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.

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.

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.

Conventional urea-based moulding compounds for investment casting patterns are manufactured using a slow “cooking” process. Nowadays in industrial processes the use of a faster process is highly recommended to increase throughput levels. At the same time, for quality control purposes, the requirements of an investment caster must be met. This study is therefore focused on: <ul><li> Finding the appropriate conventional process and conditions to prepare urea-based investment casting moulding compounds. </li><li> Optimising the composition variables to meet the mechanical, thermal, surface, flow and cost properties needed in investment casting. </li><li> Characterising the moulding compounds to meet the requirements of an investment caster by comparing them with an industrial, “cooked” urea-based compound. </li></ul> Polyvinyl alcohol (PVOH) and ethylene vinyl acetate (EVA) urea-based moulding compounds were prepared using a two-roll mill and a conventional extrusion processes respectively. It was possible to injection mould PVOH urea-based moulding compounds with a urea content of up to 90 wt % which had been compounded using a two-roll mill. Using the conventional extrusion process, it was also possible to compound and injection mould EVA urea-based moulding compounds containing up to 70 wt % urea. The effects on composition variables on the properties of the moulding compound were studied and compared to those of the existing “cooked” urea-based moulding compound (Benchmark). The mechanical properties were characterised using the three-point bending test and Charpy impact test. The thermal properties were determined using simultaneous differential thermal analysis and thermogravimetric analysis (SDTA/TGA) and differential scanning calorimeter (DSC). The thermo-mechanical and visco-elastic properties were determined using a dynamic mechanical analyser. A scanning electron microscope was used to study the surface texture of the mouldings. The EVA urea-based moulding compounds showed two endothermic melting peaks and multiple exothermic crystallisation peaks in the DSC curves. The peak at ca. 55 - 66°C corresponds to the melting of the wax/EVA blend, while the large peak at 130 - 132°C corresponds to the melting of the urea. The DSC heating curve of the PVOH urea-based moulding compounds showed two endothermic peaks. The small peak corresponds to the melting of the wax, while the large peak corresponds to the melting of the urea/PVOH blend. PVOH urea-based moulding compound had better mechanical properties than the industrial benchmark. The mechanical properties of the EVA urea-based compound were generally lower. The effect of the wax and polymer content on the mechanical properties was as follows: <ul><li> Increasing polymer content produced weaker but tougher moulding compounds. </li><li> Increasing wax content improved the strength and stiffness but gave compounds that were less tough. </li><li> Two-way Analysis of Variance (ANOVA) indicated significant polymer-wax interactions. </li></ul> The urea content determined the stiffness (elastic modulus) of the compounds. PVOH mouldings had superior stiffness compared with the EVA and cooked urea-based mouldings. The Dynamic mechanical analysis (DMA) results confirmed the result obtained from the modulus of elasticity determination in the three-point bending test. The impact strength increased with an increase in polymer content and reduced with an increase in wax content. The linear thermal expansion coefficient decreased as the urea content was increased. Measured values (100 to 156x10-6°C) were comparable to those of the benchmark. The cooked urea-based moulding compound had the lowest melt viscosity at 110°C, as indicated by its melt flow index (MFI). Fluidity increased with the polymer content. The thermo gravimetric analysis (TGA) results confirmed that both the PVOH and EVA urea-based moulding compounds decomposed readily and left less than 1 wt % ash after combustion. From the SEM results apparent surface roughness appeared to increase with wax content. The EVA urea-based moulding compound had an irregular surface texture. Based on the criteria of cost-effectiveness and environmental friendliness, the synthesis of PVOH urea-based patterns is preferable. The use of a conventional extrusion process to prepare PVOH urea-based patterns is recommended. / Thesis (PhD)--University of Pretoria, 2011. / Chemical Engineering / unrestricted

The thermal conductivities of foamed polymer based materials are much lower thermal conductivity values than unfoamed polymeric materials. Especially, thermal conductivity values of foamed polymers with closed-cell structure decreases to 0.03 W/m.K. The reinforcement of foamed polymeric materials by mixing with bitumen lowers the raw material cost. The main objective of this study is to make a new thermal insulation material with low thermal conductance. In this study, the effects of concentration of calcium carbonate as inorganic filler and the effects of cross-linking on the properties foamed and unfoamed ethylene-vinyl acetate (EVA) copolymer based bituminous blends and composites were investigated. Applications such as thermal, mechanical characteristics of foamed and unfoamed EVA based bituminous composites were investigated. Foamed EVA based bituminous composites were prepared by using Brabender Plastic Coder, PLV 151. Mixing was made at 120 &ordm / C at 60 rpm for 15 minutes. The prepared blends were molded by a technique called Hand Lay-up Self-expanding Batch Molding (HLUSEBM) which was firstly applied by our group. The molding temperature was 170 &ordm / C at which chemical blowing agent and cross-linking agent decomposes. According to test results, at moderate chemical blowing agent and EVA content, the best closed-cell structure with high porosity and low thermal conductivity values were obtained. The compressive properties of foamed polymer based bituminous composites (FPBBCs) increase with increasing CBA and EVA content. With increasing calcium carbonate and EVA concentration, the porosity of FPBBCs increases but thermal conductivity of them decreases. On the other hand, with increasing filler content but with decreasing EVA concentration elastic modulus of FPBBCs increases but elastic recovery decreases.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Cimento AsfÃltico de PetrÃleo (CAP), caracterizado como CAP 50/60, oriundo do Campo Fazenda Alegre, no estado do EspÃrito Santo, foi modificado por adiÃÃo de CopolÃmero de Etileno e Acetato de Vinila (EVA). Na modificaÃÃo foram incorporadas amostras do copolÃmero EVA puro e proveniente do resÃduo da indÃstria de calÃados (EVAR). Os CAPS, polÃmeros e CAPS modificados, foram inicialmente caracterizados por espectroscopia no infravermelho (FTIR) e ressonÃncia magnÃtica nuclear (RMN). AnÃlise tÃrmica, como a termogravimetria (TG) e caloria exploratÃria diferencial (DSC), foi utilizada para o estudo da decomposiÃÃo tÃrmica, bem como para avaliar a estabilidade termoxidativa das amostras. Testes empÃricos como penetraÃÃo, ponto de amolecimento, susceptibilidade tÃrmica e retorno elÃstico, alÃm de viscosidade, tambÃm foram realizados para caracterizaÃÃo dos materiais. Os resultados indicaram que CAPS modificados apresentaram maior estabilidade em atmosfera oxidativa do que em atmosfera inerte. A anÃlise das curvas DSC revelou que os CAPS modificados mostraram-se mais resistentes à trincas tÃrmicas, quando submetidos a temperaturas mais baixas, que o CAP convencional. Os CAPS modificados foram mais resistentes à decomposiÃÃo oxidativa, quando foram submetidos ao envelhecimento simulado. A viscosidade do ligante modificado por adiÃÃo do polÃmero foi aumentada em relaÃÃo ao ligante puro. Diferentemente do CAP convencional, o CAP modificado por EVAR apresentou comportamento nÃo Newtoniano. Os ensaios empÃricos, relativos à penetraÃÃo, ponto de amolecimento, susceptibilidade tÃrmica e retorno elÃstico, mostraram que os CAPS modificados com EVAR, tiveram uma melhoria nas suas propriedades fÃsicas, em relaÃÃo aos CAPS nÃo modificados. / The Petroleum Asphaltic Cement characterized as CAP 50/60, produced at the state of EspÃrito Santo (Fazenda Alegre), was modified by addition of copolymers of ethylene vinyl acetate (EVA) and EVA from the footwearâs industry residue (EVAR). The original and modified CAPS were characterized by infrared spectroscopy (FTIR) and nuclear magnetic resonance (RMN). Thermal analysis,as thermogravimetry (TG) and differential scanning calorimetry (DSC), was used to evaluate the thermal stability of the samples. The characterization was also performed with empirical tests such as penetration, softening point, elastic recovery and viscosity. The main results indicated that polymer modified CAPS presented larger thermal stability in oxidative atmosphere than in inert atmosphere. The analysis of DSC curves revealed that modified CAPS, when submitted to lower temperatures, were more resistant to the thermal cracks than conventional CAP. Also modified CAPS showed to be more resistant to the thermal oxidative decomposition, when submitted to a simulated aging process. The viscosity of the polymer modified binder was increased in relation to the original binder. Polymer modified CAP EVAR presented non-Newtonian behavior, whereas Newtonian behavior was observed for unmodified CAP. It was observed that modifying the asphalt binder with a copolymer EVAR leads to an improvement in the physical properties in relation to the penetration, softening point, thermal susceptibility and elastic recovery

This thesis is focused on experiments, goal of which is to separate protective glass apart from thin layer solar panel. This could lead to less expensive and more efficient recycling. We try to achieve the separation of the glass by thawing ethylene vinyl acetate layer, which serves as insulant and bonding material. Experiments are concluded in high temperature dryer and high temperature vacuum oven on samples of thin layer solar panel, which is for the purposes of experiments cut into same pieces by water jet cutting machine. The initiatory experiments in dryer and oven are to determine value of ethylene vinyl acetate thaw point in tested samples of panel. The thaw point is determined to be 340 °C. When exposed to this temperature, the ethylene vinyl acetate thaws enough for glass to be able to be extracted with minimal physical strength. The process is accompanied by fire destruction of tedlar layer and creation of exhaust gases. Following experiments in vacuum and nitrogen environment are to test their influence on thawing process. Exposing sample to temperature of 340 °C in vacuum led to no new results. Exposing sample to temperature of 340 °C in nitrogen environment prevented fire and achieved same level of thawing of ethylene vinyl acetate while creating less exhaust gases. Even though the fire was prevented, tedlar layer was still destroyed by the high temperature. Furthermore, particles of evaporated ethylene vinyl acetate condensed on surface of module in form of dust. Following experiments studied absorption of panel and influence of accessible solvents on thawing process. It was determined that panel is able to absorb approximately 2 % of acetone, 0,4 % of isopropyl alcohol and 0,11 % of distilled water in its own weight. Experiments with modules soaked in these solvents proved no new results in thawing process. By observing samples of ethylene vinyl acetate taken from module, thawed out of module after experiment in vacuum oven and dust condensed on surface of module after experiment in nitrogen environment, it was proven that the condensed dust is indeed ethylene vinyl acetate.

Master thesis deals with the influence of polyvinylacetate, polycaprolactone, poly(butylene-adipate-co-terephtalate) and talc, ethylenevinylacetate, polyethylene glycol and monosodium citrate on the flow properties, mechanical properties and crystallization ability of PLA. The flow properties were studied using the melt flow index and mechanical properties were studied using a tensile test. The crystallinity was studied by differential scanning calorimetry and on a polarization optical microscope equipped with hot stage. Isothermal crystallization was performed at 95 and 105 °C for 3 h and non-isothermal crystallization was performed with a calorimeter at two cooling rates (1 and 10 °C/min). Upon the isothermal crystallization at 95 °C, the formation of denser crystalline structure was observed and the content of crystalline phase increased in most of the samples. The formation of spherulitic structure was observed at 105 °C in samples with 30 % PVAc, 30 % EVA and PEG. Reducing the cooling rate to 1 °C/min at non-isothermal crystallization had nearly no effect on the crystallization process of the most samples; the content of crystalline phase increased in the samples containing PBAT and PEG, which revealed double melting peak during subsequent heating. The crystalline fraction was the most significantly affected by the addition of PEG. All added polymers except PVAc affected the mechanical properties; PBAT, PCL, EVA and PEG increased the strain and decreased the strength and modulus of elasticity. The samples containing monosodium citrate showed unsatisfactory mechanical properties and could not be measured. The samples containing higher concentration of EVA copolymer showed the phase separation.

The Diploma thesis is adressing the issue of polymer-modified mortars (PMM) and theirs properties in dependence on curing conditions. The reasons of using polymer additives and some selected applications of PMM are described in theoretical part of this work. Cementitious composite (mortar) hardening is especially focused on mechanism of formation co-matrix system based on cement hydration products and polymer film in dependence on curing conditions. The knowledge of interaction of cement and ethylene-vinyl acetate (EVA) copolymer is presented in the latest paragraphs of theoretical work. Following practical part presents influence of EVA to physical and mechanic properties of PMM in dependence of dosage polymer additive and exogenous factors. The study of microstructure was investigated by scanning electron microscope and high-pressure mercury porosimetry. Tests and investigations are described and evaluated.

A presente dissertação teve por objetivo analisar o comportamento de misturas asfálticas modificadas, pelo processo seco, com o copolímero etileno acetato de vinila (EVA), resíduo sólido descartado pela indústria calçadista. Em razão das características do EVA, acredita-se que ele possa melhorar as características mecânicas de misturas asfálticas e a resistência ao desgaste. A maioria dos pesquisadores tem direcionado seus esforços em estudos de misturas asfálticas modificadas pelo processo úmido, porém, devido à natureza do resíduo analisado neste trabalho, optou-se pelo processo seco, que demanda menos energia por não necessitar de moagem do material. A pesquisa compreendeu o estudo de amostras de misturas asfálticas não envelhecidas e com envelhecimento de duas e quatro horas em estufa, com moldagem de corpos-de-prova para realização dos ensaios de resistência à tração por compressão diametral estática, módulo de resiliência por compressão diametral, fluência por compressão uniaxial estática e dinâmica, vida de fadiga e desgaste por abrasão (ensaio Cantabro). Os resultados mostram que a utilização deste resíduo aumentou a resistência das misturas à fadiga e ao desgaste de forma significativa, porém as misturas tornaram-se mais susceptíveis à deformação permanente. O tempo de envelhecimento de curto prazo se mostrou importante, pois aumentou a resistência das misturas à fadiga e à deformação permanente. / The main purpose of the present master thesis was to analyze the behavior of modified hot-mix asphalt, through the dry process, with the copolymer ethylene vinyl acetate (EVA) discarded by the footwear industry. Since the EVA characteristics, it is believed that it can improve hot-mix asphalt mechanic characteristics and the wear and tear resistance. Most of the researchers have been addressing efforts in studies on modified hot-mix asphalt by the wet process, however, due to the nature of the solid residue analyzed in this work, the dry process will demand less energy for not needing of grinding. The research evolved the study of samples of asphalt mixtures not aged and with aging of two and four hours in oven, submitted to indirect tension test, resilient modulus, static and dynamic creep, fatigue life and loss due to abrasion (Cantabro test). The results show that the use of this residue increased the resistance of the mixtures to the fatigue and loss of mass due to abrasion, however the mixtures became more susceptible to the permanent deformation. The short-time aging was shown important, because it increased the resistance of the mixtures to the fatigue and the permanent deformation.