Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, copolímeros à base de acrilonitrila e divinilbenzeno foram sintetizados, utilizando a técnica de polimerização em suspensão, na presença de três agentes porogênicos diferentes (álcool isoamílico, metil-etil-cetona e tolueno). Esses copolímeros foram caracterizados por meio da determinação da densidade aparente, do volume e diâmetro de poros, por microscopia ótica e microscopia eletrônica de varredura e foram avaliados quanto à capacidade de inchamento em heptano e tolueno. O principal intuito dessa pesquisa foi correlacionar a formação da estrutura porosa desses materiais com os principais parâmetros de síntese (grau de diluição dos monômeros, poder solvatante do diluente e teor do agente de reticulação). Desses parâmetros, o que mais influenciou na formação da estrutura porosa desses materiais foi o poder solvatante do diluente. A teoria dos parâmetros de solubilidade de Hansen e Hildebrand foi utilizada com o intuito de fazer uma previsão das características porosas dos copolímeros à base de acrilonitrila e divinilbenzeno sintetizados na presença de três diluentes diferentes. Dentre esses diluentes, o álcool isoamílico foi o pior solvente para os copolímeros de AN-DVB, em todos os teores de agente de reticulação e em todas as diluições utilizadas. O tolueno foi o melhor solvente para os copolímeros que contêm altos teores de agente de reticulação. Estas observações estão de acordo com as previsões dos parâmetros de solubilidade de Hansen e Hildebrand. A metil-etil-cetona foi o melhor solvente para os copolímeros que contêm teores intermediários de agente de reticulação. Esta observação só está condizente com o parâmetro de solubilidade de Hansen. / In this work, acrylonitrile-divinylbenzene copolymers were synthesized using the technique of suspension polymerization in the presence of three different solvents (isoamyl alcohol, methyl-ethyl-ketone and toluene). These copolymers were characterized by apparent density, pore volume and pore diameter, optical and scanning electron microscopy, and were evaluated for their ability to swell in heptane and toluene. The principal aim of this research was to correlate the porous structure formation of these materials, with the main synthesis parameters (degree of dilution, solvating power of the diluent and crosslinking degree). Among these parameters, the most important on the formation of the materials porous structure was the solvating power of the diluent. The theory of solubility parameters of Hansen and Hildebrand was used in order to make a prediction of the porous characteristics of acrylonitrile-divinylbenzene copolymers synthesized in the presence of three different diluents. Among these solvents, the isoamyl alcohol was the worst solvent for acrylonitrile-divinylbenzene copolymers, at all levels of crosslinking degree and at all dilutions used. Toluene was the best solvent for the copolymers containing high levels crosslinking degree. These observations are consistent with the predictions of the solubility parameters of Hansen and Hildebrand. The methyl-ethyl-ketone was the best solvent for the copolymers containing intermediate crosslinking degree. This observation is only consistent with the Hansen solubility parameters. In this work, acrylonitrile-divinylbenzene copolymers were synthesized using the technique of suspension polymerization in the presence of three different solvents (isoamyl alcohol, methyl-ethyl-ketone and toluene). These copolymers were characterized by apparent density, pore volume and pore diameter, optical and scanning electron microscopy, and were evaluated for their ability to swell in heptane and toluene. The principal aim of this research was to correlate the porous structure formation of these materials, with the main synthesis parameters (degree of dilution, solvating power of the diluent and crosslinking degree). Among these parameters, the most important on the formation of the materials porous structure was the solvating power of the diluent. The theory of solubility parameters of Hansen and Hildebrand was used in order to make a prediction of the porous characteristics of acrylonitrile-divinylbenzene copolymers synthesized in the presence of three different diluents. Among these solvents, the isoamyl alcohol was the worst solvent for acrylonitrile-divinylbenzene copolymers, at all levels of crosslinking degree and at all dilutions used. Toluene was the best solvent for the copolymers containing high levels crosslinking degree. These observations are consistent with the predictions of the solubility parameters of Hansen and Hildebrand. The methyl-ethyl-ketone was the best solvent for the copolymers containing intermediate crosslinking degree. This observation is only consistent with the Hansen solubility parameters.

Orientador: Alexandre Luiz Souto [Unesp] Borges / Resumo: Este estudo visou sintetizar e caracterizar mantas não tecidas de nanofibras (NFs) do acrilonitrila butadieno estireno (ABS), poliamida 6 (PA6) e poliestireno (PS), e avaliar sua capacidade de ser utilizada como reforço no polimetilmetacrilato (PMMA). O ABS foi dissolvido em diclorometano e acetona, a PA6 pelo 1,1,1,3,3,3-hexafluoro-2-propanol e o PS pela dimetilformamida, em uma concentração definida em estudo piloto. Após determinados os melhores parâmetros de eletrofiação (tensão contínua, razão de fluxo e distância agulha/anteparo) as amostras de cada grupo foram analisadas em microscopia eletrônica de varredura, análise de molhabilidade, análise de difratometria de raios X, espectroscopia de infravermelho por transformada de Fourier, diâmetro das fibras e resistência a tração. As NFs produzidas foram incluídas na área de tração dos corpos de prova em resina acrílica ativada termicamente (RAAT) conforme ISO1567, perfazendo 4 grupos (n=20), 1 controle (Grupo 1) e 3 experimentais (Grupo 2, RAAT+NF/ABS; Grupo 2, RAAT+NF/PA6; Grupo 4, RAAT+NF/PS), para ensaio de flexão três pontos para analisar suas propriedades mecânicas, como: módulos de elasticidade e resistência a flexão. De acordo com os testes de caracterização, as mantas se apresentaram hidrofóbicas, não houve mudança de sua estrutura polimérica, concluindo-se então que a técnica da eletrofiação foi promissora na síntese de mantas de NFs. A variação dos parâmetros afetou diretamente a morfologia, resultando em fibras u... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This study aimed to synthesize and characterize non-woven blankets of acrylonitrile butadiene styrene (ABS), polyamide 6 (PA6) and polystyrene (PS) nanofibers (NFs), and to evaluate their ability to be used as reinforcement in polymethyl methacrylate (PMMA). ABS was dissolved in dichloromethane and acetone, PA6 by 1,1,1,3,3,3- hexafluoro-2-propanol and PS by dimethylformamide at a concentration defined in a pilot study. After determining the best electrospun parameters (continuous voltage, flow rate and needle/shield distance) the samples from each group were analyzed by scanning electron microscopy, wettability analysis, X-ray diffraction analysis, Fourier transform infrared spectroscopy, fiber diameter and tensile strength. The NFs produced were included in the tensile area of the thermally activated acrylic resin (RAAT) specimens according to ISO1567, making up 4 groups (n = 20), 1 control (Group 1) and 3 experimental (Group 2, RAAT+NF/ABS; Group 3, RAAT+NF/PA6 and Group 4 (RAAT+NF/PS), for three point bending test to analyze their mechanical properties, as: modules of elasticity and flexural strength. According to the characterization tests, the blankets were hydrophobic, there was no change in their polymeric structure, concluding that the electrospinning technique was promising in the synthesis of NFs blankets. The parameters variation affected directly in the morphology, resulting in uniform, bulky and without defects (beads) NFs blankets. The Groups 3 and 4 (NF/PA6+RA... (Complete abstract click electronic access below) / Mestre

This master‘s thesis deals with 3D printing for non-commercial RepRap 3D printer type and materials used in printing. The outcome of this work is a brief introduction to 3D printing, the theory of heat transfer and analysis of the two most important parts of the printer hot bed and hot end. To analyze and optimize the temperature profile of the hot bed and hot end are used Computer Aided Engineering systems CAD and CAE, SolidWorks and SolidWorks Flow Simulation.

Diploma thesis studies the effect of temperature (75 and 105 °C) and the effect of 3 kinds of liquids (silicone and hydraulic oil and coolant) at room temperature and at 105 °C on change of the structure of 3 species butadiene-acrylonitrile (NBR) seals (o-ring and two types of bolts). The seals are inspected by the thermogravimetric analysis, differential scanning calorimetry and infrared spectroscopy, the influence of 105 °C on the o-rings is also evaluated in terms of changes in tensile properties. The greatest changes in the composition and structure are observed on o-rings particularly due to temperature of 105 °C, there was a significant reduction in dilatability and an increase in stiffness and glass transition temperature. The root cause is the surface and centre additive decomposition and oxidation. The bolts have suffered from decomposition of the protective surface layer and the additives in the centre, structural change was minor. Exposure to 75 °C has resulted in a gradual loss of low molecular weight substances. Liquids at room temperature didn‘t affect the structure of the seals, at 105 °C it caused a loss of weight due to decomposition of the protective surface layer and release of additives and the products of their decomposition. Results showed that the common use of the NBR seals at 105 °C is unsuitable, at 75 °C it leads to gradual changes, loss in mechanical and sealing properties.

No description available.

[pt] O Acrilonitrila-Butadieno-Estireno (ABS) é um polímero de grande uso industrial, sendo empregado em inúmeros produtos. Muitas de suas aplicações necessitam de uma elevada resistência a combustão seja pela presença de cargas elétricas (Efeito Joule) ou a exposição a ambientes de altas temperaturas. No entanto, o ABS, de modo semelhante a maioria dos polímeros, não é tão resistente a combustão, sendo necessário o emprego de aditivos Retardantes de Chamas (RC). A introdução desses aditivos pode, entretanto, acarretar alteração nas propriedades mecânicas, de forma que é necessário se comparar o comportamento do material com e sem aditivos. Particularmente importante é o comportamento a longo prazo, como a fluência. Assim, nesse trabalho foi avaliado o comportamento a fluência do ABS sem aditivo e de três sistemas ABS/RC. Foi usado um sistema empregando um aditivo comercial à base de bromo (ABS − Br), que serviu como base de comparação e dois sistemas recentemente desenvolvidos, empregando bio-retardantes, a saber: ácido tânico (TA) e polifosfato de amônio (APP). Os resultados dos ensaios mostraram que o aditivo comercial não acarretou variação da vida em fluência em relação ao ABS sem aditivo. Por outro lado, os resultados indicaram que a vida em fluência foi reduzida quando o aditivo APP foi incorporado e que aumentou quando o TA foi adicionado. Os dados experimentais dos ensaios de fluência foram usados para avaliar o comportamento viscoelástico dos quatro grupos de materiais. O ABS teve seu comportamento adequadamente representado pelo modelo de Burgers, assim como a ABS com aditivo à base de bromo. O modelo que melhor descreveu o comportamento do ABS com APP foi o modelo modificado de Burgers (Streched Burgers). Nem todas as amostras do ABS com TA apresentaram fluência no intervalo de tempo usado e o modelo que melhor descreveu o comportamento foi o do sólido linear padrão. / [en] Acrylonitrile-Butadiene-Styrene (ABS) is a polymer of great industrial use, being used in numerous products. Many of its applications require a high resistance to combustion, either due to the presence of electrical charges (Joule Effect) or exposure to high temperature environments. However, ABS, like most polymers, is not as resistant to combustion, requiring the use of Flame Retardant (RC) additives. The introduction of these additives can, however, lead to changes in the mechanical properties, so it is necessary to compare the behavior of the material with and without additives. Particularly important is long-term behavior such as fluency. Thus, in this work, the creep behavior of ABS without additive and of three ABS/RC systems was evaluated. A system employing a commercial bromine-based additive (ABS − Br) was used, which served as a basis for comparison and two recently developed systems employing bio-retardants, namely: tannic acid (TA) and ammonium polyphosphate (APP) . The test results showed that the commercial additive did not cause a change in creep life compared to ABS without additive. On the other hand, the results indicated that the creep life was reduced when the APP additive was incorporated and that it increased when the TA was added. Experimental data from creep tests were used to evaluate the viscoelastic behavior of the four groups of materials. ABS had its behavior adequately represented by the Burgers model, as well as ABS with bromine-based additive. The model that best described the behavior of ABS with APP was the modified Burgers model (Streched Burgers). Not all ABS samples with TA showed fluence in the time interval used and the model that best described the behavior was the standard linear solid.

Several approaches have been used to develop carbon nanotube (CNT) based electrochemical supercapacitors. These approaches include the following: (a) stabilization and carbonization of ternary composites of polyacrylonitrile (PAN), poly (styrene co-acrylonitrile) (SAN) copolymer, and single wall carbon nanotubes (SWNTs); (b) SWNT membranes functionalized with aryl chloride, sodium sulfonate, aryl sulfonic acid, bis(3,5-di-tert-butylphenyl)5-aminobenzene-1,3-dioate, and 4,4 -methylenedianiline; and (c) pyrrole treated SWNTs. In addition nitric acid functionalized and heat-treated SWNT membranes have been studied. The electrochemical supercapacitor behavior of these membrane electrodes has been characterized by cyclic voltammetry, constant current charging-discharging, and impedance analysis in aqueous and ionic liquid electrolytes. Long term performance of selected electrodes has been evaluated. The surface area and pore size distribution was quantified by N2 gas adsorption/desorption and correlated with capacitance performance. The surface functional groups have been characterized by X-ray photoelectron spectroscopy. CNT electrode/electrolyte interaction has been characterized using contact angle measurements. Electrolyte absorption by the electrodes has also been characterized. Carbonized PAN/SAN/SWNT ternary composites exhibit double layer capacity of over 200 μF/cm2. By comparison, the double layer capacity of classical meso-porous carbons is in the range of 10-50 μF/cm2. The capacitance of functionalized SWNTs is up to 2 times that of the control bucky paper made from unfunctionalized SWNTs. Energy density of functionalized electrodes when evaluated in an ionic liquid is as high as 28 kJ/kg. High capacitance (up to 350 F/g) was obtained for pyrrole-treated functionalized SWNT membranes in 6 M KOH. This value is almost seven times that of the control bucky paper. Correlating the capacitance with surface area and pore size distribution, it was observed that macropores (pore width greater than 50 nm) play an important role for achieving high capacitance.

The aim of this study was to investigate rubber toughening of resol type phenol-formaldehyde resin. For this purpose, phenolic resin was first modified by only acrylonitrile butadiene rubber, and then by using nitrile rubber together with 3-aminopropyltriethoxysilane. Test specimens were prepared by mixing and casting of liquid phenolic resin in three groups. In the first one, neat phenolic resin specimens were produced. In the second group, phenolic resin was modified with 0.5, 1, 2, and 3 wt.% nitrile rubber, while in the last group modification was carried out by using 0.5 wt.% nitrile rubber together with 1, 2, and 4wt.% amino silane (with respect to nitrile rubber). All specimens were heat cured in the oven. In order to observe behaviors of the specimens, Three-Point Bending, Charpy Impact, Plane-Strain Fracture Toughness, and Dynamic Mechanical Analysis tests were conducted according to the related ISO standards for all specimens groups. Scanning Electron Microscopy was also used for the fractographic analysis of some samples. It can be concluded that, although there were problems in mixing and casting of liquid resol type phenolic resin, its toughness could be improved by using nitrile rubber and amino silane. Modification by using nitrile rubber and amino silane together was much more effective than by using only nitrile rubber. In this synergistic case for instance, Charpy impact strength and fracture toughness values of the neat phenolic specimens were increased 63% and 50%, respectively. SEM studies indicated that the main rubber toughening mechanism was shear yielding observed as deformation lines especially initiated at the domains of nitrile rubber and amino silane.

In an attempt to improve the quality in finite element analysis of thermoformed components, a method for predicting the thickness distribution is presented. The strain induced anisotropic material behaviour in the amorphous polymers of concern is also taken into account in the method. The method comprises of obtaining raw material data from experiments, followed by a simulation of the vacuum thermoforming process where hyperelastic material behaviour is assumed. The theory of hyperelasticity that was applied was based on the Ogden model and implemented in the FE-software LS-DYNA. Material behaviour from thermoformed prototypes is examined by experiments and implemented together with the mapped results from the thermoforming simulation in a succeeding FE-model. For the latter, the three-parameter Barlat model was suggested, giving the possibility to account for anisotropic material behaviour based on an initial plastic strain.

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2014-12-19T17:14:06Z No. of bitstreams: 0 / Made available in DSpace on 2014-12-19T17:14:06Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP