Submitted by RENATO CARVALHO RESENDE (htc.renato@gmail.com) on 2017-03-30T23:23:31Z No. of bitstreams: 1 Dissertação Mestrado Renato Carvalho Resende.pdf: 9175175 bytes, checksum: 3d504c6ae855f8c5ee734700afd5a7cc (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2017-04-06T14:17:14Z (GMT) No. of bitstreams: 1 resende_rc_me_bauru.pdf: 9175175 bytes, checksum: 3d504c6ae855f8c5ee734700afd5a7cc (MD5) / Made available in DSpace on 2017-04-06T14:17:14Z (GMT). No. of bitstreams: 1 resende_rc_me_bauru.pdf: 9175175 bytes, checksum: 3d504c6ae855f8c5ee734700afd5a7cc (MD5) Previous issue date: 2017-03-06 / Os elastômeros termoplásticos (TPE) têm sido bastante empregados em substituição às borrachas tradicionais, por terem custo reduzido de matéria prima, facilidade no processamento e serem recicláveis. Apresentam propriedades mecânicas semelhantes, porém quando utilizados em componentes de vedação apresentam limitada resistência à corrosão em água clorada. Assim, o desenvolvimento de tratamento superficial que não modifique as características originais, mas tornem o material mais resistente são desejáveis. Para tanto, este trabalho pretende desenvolver uma metodologia a plasma para melhorar esse quesito. O elastômero termoplástico de copoliéster (COPE) foi escolhido por ser o mais empregado em componentes de vedação. O tratamento a plasma de baixa pressão com hexafluoreto de enxofre (SF6) foi empregado visando tornar a superfície do COPE hidrofóbica através da incorporação de grupos fluorados. A implantação iônica por imersão em plasmas (IIIP) de argônio foi utilizada para criar uma camada superficial mais coesa e entrelaçada, além da possibilidade de torná-la hidrofóbica após envelhecimento. Para o tratamento com SF6, os parâmetros de excitação do plasma (12 Pa e 80 W) foram mantidos, variando-se o tempo do tratamento entre 2 e 180 minutos de modo a encontrar uma condição ótima para esse processo. Para a IIIP de Ar os parâmetros de excitação do plasma (5 Pa e 60 min) foram mantidos e a potência da radiofrequência foi variada entre 10 e 150 W. A energia de superfície e ângulo de contato foram obtidos pelo método da gota séssil em um goniômetro automatizado. A morfologia da superfície foi avaliada por microscopia eletrônica de varredura (MEV) e microscopia de força atômica (AFM). Espectroscopia de energia dispersiva (EDS) e espectroscopia de fotoelétrons de raios X (XPS) foram utilizadas para análises da composição química e estrutura molecular. Corrosão por plasma de O2 e imersão em água clorada foram utilizados para avaliar a resistência antes e após os tratamentos a plasma. Os resultados mostram que as amostras tratadas por 90, 120 e 180 minutos em plasmas de SF6 tornam-se hidrofóbica, mesmo após o envelhecimento, apresentando incorporação de flúor, alterando assim a composição química e morfológica da superfície do COPE. Melhorias substanciais foram observadas nessas amostras após os ensaios de corrosão, indicando que um aumento na vida útil do material em situações reais de uso possam ter sido alcançadas. A IIIP de Ar tornou as amostras inicialmente mais hidrofílicas do que a amostra como-recebida, porém após a ação do tempo, algumas amostras permaneceram hidrofóbicas enquanto outras amostras retornaram à condição inicial. Apesar da hidrofobicidade não ter sido alcançada em todas as amostras, alterações na rugosidade e na morfologia foram verificadas, principalmente nas amostras tratada com 100 W de potência do plasma, ocasionando em melhora na resistência do COPE à água clorada. Essa melhora na resistência é atribuída ao aumento da conectividade da estrutura pelo estabelecimento de reticulações geradas pelo processo de IIIP, densificando o material tornando a permeação de íons da solução mais difícil. / Thermoplastic elastomers have been widely used in substitution for conventional rubber, given that the feedstock is cheaper, easier to process and recyclable. Its mechanical properties are similar, but when applied to sealing components its resistance is limited due to the chlorine present in water, therefore, it is interesting to develop a surface treatment that do not alter the original characteristics, but make the material more robust. To achieve such result, we chose to submit the copolyester thermoplastic elastomer (COPE) to plasma. This material was naturally chosen, once it is widely used for sealing purposes in this specific industry. By using low pressure plasma with sulfur hexafluoride, we expect to alter COPEs surface by incorporating fluorine groups, thus making it hydrophobic. We also submitted the sample to a second treatment, by submersion to argon plasma, making the outer layer less defective and more entangled with aging, as observed in previous experiments. For SF6 treatment, the exiting plasma parameters (12Pa and 80W) were kept and the treatment time was varied between 2 to 180 minutes in order to find the optimal treatment time. For Argon IIIP, the plasma exciting parameters (5Pa and 60 min) were maintained, while the radio frequency variation was between 10 to 150W. Surface energy and contact angle were obtained by and automatic goniometer, through the sessile drop method. The surface's morphology was analyzed by electronic scanning microscope and atomic force microscopy. Dispersive energy spectroscopy and X-ray photoelectric spectroscopy were responsible for the chemical composition and molecular structure analyses the new surface's resistance was tested by O2 plasma corrosion and immersed in chlorinated water. Results show the samples treated for 90,120 and 180 minutes in SF6 plasma became hydrophobic, even after aging. The samples were substantially improved and its resistance prolonged its lifespan in conventional usage. Argon IIIP made the surface more hydrophilic. However, after time part of the material restored its original characteristics. Although hydrophobic it was not achieved, the roughness and morphology alteration (especially when treated with 100W of plasma) improved COPE'S resistance. The results are explained by the increase in the structure's ability to connect by the establishment of reticulate one generated by the IIP process, making the component denser and the ionic solution less permeable.

A preocupação com a saúde tem levado ao uso de produtos com propriedades antimicrobianas, visando reduzir a proliferação de micro-organismos patogênicos. Ao mesmo tempo em que aditivos antimicrobianos são benéficos, pois reduzem a transmissão de doenças, os efeitos negativos, ainda, não estão bem elucidados. Estes aditivos podem afetar organismos essenciais ao meio ambiente e no desenvolvimento de plantas de interesse agrícola. Este trabalho tem o objetivo de avaliar o impacto ambiental causado por resíduos de elastômeros termoplásticos aditivados com três antimicrobianos comerciais à base de prata e pelos aditivos puros: (1) nanopartículas de prata adsorvida em sílica pirogênica (AgNp_sílica); (2) bentonita organomodificada com prata (Ag+_bentonita) e (3) prata em vidro fosfato (Ag+_fosfato). Os aditivos foram incorporados em uma formulação de composto termoplástico, a base de copolímero em bloco estireno-etileno/butileno-estireno (SESB), polipropileno (PP) e óleo mineral por mistura no estado fundido em extrusora dupla rosca e moldados por injeção. Os aditivos foram caracterizados por tamanho, forma e composição com o objetivo de avaliar a influência destas características nas seguintes propriedades do composto: mecânicas, térmicas, químicas, físicas, morfológicas e antimicrobianas. Além disso, foram avaliadas a variação na degradação abiótica e biótica dos compostos termoplásticos. A influência na degradação abiótica e a consequente redução de vida útil dos compostos foram avaliadas pelo ensaio de intemperismo. Já para a avaliação do impacto no solo foi realizado ensaio de biodegradação em câmara respirométrica (degradação biótica) e germinação de plantas no solo contendo os aditivos. O microcrustáceo aquático Daphnia magna (D. magna) foi utilizado como bioindicador de toxicidade dos aditivos na água. Os resultados indicam que compostos com AgNp_sílica possuem melhor propriedade antibacteriana que os demais aditivos testados, eliminando mais de 95% da população de Escherichia coli e 80% da população de Staphylococcus aureus após 24 horas de contato. A incorporação dos aditivos teve pouco efeito sobre as propriedades mecânicas, térmicas, químicas, físicas e morfológicas dos compostos. Os compostos aditivados e sem aditivo não apresentaram diferença no ensaio de intemperismo. No ensaio respirométrico, as amostras aditivadas tiveram pouca variação na produção de gás carbônico em comparação ao composto padrão. No teste de toxicidade em água com D. magna, houve mortalidade de todos os organismos, mesmo na concentração de 0,0001 mg L-1 de aditivo. No ensaio de germinação, os resultados foram adversos, não possibilitando estabelecer um padrão de toxicidade. Por fim, conclui-se que com o manejo adequado dos resíduos, compostos termoplásticos antimicrobianos são ambientalmente seguros, além de auxiliar no controle da propagação de doenças. / The concern with health has led to the use of products with antimicrobial properties aiming to reduce the proliferation of pathogenic microorganisms. At the same time that antimicrobial additives are useful to reduce the transmission of disease, adverse effects under human and environmental health still not well understood. These additives can affect organisms essential to the environment and plant development. The objective of this work was to evaluate the environmental impact caused by residues from thermoplastic elastomers (TPE) containing three commercial, silver-based antimicrobial additives and the pure additives. The additives tested were: (1) silver nanoparticles adsorbed on fumed silica (AgNp_silica); (2) bentonite organomodified with silver (Ag+_bentonite) and (3) silver phosphate glass (Ag+_phosphate). The additives were incorporated into a thermoplastic compound formulation, based on styrene-ethylene/butylene-styrene block copolymer (SESB), polypropylene (PP) and mineral oil by melt-blend in a twinscrew extruder and injection molded. A non loaded sample (standard) was used as control. The additives were characterized according to their size, shape and composition to evaluate the influence of these characteristics on the properties of the compound (mechanical, thermal, chemical, physical, morphological and antimicrobial). The influence on the abiotic degradation and consequent reduction in the life cycle of the compounds was evaluated by weathering test. To evaluate the impact of loaded TPE in soil, a soil biodegradation test was carried out in a respiratory chamber (biotic degradation) and germination of plants. The aquatic microcrustacean Daphnia magna (D. magna) was used as a bioindicator of toxicity of the additives in water. The results indicate that AgNp_silica compounds have better antibacterial properties than the other additives tested, eliminating more than 95% of the Escherichia coli population and 80% of the Staphylococcus aureus population after 24 h of contact. The incorporation of the additives had little effect on the mechanical, thermal, chemical, physical and morphological properties of the compounds. The results indicated that the additives presented a moderate effect on the properties of the above-mentioned metal loaded TPE compounds. The loaded and standard samples showed no difference in the weathering tests. In the respirometric assay, loaded samples had little variation in the production of carbon dioxide compared to the standard one. In the D. magna assay, there was mortality of all organisms, even at the concentration of 0.0001 mg L-1 of additive. In the germination test, the results were inconsistent and it was not possible to determine the toxicity potential of the additives tested. Lastly, it is possible to conclude that, taking into account the correct final disposition of TPE residues; thermoplastic compounds are environmentally safe and can assist in the control of diseases.

Este trabalho tem como objetivos a preparação e a caracterização de blendas de amido termoplástico e borracha natural, obtidos a partir dos amidos de mandioca e milho e do látex de borracha natural utilizado diretamente como extraído da seringueira, sem nenhum tipo de tratamento prévio. Os amidos termoplásticos (TPS) foram processados em misturador intensivo em duas temperaturas diferentes (120oC e 150oC), utilizando como plasticizantes a glicerina, o etilenoglicol e o propilenoglicol na proporção de 30 % em massa na matriz, e teores de látex de borracha natural (NRL) variando na proporção de 2,5 a 10 % em massa na blenda. As propriedades das blendas foram avaliadas por difração de Raios-X, por termogravimetria (TG), ensaios mecânicos de resistência à tração, por ensaios de absorção de água e por microscopia eletrônica de varredura (SEM). O cisalhamento desenvolvido durante o processamento em misturador intensivo levou à perda da estrutura cristalina e à desestruturação dos grânulos de amido. A adição de látex diminuiu os valores de índice de cristalinidade dos TPS, não alterando, entretanto, o comportamento cristalográfico com relação ao tipo de padrão de cristalinidade apresentado pelos TPS. Com relação à estabilidade térmica, os TPS mostraram-se dependentes da fonte de amido utilizado, do tipo de plasticizante, da temperatura de processamento e do teor de látex presente. Quanto à resistência mecânica, o TPS de milho se mostrou mais resistente que o de mandioca, principalmente quando plasticizado com glicerina, tendo a temperatura de processamento pouca influência sobre os resultados. Com relação aos teores de látex adicionados, não foi observada nenhuma melhora significativa sobre a resistência mecânica dos TPS, exceto um pequeno aumento nos valores de alongamento à ruptura. A adição de látex proporcionou uma diminuição linear na absorção máxima de água no equilíbrio, assim como uma redução nos valores de coeficiente de difusão de água apresentado pelos TPS. Uma vez que o processo de mistura desempenha uma função importante na morfologia destas blendas, na maioria dos TPS plasticizados com glicerina, entretanto, para os TPS plasticizados com etilenoglicol e com propilenoglicol não houve uma boa dispersão dos componentes das misturas. Os TPS de milho plasticizados com glicerina à 150oC foram os que apresentaram uma melhor dispersão das partículas de látex quando comparado com os demais. A qualidade destas dispersões foi uma conseqüência da utilização do látex ao invés da borracha sólida, uma vez que o primeiro apresenta a presença de proteínas e lipídeos na superfície das partículas de borracha presentes no látex, atuando como um compatibilizante entre o amido, uma matriz polar, e a borracha, um material não-polar. / The aim of the study reported here was to prepare and characterize blends of thermoplastic starch and natural rubber, based on manioc starch (tapioca), corn starch and natural rubber latex used directly as extracted from Hevea brasiliensis (Brazilian rubber tree), without prior treatment. The thermoplastic starch (TPS) matrices were prepared in a high-intensity mixer at two temperatures (120°C and 150°C), with 30% (w/w) glycerol, ethylene glycol or propylene glycol as plasticizer, and from 2.5% to 10% (w/w) natural rubber latex (NRL) was added to form the blends. The properties of the composite blends were assessed by XRD, TGA, tensile strength tests, water absorption tests and SEM. The shearing forces developed during mixing resulted in a loss of crystallinity and breakdown of the starch granule structure. The addition of NRL reduced the crystallinity index of the TPS, but did not change the type of crystal structure exhibited by this phase. The thermal stability of the TPS matrix was found to depend on the origin of the starch, the type of plasticizer, the processing temperature and the latex content. In the mechanical strength tests, the cornstarch TPS proved stronger than the manioc product, especially when plasticized with glycerol, while the mixing temperature had little influence. With the addition of NRL, no significant was observed in the mechanical properties, except for a small increase in the elongation of the material at breakpoint. As latex was added there was a linear decrease in the maximum absorption of water at equilibrium, as well as a reduction in the diffusion coefficient of water in the matrix. While the mixing process played an important part in producing an adequate blend morphology in most of the mixtures containing glycerol, the components of blends in which the TPS was plasticized with ethylene or propylene glycol were not well-dispersed. The TPS that afforded the best dispersion of latex particles was composed of cornstarch and glycerol and plasticized at 150°C. The highquality dispersion achieved was a consequence of using raw latex instead of solid rubber, since in the latex the rubber particles are coated with surface proteins and lipids that help to compatibilize the starch, a polar matrix, with the nonpolar rubber.

Dans le cadre du développement de boîtiers à cavités pour composants électroniques, les polymères à cristaux liquides (LCP) offrent des propriétés intéressantes capables de rivaliser avec les matériaux en céramique : une faible perméabilité aux gaz, une résistance à haute température, une stabilité thermique et une faible constante diélectrique (3,1 à 1 MHz et 2,8 à 10 GHz). Cette nouvelle génération de thermoplastiques permettra de concurrencer les boîtiers métalliques et céramiques à cavité plus coûteux et de s’ouvrir à de nouvelles applications comme l’imagerie médicale par exemple.Dans ce contexte, nous proposons une technique de fonctionnalisation de nanoparticules minérales (via procédé Sol-Gel) et leur incorporation à la matrice polymère afin de modifier ces propriétés mécaniques (Module de Young et CTE) et son anisotropie. La fiabilité de boîtiers est évaluée à l’aide de simulations thermomécaniques. Le but est d’établir un lien entre les propriétés mécaniques des composites à base de LCP et la durée de vie des boîtiers électroniques. Le développement de capots optiques pour ces boîtiers est aussi étudié afin d’obtenir une filtration dans la proche infrarouge pour des applications dans le secteur de la téléphonie mobile. / As part of the development of cavities packages for electronic components, Liquid Crystal Polymers (LCP) offer interesting properties and compete with ceramic materials: low gas permeability, high temperature resistance, thermal stability and low dielectric constant (3.1 to 2.8 for 1 MHz and 10 GHz). This new generation of thermoplastic will compete with classic packages more expensive and open to new applications such as medical imaging for example.In this context, we propose an original approach of mineral nanoparticles functionalization (via sol-gel process) and their incorporation into the polymer matrix to modify the mechanical properties (Young's modulus and CTE) and the anisotropy. Packaging reliability is assessed using thermomechanical simulations. The goal is to establish a link between the mechanical properties of composites based on LCP and the characteristic lifetime of the package. The development of optical covers for these packages is also study to obtain a filter in the near infrared for applications in the mobile phone sector.

This dissertation focuses on the versatility and integrity of a novel, ultrasoft polycarbonate polyurethane (PCPU) by the introduction of nanoparticles and lithium salts. Additionally, the research takes into account the use of electrospinning as a technique to create PCPU and polyimide (PI) fibers. These polymers are of interest as they offer a wide range of properties and uses within the medical and industrial fields. An industrial batch of an ultrasoft thermoplastic polyurethane (TPU) was synthesized using a two-step process. The first was to create an end capped pre-polymer from methylene bis (4-cyclohexylisocyanate), and a polycarbonate polyol made up of 1,6- hexanediol and 3-methyl-1,5-pentanediol. The second step was done by reacting the pre-polymer with an excess of the polycarbonate polyol with a chain extender, 1,4-butanediol. Biocompatibility testing such as USP Class VI, MEM Elution Cytotoxicity and Hemolysis toxicology reported that PCPU showed no toxicity. This novel type of polyurethane material targets growing markets of biocompatible polymers and has been used for peristaltic pump tubing, but also can be utilized as balloon catheters, enteral feeding tubes and medical equipment gaskets and seals. This material is ideal for replacing materials such as soft plastisols containing diethylhexyl phthalate for use in biomedical and industrial applications. After extensive characterization of this polymer system another dimension was added to this research. The addition of nanoparticles and nanofillers to polyurethane can express enhanced mechanical, thermal and adhesion properties. The incorporation of nanoparticles such as nanosilica, nanosilver and carbon black into polyurethane materials showed improved tensile strength, thermal performance and adhesion properties of the PCPU. Samples were characterized using contact angle measurements, Fourier transform spectroscopy (FTIR), differential scanning calorimetry (DSC), parallel plate rheology and tensile testing. The second chapter entails the fabrication and characterization of PCPU nanofibers and nanomembranes through a process known as electrospinning. The resulting PCPU nanomembranes showed a crystalline peak from the WAXS profile which is due to electrospun and solution strain induced crystallinity. The PCPU nanocomposite nanomembranes displayed increased thermal stability and an increase in tensile performance at higher weight percent. The nanomembranes were investigated using contact angle measurements, thermogravimetric analysis (TGA), DSC, WAXS, SAXS and tensile testing. The final chapter focuses on investigating the rheological properties of PCPU/lithium electrolytes as well as transforming an unprocessable polyimide powder into a nanomembrane. The PCPU/ lithium composite electrolyte showed an increase in the activation energy and conductivity, while the PI/lithium showed increased conductivity over time. Dynamic mechanical analysis and four-point probe was used to investigate the samples.

<p>A novel strategy for synthesising segmented poly(urethane urea) (PUU) without using a chain extender but nevertheless with the opportunity to vary the hard segment content has been developed. The strategy is based on amine formation from isocyanate upon reaction with water. By adding a dissolved soft segment to an excess of diisocyanate followed by the addition of water in the gas phase, amines are formed <i>in situ</i>. Urea linkages are then formed when these amines react with the excess of isocyanate groups. The gas phase addition facilitates addition in a slow and continuous manner. The hard segment content can easily altered by varying the diisocyanate/soft segment ratio. Even though the strategy is shown to be applicable to different diisocyanates, the focus has been on the potentially biodegradable methyl-2,6-diisocyanatehexanoate (LDI) and 1.4-butanediisocyanate (BDI) and various well known biodegradable polyesters and polycarbonates. </p><p>All the synthesised materials exhibited pronounced phase separation and hydrogen bonding within the hard domains. However, a major increase in hydrogen bonding strength was seen when a symmetric diisocyanate was used instead of an asymmetric. Based on FTIR measurements, PUUs with BDI and a polydisperse hard segment can exhibit the same degree of phase separation and hydrogen bonding as the monodisperse product.</p><p>The elastic properties of this new group of PUUs were exceptional with an elongation at break from 1600% to almost 5000% and the elastic modulus could be varied from a few MPa up to a couple of hundreds. </p><p>Hydrolytic degradation was greater in the polyester-based than in the polycarbonate-based PUUs due to the more reactive ester bonds. Low mass loss but a considerable loss in molecular weight was seen in the polyester PUUs. The tensile strength decreased dramatically due to the loss of strain hardening.</p><p>An MTT seeding assay using human fibroblasts and an in vivo biocompatibility study were performed and no signs of cytotoxicity were seen and the inflammatory response was comparable to other inert polymers.</p><p>A biodegradable PUU with properties that can be tailored through an easy synthesis is here presented. </p>

Graduation date: 1999

A novel strategy for synthesising segmented poly(urethane urea) (PUU) without using a chain extender but nevertheless with the opportunity to vary the hard segment content has been developed. The strategy is based on amine formation from isocyanate upon reaction with water. By adding a dissolved soft segment to an excess of diisocyanate followed by the addition of water in the gas phase, amines are formed in situ. Urea linkages are then formed when these amines react with the excess of isocyanate groups. The gas phase addition facilitates addition in a slow and continuous manner. The hard segment content can easily altered by varying the diisocyanate/soft segment ratio. Even though the strategy is shown to be applicable to different diisocyanates, the focus has been on the potentially biodegradable methyl-2,6-diisocyanatehexanoate (LDI) and 1.4-butanediisocyanate (BDI) and various well known biodegradable polyesters and polycarbonates. All the synthesised materials exhibited pronounced phase separation and hydrogen bonding within the hard domains. However, a major increase in hydrogen bonding strength was seen when a symmetric diisocyanate was used instead of an asymmetric. Based on FTIR measurements, PUUs with BDI and a polydisperse hard segment can exhibit the same degree of phase separation and hydrogen bonding as the monodisperse product. The elastic properties of this new group of PUUs were exceptional with an elongation at break from 1600% to almost 5000% and the elastic modulus could be varied from a few MPa up to a couple of hundreds. Hydrolytic degradation was greater in the polyester-based than in the polycarbonate-based PUUs due to the more reactive ester bonds. Low mass loss but a considerable loss in molecular weight was seen in the polyester PUUs. The tensile strength decreased dramatically due to the loss of strain hardening. An MTT seeding assay using human fibroblasts and an in vivo biocompatibility study were performed and no signs of cytotoxicity were seen and the inflammatory response was comparable to other inert polymers. A biodegradable PUU with properties that can be tailored through an easy synthesis is here presented.

Thermoplastic composites using natural fibres are studied intensively and widely used in applications including automotive, packaging, consumer goods and construction. Good balance of mechanical properties, processability and low cost are great advantages of these materials on top of the environmental benefits. Recently, there have been various efforts to amplify the positive effects on the environment by replacing the conventional polymers by bio-derived renewable polymers in the composites. Recent studies conducted from our research group showed competitiveness of plant fibre-thermoplastic composites. Implementing the promising results and experience, a new composite design using renewable polyethylene as the matrix material was studied. This polyethylene is a renewable thermoplastic that was derived from sugar cane ethanol. The objectives of this study were to employ renewable high density polyethylene (HDPE) into composites using wheat straw and flax fibre to extend the range of properties of the HDPE while keeping the amount of renewable content to nearly 100%. The chemical resistance of these materials has not been reported before and it was investigated here by measuring and comparing the properties before and after accelerated chemical ageing. Both wheat straw and flax fibre had two different grades in size. Each of them was compounded with HDPE and additives (antioxidant and coupling agent) in a co-rotating twin screw extruder. The concentrations of fibres were varied from 0 to 30 wt-%. Then, injection molded samples were prepared for measurement of properties: tensile, flexural, impact tests. The effects of reinforcing fibre size were studied first. Both length and aspect ratio were considered. For both types of fibre composites, a general trend was observed. There was no clear evidence of improvements in flexural (strength and modulus) and tensile (strength, percentage elongation at break) properties with respect to the change in fibre size. However, impact (IZOD impact strength, Gardner impact failure energy) properties showed some improvements. This result was due to no substantial difference in size and aspect ratios in post-processed fibres that were actually residing in the matrix. There were remarkable improvements in flexural strength and modulus when the fibre content increased. However, minor decreases in tensile properties were observed. Furthermore, the impact properties were very sensitive to the concentration of fibres. As the fibre concentration went up, there were significant decreases in both IZOD impact strength and Gardner impact failure energy. Chemical resistance of these composites was studied by exposing them in six different chemical solutions (hydrochloric acid, acetic acid, sodium hydroxide, ethyl alcohol, industrial detergent, water) for up to thirty days. The increase in weight and leaching behaviour was observed. As the fibre content increased within the composites, the weight gain was more rapid during chemical ageing. Because there were more fibres exposed on the surface after chemical ageing, it is likely that they contributed to the higher flux of liquids (used for chemical ageing) inside the sample. Among the physical properties, tensile properties were most susceptible to the chemical ageing. One possible reason could be due to the exposed surface area to volume ratio, which was the highest in tensile bars and therefore faster mass transfer taking place into the matrix per volume. Finally, morphological study using scanned electron spectroscopy (SEM) revealed the damage on the surface when exposed to the chemicals. The fibres on the surface had been leached out in the sodium hydroxide solution leaving empty spaces. The fractured surface was also monitored via SEM. Though there was not enough evidence of strong interfacial interactions between the fibre and the polymer, good dispersions were observed.

Results from a research program to investigate the long term effects of through-the-thickness fastener clamp-up force (preload) relaxation on the strength of mechanically fastened joints for two graphite/thermoplastic composite materials (Dupont's IM6/KIII and ICI-Fiberite's IM8/APC(HTA)) are summarized and compared with analytical methods. An experimental program was conducted in which 56 mechanically fastened single-shear joints were tested. Phase I static tests established joint bearing strength as a function of clamp-up force for two types of fasteners (protruding head and countersink) with no relaxation of preload. Phase II testing monitored short-term fastener preload relaxation (up to 1 ,000 hours), with special bolt force sensor washers. Inservice parameters included were temperature, in-plane loads, and torque. The jOints were tested to failure at the end of the relaxation time period to determine any subsequent effect on joint strength. Phase I test results indicated that joint bearing strength increased by as much as twenty-eight percent over the clamp-up force range of a Ibs (fingertight) to 3,500 Ibs for both materials. Fastener head type, material, and temperature also affected the resultant bearing strength. For Phase II, fastener clamp-up force at room temperature (78°F) relaxed an average of six percent from the initial value during the short-term test period. The relaxation was projected to be as high as fourteen and sixteen percent at 100,000 hours for HTA and Kill, respectively. The elevated temperature condition (250°F) significantly increased the relaxation rate with the projected 100,000 hour relaxation amount being as high as thirty-seven percent for HTA and sixty percent for Kill. Comparison of the Phase II bearing strengths to the Phase I results indicated that portions of the data correlated well, while others did not. It was concluded that relaxation of the clamp-up force over the short-term time period did not significantly lower the bearing strength of either material, however an extended exposure to 250°F could affect the bearing strength. / Thesis (M.S.)--Wichita State University, College of Engineering, Dept. of Aerospace Engineering.