiator, by fitting literature data to a model based on this mechanism. The reported independence of the rate of polymerization from the monomer concentration in the emulsion polymerization of vinyl acetate has been investigated. Possible explanations for this behaviour have been proposed and tested in this work, by measuring radical-loss rates directly with y-relaxation techniques. Although the Y relaxations were found to be affected by experimental artefacts, it has been demonstrated that rapid exit is not responsible for the high radical-loss rates in this system. The major artefact identified in the y relaxations was the significant effect of relatively small exotherms on relaxation behaviour, Methodologies were developed for correcting affected data and for avoiding exotherms under certain conditions. Arrhenius parameters were determined for the rate coefficient for chain transfer to monomer using the In^M method, which utilises the whole MWD. This section of the work is incomplete, for reasons detailed in chapter 5. However, as a preliminary indication it was found that the frequency factor was 106.38 M-1 s-1 and the activation energy was 38.8 kJ mol-1.

Ethylene-vinyl acetate co-polymers are widely used as cold-flow improving additives in diesel fuels. Although their functionality is undisputed, the mechanisms of action at a molecular level are not fully understood. Theories that EVA acts as both a nucleating agent for small wax crystals and as a crystal growth inhibitor are generally acknowledged, however the understanding of the effect of structure on additive performance is limited. Studies have been carried out using molecular simulation techniques with the aims of improving the understanding of the interactions between EVA and diesel fuels, and assessing the potential of these methods for the analysis of different additive structures and fuel compositions. Firstly, the ability of Monte Carlo simulations to predict the chemical potentials of n-alkanes in organic solvents was studied. This information would be of use in determining the characteristics of different fuel compositions. It was found that the particle insertion method used becomes more efficient as the aspect ratio of the solvent increases relative to that of the solute. Despite the identification of expected linear trends in the chemical potential of n-alkanes, it was not possible to produce high quality quantitative data using this method. The effect of vinyl acetate spacing and solvent environment on the configuration of lone EVA molecules in the liquid phase was studied. Molecular dynamics showed that closely spaced vinyl acetate groups increase the tendency of the molecule to fold at that point, whilst molecules with 2 or 3 ethylene groups in between show resistance to folding. It was shown that n-hexane as a solvent produced more folded configurations than benzene and n-hexadecane respectively. Monte Carlo simulations were also performed but were largely unsuccessful. Finally, molecular dynamics simulations were performed to study the effect of different EVA structures on the spontaneous crystallisation of n-hexadecane, and the interaction of the EVA with the resulting structures at a molecular level. It was shown that different EVAs had varying effects on the crystallisation, with trends attributed to the spacing of the vinyl acetate groups and the length and position of extended aliphatic sections of the EVA molecules. One molecule, with evenly spaced side-groups and no extended aliphatic sections was shown to fully prevent the formation of any crystalline structure within the time of the simulation where all other EVA molecules allowed some degree of wax formation to occur.

Orientador: Beatriz Eleutério Goi / Coorientador: Valdemiro Pereira de Carvalho Júnior / Banca: Pedro Ivo da Silva Maia / Banca: Ana Maria Pires / Resumo: Nas últimas décadas, a polimerização radicalar controlada (CRP) tem se tornado muito importante, pois permite a síntese de macromoléculas de arquiteturas específicas com um controle sobre as propriedades químicas e físicas. Sendo assim, este trabalho apresenta a síntese de novos complexos de Mn(II) e Fe(II) coordenados à ligantes bases de Schiff bidentados, que são resultantes da condensação do salicilaldeído com as seguintes cicloalquilaminas: (1) Ciclopentilamina, (2) Cicloexilamina, (3) Cicloeptilamina e (4) Ciclooctilamina, de forma que estes possam ser utilizados como mediadores da polimerização radicalar mediada por organometálicos. Os ligantes foram caracterizados pelas seguintes técnicas: espectroscopia de ressonância magnética nuclear de hidrogênio (RMN de 1H), espectroscopia de absorção na região do ultravioleta-visível (UV-Vis) e espectroscopia vibracional na região do infravermelho (FTIR). Já os complexos de Mn(II) e Fe(II) foram caracterizados pelas técnicas de FTIR, UV-Vis, voltametria cíclica (VC) e ponto de fusão (p.f.). Os estudos cinéticos de polimerização foram realizados para os complexos de manganês e ferro. O complexo [MnIIbis(N-Salicilideno-Ciclopentilamina)], Mn(L1)2, apresentou um melhor controle na polimerização do acetato de vinila com menores valores de polidispersidade e a curva de massa molecular (Mn) mais próxima aos valores da curva teórica. Já os complexos de ferro mediadores apresentaram um comportamento mais similar, não havendo muita... / Abstract: In the last decades, controlled radical polymerization (CRP) has become very important, since it facilitates the synthesis of macromolecules of specific architectures with excellent control over the chemical and physical properties. Thus, this work presents the synthesis of new Mn(II) and Fe(II) complexes coordinated with the bidentate Schiff bases ligands, which are the result of the condensation of salicylaldehyde with cycloalkylamines: (1) cyclopentylamine, (2) cyclohexylamine, (3) cycloheptylamine and (4) cyclooctylamine, so that they can be used as mediators of radical polymerization mediated by organometallic (OMRP). The ligands synthesized were characterized by proton nuclear magnetic resonance (1H-NMR) spectroscopy, ultraviolet-visible (UV-Vis) absorption spectroscopy and Fourier-transform infrared spectroscopy (FTIR) techniques. The synthesized Mn(II) and Fe(II) complexes were studied by FTIR, UV-Vis, cyclic voltammetry (CV) and melting point (m.p.). Kinetic polymerization studies were performed for the manganese and iron complexes. The [MnIIbis (N-Salicylidene-Cyclopentylamine)], Mn(L1)2, complex showed a better control in the polymerization of vinyl acetate with lower values of polydispersity and the molecular mass curve (Mn) closer to the values of the theoretical curve. However, the iron mediator complexes presented a more similar behavior, not having much difference in the kinetic curves / Mestre

Scanning Tunnelling Microscopy (STM) was utilised together with the high resolution depth-profiling capabilities of Medium Energy Ion Scattering (MEIS), a technique traditionally associated with single crystal substrates, to probe the mean size and depth dependent composition profile of bimetallic PdAu nanoparticles on planar oxide surfaces as functions of the starting composition and annealing temperature. In order to fit composition profiles to experimental MEIS data, a new analysis tool has been designed that models the particles as flat-topped structures with a hexagonal base which can be divided into a number of shells, each shell corresponding to a particular ion pathlength inside the material. The reliability of this method will be discussed in detail. Fitting results show that the surface layers are always significantly enriched in Au compared to the bulk alloy composition. By comparing MEIS data for clean surfaces data for modified surfaces it was found that Pd generally segregates towards the particle surface on adsorption of acetic acid. The interaction of potassium acetate with Au/Pd{111} alloy surfaces of varying composition has been investigated using Temperature Programmed Desorption (TPD) and Reflection Absorption Infra Red Spectroscopy (RAIRS). At lower coverage, potassium acetate reacts reversibly with the surface to form CO and carbonate. Formation of surface acetate is observed on Pd-rich surfaces only. At higher coverage, acetate is the major surface species formed on all samples examined.

Wood disks in various states of decay can be inexpensively preserved and prepared for accurate crossdating and precise tree-ring measurement by impregnation with commercial wood glue. The technique does not affect the dimensions or physiological features of samples preserved in this manner. Dead red spruce trees on Mt. Washington, New Hampshire, remain available for dendrochronological examination as long as 29 years after their last year of stem growth.

Os processos industriais de polimerização em emulsão são normalmente realizados em reatores batelada ou semi batelada ou em tanques agitados contínuos (CSTR). Os reatores contínuos têm a vantagem de terem menor porte e de propiciarem melhor controle de qualidade do produto através da redução de variações de batelada a batelada. Além disso, as oscilações periódicas autosustentadas na conversão de monômero e no tamanho da partícula, que são normalmente observadas em reatores do tipo CSTR, podem ser minimizadas em reatores tubulares mediante o uso de dispositivos de mistura estáticos adequados combinados com escoamento pulsado (oscilatório). O objetivo deste trabalho é apresentar o desenvolvimento de uma copolimerização em emulsão de acetato de vinila e acrilato de butila em uma coluna pulsada com pratos perfurados (CPPP). A fim de aumentar a sua flexibilidade operacional, a coluna é composta de 5 seções, cada uma apresentando controles independentes de alimentação lateral e temperatura. Dependendo da estratégia de alimentação de monômero, pode-se notar uma deriva de composição durante o processo de copolimerização em emulsão do acetato de vinila e acrilato de butila devido às grandes diferenças entre estes monômeros em suas razões de reatividade e nas solubilidades na fase aquosa. Neste caso, a CPPP propicia diferentes possibilidades de alimentação que permitem controlar a composição do copolímero através da alimentação do monômero mais reativo ao longo da coluna. Por esta razão, foi avaliado neste estudo o efeito do número de correntes de alimentação sobre as propriedades do polímero. Diferentes números de correntes laterais de alimentação de monômero foram empregadas nos ensaios experimentais. Diferenças na uniformidade da composição do copolímero podem ser notadas dependendo do número de correntes laterais de alimentação aplicadas em cada teste. A fim de permitir variações de temperatura, somente a temperatura de entrada das camisas de resfriamento foi fixada. Para simular as reações foi utilizado um modelo matemático desenvolvido baseado no modelo de escoamento pistonado (plug-flow) axialmente disperso. No presente trabalho, um balanço de energia foi incluído ao modelo matemático anterior de modo que a influência de diferentes perfis de temperatura pudesse ser considerada. O efeito das correntes laterais de alimentação de monômero sobre as propriedades do copolímero puderam ser previstas com suficiente precisão pelas simulações do modelo, as quais foram também validadas pelos resultados experimentais. Com base nas simulações matemáticas, um perfil ótimo de alimentação pôde ser calculado e experimentalmente aplicado na CPPP permitindo a produção de um copolímero mais homogêneo. Os resultados também permitiram a validação do modelo matemático como uma ferramenta confiável na predição de ensaios experimentais. Além disso, as vantagens da CPPP puderam ser verificadas pelo seu desempenho adequado como reator tubular para processos contínuos de copolimerização em emulsão. Finalmente, os resultados indicaram a possibilidade de melhorias adicionais nas propriedades do polímero através do emprego de diferentes temperaturas e perfis de alimentação de outros reagentes ao longo da coluna. / Industrial emulsion polymerization processes are usually performed in batch or semi-batch stirred tanks, or in continuous stirred tank reactors (CSTR). Continuous reactors have the advantage of being smaller and providing a better product quality control by the reduction of the batch-to-batch variations. In addition, periodical self-sustained oscillations in monomer conversion and in particle size that are usually observed in CSTR can be minimized in tubular reactors presenting good radial mixing. Such conditions can be achieved in tubular reactors by using adequate static mixing devices combined with pulsed (oscillatory) flow. The aim of this work is to report the development of a continuous emulsion copolymerization of vinyl acetate and butyl acrylate performed in a pulsed sieve plate column (PSPC). In order to improve its operational flexibility, the column is composed of five sections, each one presenting independent lateral feed and temperature controls. Depending on the monomer feeding strategy, a composition drift can be noticed during the emulsion copolymerization process of vinyl acetate and butyl acrylate, due to the large differences in reactivity ratios and aqueous phase solubility between these monomers. In this case, the PSPC provides different operational feeding possibilities which allow controlling the copolymer composition by feeding the more reactive monomer along the column. For this reason, in this study the effect of the number of lateral feed streams on the polymer properties was evaluated. Different numbers of lateral monomer feed streams were employed in the experimental runs. Differences in the uniformity of the copolymer composition can be noticed along the reactor depending on the number of lateral feed streams applied in each test. In order to allow temperature variations, during each reaction only the inlet temperature of the cooling jackets was fixed. A developed mathematical model based on the axially dispersed plug-flow model was used to simulate the reactions. In the present study the energy balance was included in the mathematical model so that the influence of different temperature profiles could be taken into account. The effect of lateral monomer feed streams over the copolymer properties could be predicted with sufficient accuracy by model simulations which were also validated by the experimental results. Based on mathematical simulations, an optimal feeding profile could be calculated and experimentally applied in the PSPC allowing the production of a more homogeneous copolymer. The results also permitted the validation of the mathematical model as a reliable tool in the prediction of experimental runs. Furthermore, the advantages of the PSPC could be verified by its adequate performance as a tubular reactor for continuous emulsion copolymerization processes. Finally, the results indicate the possibility of further improvements in other polymer properties by employing different temperature and feeding profiles of other reagents along the column.

Carbon nanotubes (CNTs) have been a major interest of study since 1991. A panel of properties and phenomena associated with carbon nanotubes due to their special combination of dimension, structure and topology have been investigated in the last years. Recently, it appears interesting to use carbon nanotubes at low loading content to obtain materials with enhanced mechanical and thermal properties. One of the major challenges is actually to disperse easily and individually these nanotubes in polymer matrices to obtain materials with increased properties for different application uses. Ethylene-vinyl acetate (EVA) copolymer is commonly used in cable industry. It is required to introduce high contents of alumina trihydrate (ATH) or magnesium dihydroxide (MDH) as fire retardant, to avoid fire hazards and reduce flammability. But this high mineral loading results in a decrease of the mechanical performances of the materials. This work aims at studying the influence of the incorporation of multiwall carbon nanotubes (MWNTs) on the tensile properties and the fire behavior of EVA nanocomposites. This work demonstrates, on one side, the significant effect of the previous nanotube coating by a thin layer of high density polyethylene (HDPE-coating) on the mechanical behavior of the so-obtained nanocomposites and explain, on the other side, the flame retardant efficiency of MWNTs in EVA nanocomposites. An original mechanism related to the action of the MWNTs during the combustion process is proposed and the effect of the HDE-coating on the cohesion of the residues is discussed.

Vinyl acetate (VA) is an important monomer used in the production of paints, surface coatings and adhesives. Synthesis of VA is usually carried out over supported Pd alloy catalysts with a selectivity as high as 96% and described as C2H4 + CH3COOH + ½ O2 -> C2H3OOCCH3 + H2O Although the VA synthesis reaction has been industrially carried out for many years, the nature of the active sites and the reaction mechanism is still unclear. The goal of this study was to acquire a fundamental understanding of the VA reaction mechanism by carrying out detailed kinetic and spectroscopic investigations on single crystals and supported Pd catalysts, and to detail the role of alloying in optimizing the selectivity of this important industrial reaction. A combination of surface science techniques and kinetic measurements has been used to address the mechanism. Supported catalysts, 1 wt% Pd/SiO2 and 5 wt% Pd/SiO2, and 1 wt% Pd-0.5 wt% Au/SiO2, were prepared by an incipient wet-impregnation method and characterized using XRD and TEM. On Pd-only catalysts the reaction rates were found to be: Pd(100) < 5 wt% Pd/SiO2 (dpd = 4.2 nm) < 1 wt% Pd/SiO2 (dpd = 2.5 nm). Particle size-dependence of the reaction rates is evident for the Pd-only catalysts, which suggests a degree of structure sensitivity of the reaction. There is an increased availability of uncoordinated, edge atoms on small particles. With a Pd single crystal, fewer less-coordinated surface sites are present compared to a comparable area on a small Pd particle on a supported Pd catalyst. The formation of Pd carbide (PdCx) during the synthesis of VA was investigated over Pd/SiO2 catalysts with two different Pd particle sizes, as well as over a Pd-Au/SiO2 mixed-metal catalyst. XRD data indicate that smaller Pd particles show greater resistance to the formation of PdCx. The alloying of Au with Pd is apparently very effective in preventing PdCx formation in Pd-based catalysts for VA synthesis. Addition of Au to Pd/SiO2 catalysts significantly enhances the VA formation rate and selectivity. Infrared reflection absorption spectroscopy (IRAS) of CO on Pd/Au(100) and Pd/Au(111) confirms the presence of Pd as isolated monomers on a Au-rich surface. A pair of Pd monomers is the most favorable active site for the formation of VA. The spacing between the two active isolated Pd atoms is critical and is demonstrated by the relative rates of VA formation on Pd/Au model catalysts, i.e. Pd/Au(111) < Pd/Au(100). The role of Au is to isolate the surface Pd atoms and thus suppress the formation of by products, CO and CO2. A pair of Pd monomers required for VA synthesis is further confirmed by the results from model studies of Sn-Pd.

The variation in properties of Polypropylene (PP) / Ethylene Vinyl Acetate (EVA) blends upon EVA content, temperature, and light stability were followed by using tensile testing, impact testing, and differential scanning calorimetry (DSC). Young&rsquo / s modulus of the blends decreased with increasing drawing temperature and EVA content. The stress at break values of the blends slightly increased with EVA whereas decreased with drawing temperature. The percent strain at break values of the blends were found to increase abruptly by increasing EVA content and drawing temperature. These changes in the mechanical properties are the indication of compatibility. The impact tests were performed only at 0&deg / C, 25&deg / C and the impact strength increased with the temperature and EVA content, but none of the samples were broken at higher testing temperatures. The effect of stabilizer was very obvious because stabilizer-free samples failed after 400 hours whereas, the samples with stabilizer resisted up to 750 hours. Elongation values of the samples decreased because of increasing brittleness by UV irradiation. We also observed chain stiffening effect by crosslinking in all samples upon UV irradiation. Thermal analysis of the blends of the drawn samples showed an increasing trend of crsytallinity with increasing drawing temperature. Increasing drawing temperature made polymer chains more flexible because of the increasing chain mobility. These flexible chains were then oriented in one direction during tensile testing and therefore uniaxial crystallization occurred. The morphology of impact and tensile tests samples were also analyzed by scanning electron microscope (SEM). The fibrillation of pure PP is higher than the fibrillation of the blends.