O poli(cloreto de vinila) - PVC é considerado um polímero muito versátil devido à possibilidade deste ser formulado mediante a incorporação de aditivos, alterando suas características originais. Plastificantes a base de ftalatos, como o di(2-etilhexil) ftalato (DOP) são os mais utilizados, porém, existem regulamentações que estão restringindo a sua utilização, intensificando-se os estudos com possíveis alternativos. Desta forma, este trabalho visa avaliar a influência de plastificantes de diferentes naturezas nas propriedades físicas, mecânicas, térmicas e reológicas do PVC plastificado. Para formulação dos compostos foi utilizado a resina Norvic SP1000 produzida via suspensão, com VK65 e portanto, propícia para aplicações de materiais flexíveis, além disso, para cada composto utilizou-se uma dosagem de 60 pcr de sete diferentes plastificantes: DOP, considerado como referência para comparação dos resultados, diisononil ciclohexano (DINCH), di(2-etilhexil) ciclohexanoato (DOCH), di(2-etilhexil) adipato (DOA), di(2-etilhexil) tereftalato (DOTP), óleo de soja epoxidado (OSE) e plastificante de óleos vegetais (DIMIT) Neste estudo foram efetuadas avaliações nos compostos como, gelificação e fusão, reologia via reômetro de placas paralelas, densidade, índice de fluidez entre outras para compreender a influência de cada plastificante no processamento do composto e várias caracterizações no produto final como estabilidade térmica dos compostos via TGA, Metrastat, propriedades óticas, propriedades mecânicas como dureza Shore A, tração, resistência a abrasão, resiliência, envelhecimento em câmara UV assim como ensaios de exsudação dos plastificantes. Os resultados indicam comportamentos distintos do PVC em função da natureza química do plastificante utilizado. O plastificante DIMIT possui boa estabilidade térmica, porém os resultados de cor e parâmetros de processamento foram insatisfatórios quando comparados ao DOP, já os plastificantes OSE e DOA apresentaram bons resultados para as propriedades avaliadas. Conclui-se que dentre os plastificantes analisados não foi possível determinar qual seria o melhor para substituição direta do DOP considerando toda a gama de produtos flexíveis de PVC, contudo esse trabalho colabora para a avaliação e seleção do melhor plastificante com base nos requisitos de cada aplicação do produto. / The poly (vinyl chloride) - PVC is a very versatile polymer due to the possibility of being formulated by incorporating additives, which can change the resin characteristics. Plasticizers composed of phthalates, such as di(2-ethylhexyl) phthalate (DOP), are the most used, however, there are regulations restricting the use of this kind of plasticizers, intensifying studies with possible replacement alternatives. In this way, the objective of this work is to evaluate the influence of plasticizers from different sources in PVC, mainly physical, mechanical thermal stability, and rheological properties in the plasticized PVC. In the formulation of the compounds it was used the resin Norvic SP1000, product with VK65 and produced by suspension, suitable for flexible materials applications. In addition, it was used 60 phr of seven different plasticizers for each compound: DOP, considered as reference for all results, cyclohexane diisononyl (DINCH), di(2-ethylhexyl) cyclohexanoate (DOCH), di(2-ethylhexyl) adipate (DOA), di(2-ethylhexyl) terephthalate (DOTP), epoxidized soybean oil (OSE) and plasticizer produced from vegetable oils (DIMIT). In this study, the compounds were evaluated with many characterization analyzes, such as gelling and melting point in a torque rheometer, rheology by parallel plate rheometer, density, melt flow index in order to understand the influence of each plasticizer on the material processing Some characterizations in the final product as thermal stability through TGA, Metrastat, optical and mechanical properties such as hardness Shore A, tensile strength, abrasion resistance, resilience, aging in UV chamber as well as exudation tests. The results indicate different behaviors of PVC depending on the chemical nature of the plasticizer used. Results indicate that the DIMIT plasticizer had good thermal stability, but the color and processability results were unsatisfactory when compared to the DOP. In the other hand, the OSE and DOA presented good results for the evaluated properties. It can be concluded that among the plasticizers analyzed it wasn´t possible to determine the best for direct DOP replacement considering the entire range of flexible PVC products. However, this work contributes to the evaluation and selection of the best plasticizer based on the requirements of each application.

The main purpose of this thesis was to investigate and characterize the use of piezoelectric yarn for use in textile (fingertip) pressure sensors in glove applications. Such applications could include healthcare, security and safety, game applications or intelligent control. Piezoelectric materials generate a voltage when pressed or squeezed. Poly(vinylidene fluoride) (PVDF) is a polymorphic material with piezoelectric properties. PVDF yarns were integrated into block sensors. These blocks consist of thermoplastic material glued to a knitted supporting fabric. The electrical signal given off by the PVDF yarn was measured with the help of an oscilloscope. The block sensor generated a distinguishable signal under a dynamic compression of 0.003 N, indicating that the structure is sensitive enough compared to the average male fingertip sensitivity threshold (0.0054N). / Program: Master programme in Textile Engineering

Lactic acid based thermoset were synthesised by reacting lactic acid with glycerol andfunctionalizing lactic acid branches by methacrylic anhydride. Resins with different chainlength were prepared and their thermo mechanical properties were examined through DMAanalysis and their molecular structures were analyzed by NMR method and their viscositywere investigated through rheometry analysis and three monomers were selected as the bestchain length. Degree of reaction in different reaction times was evaluated by a modifiedtitration method and bulk preparation of resin was performed by optimal process condition.DSC analysis was conducted in order to evaluate curing behaviour of resin with benzoylperoxide as cross-linking initiator. TGA analysis was performed to check thermo stability ofthe resin. Bio composites by viscose unidirectional and bidirectional knitted fabrics and alsonon woven viscose fiber with different fiber loads were prepared by ordinary hand layupimpregnation followed by compress moulding and their mechanical and thermo mechanicalproperties were characterized by tensile, flexural, charpy and DMA analysis and optimumfiber loads were identified for each fiber type. Ageing properties of prepared composites wereexamined by placing samples in climate chamber to simulate long time ageing and ageingexperiment was followed by tensile and flexural test to evaluate mechanical properties afterageing simulation. Composite`s swelling properties for water and some other solvents wereinvestigated and also their chemical resistance were evaluated by immersing them in 1M HCland KOH. The resin was also compared with a commercial oil based thermoset by preparingglass fiber reinforced composites and also effect of adding styrene to the resin were evaluated.Results of this work demonstrated that the novel synthesised have very high mechanical andthermo mechanical properties surpassing commercial oil based poly esters but ageingbehaviour is not very good however adding styrene can improve ageing properties. Also theresin is compatible with cellulosic natural fibers and forms strong composites. / Program: Masterutbildning i energi- och material

Bone undergoes constant turnover throughout life and has the capacity to regenerate itself. However, the repair of critical size defects, caused by bone diseases such as osteoporosis, can be more problematic. Therefore, there is a clinical need for a bone graft substitute that can be used at sites of surgical intervention to enhance bone regeneration. Poly(vinylphosphonic acid-co-acrylic acid) (PVPA-co-AA) has recently been identified as a potential candidate for use in bone tissue scaffolds. It is hypothesised that PVPA-co-AA can mimic the action of bisphosphonates – a class of drugs used in the treatment of osteoporosis – by binding to calcium ions from bone mineral surfaces. In this way, bisphosphonates can affect bone turnover by increasing the activity of osteoblasts and reducing osteoclast activity. Although PVPA-co-AA has been shown to improve bone formation, the mechanism of action has so far not been fully elucidated. Therefore, this work aims to understand the effect of copolymer composition on the properties of PVPA-co-AA, and thus to determine its effect on osteoblast adhesion and proliferation. PVPA-co-AA copolymers have been synthesised with a range of monomer feed ratios. It was found that a VPA content of 30 mol % led to the greatest calcium binding affinity of the copolymer and is thus expected to lead to enhanced bone formation and mineralisation of the matrix produced by osteoblast cells. The release profile of PVPA-co-AA from electrospun PCL scaffolds was investigated. It was shown that all of the PVPA-co-AA was released into aqueous media within 8 h of immersion. It was also found that the calcium chelation from osteogenic differentiation media significantly increased within the first 8 h. Therefore, it was concluded that PVPA-co-AA is released from the scaffolds, where it can then bind to calcium ions from the bone mineral surface to promote mineralisation, thus acting as a mimic of non-collagenous proteins, which are present in the extracellular matrix (ECM) of bone. Hydrogels of PVPA-co-AA have been produced and the effect of monomer feed ratio (0-50 mol % VPA) on the properties of the gels was explored. It was found that an increase in VPA content led to greater hydrogel swelling and increased porosities. Hydrogels that contained 30 and 50 mol % VPA were shown to have similar morphologies to the native ECM of bone. Rheological testing showed that hydrogels with higher VPA contents were more flexible and could be deformed to a large extent without permanent deformation of their structure. An increase in osteoblast adhesion and proliferation was observed for hydrogels with 30 and 50 mol % VPA content as well as superior cell spreading. Osteoblast cell metabolic activity also increased as a function of VPA content in the hydrogels. This work indicates that hydrogels of PVPA-co-AA, with VPA contents of 30 or 50 mol %, are ideal for use as bone tissue scaffolds. Furthermore, the mechanical and cell adhesion properties of the gels can be tuned by altering the copolymer composition. Finally, composite hydrogels of PVPA-co-AA and hydroxyapatite (HA) have been produced and investigated for their ability to remove fluoride ions from groundwater. It was found that the fluoride uptake ability of PVPA-HA hydrogels was significantly enhanced when compared with HA powder alone. Furthermore, the fluoride uptake was dependent on many factors, including pH, contact time and the presence of competing ions. It was possible to regenerate the hydrogel to remove the fluoride ions, and thus it was shown that the material can be used a number of times with only a slight reduction in its fluoride uptake capacity.

Obesity can lead to a range of health problems including type 2 diabetes (T2DM), cardiovascular disease and non-alcoholic fatty liver disease (NAFLD), and causes an estimated 2.8 million deaths annually (2016). It is a growing epidemic affecting over 600 million people worldwide (in 2014), with 26.8% of the adult population in England alone being obese, an increase of 10% in the last decade, and 62.9% overweight or obese. This trend is predicted to continue, and is attributed to an increasingly sedentary lifestyle, coupled with a high calorie “western diet”, which is estimated to cost >£25billion/year in the UK (2015), which is predicted to rise to £49.9 billion by 2050. It is clear that both sex and genetics affect the extent to which individuals exposed to a high fat diet develop adiposity and its associated morbidities, although the mechanisms underlying these differences are not well understood. Here we explore this aetiology, focusing on poly(A)-binding protein 4 (PABP4), an RNA-binding protein in which polymorphisms associated with altered cholesterol levels and cardiovascular disease risk were identified in human GWAS studies. To this end, I take advantage of an unpublished Pabp4 knock-out mouse, maintained on either normal (ND) or high fat diet (HFD), to explore the role of PABP4 in determining the response to high fat diet. PABP4 is a poorly characterised member of the PABP family, which are multifunctional central regulators of global and mRNA-specific translation, and stability. In cell lines, PABP4 is predominantly cytoplasmic, consistent with such functions. However, analogously to PABP1, the prototypical PABP family member, PABP4 is relocalised to stress granules or the nucleus in response to specific cellular stresses and/or viral infections, suggesting a role in altering gene expression programs in responses to changing cellular conditions. Whilst the expression pattern of PABP4 within tissues has not been previously characterised, western blotting of adult mouse tissues revealed that PABP4 is highly expressed in tissues relevant to obesity, T2DM and NAFLD, such as adipose, pancreas, liver and muscle, consistent with the idea that it may play a role in regulating gene expression programs in response to HFD. Immunohistochemistry of tissue sections provided additional insight, revealing a distinct cellular distribution of PABP4 in some tissues, when compared to the well characterised PABP1. Birth weight and post-birth growth can affect adult metabolism. In particular, low birth weight and catch-up growth, characterised by preferentially putting down adipose over lean mass, increases the risk of metabolic conditions in adulthood, such as obesity, T2DM and cardiovascular disease. Therefore, Pabp4-/- and wildtype mice were weighed at birth and daily until weaning. Interestingly this revealed that Pabp4-/- mice have a reduced weight at birth that is exacerbated to weaning (21days (P21)) (5.7% and 18.3% reductions respectively). This analysis also uncovered a reduced survival to weaning, with both male and female Pabp4-/- mice being present at sub-Mendelian ratios by P21 (p=0.0056). Whilst most death occurred neonatally, Pabp4-/- mice showed an increased rate of attrition until weaning, preceded in some cases by an arrest of weight gain. Weight gain was also tracked from 4 weeks to 12 weeks of age on normal diet showing that Pabp4-/- mice had reduced weight into adulthood (12% reduction at 12wks). Analysis of weight gain by sex uncovered a sexually dimorphic effect of Pabp4-deficiency, with female, but not male, Pabp4-/- mice remaining reduced in weight compared to wildtype after 8 weeks on ND (13.4% reduction in female weight). Body composition analysis showed that fat mass was equivalent to wildtype at 12 weeks of age in both sexes but that female Pabp4-/- mice had a 14.3% reduction in lean mass. Neither the catch-up growth in males nor the reduced lean mass in females was sufficient to result in a change in glucose homeostasis. As the risk of developing metabolic disorders in adult life is a consequence of both genetic and environmental factors, such as diet, Pabp4-/- were placed on a HFD at 4 weeks of age for 8 weeks. HFD models the ‘western’ diet, and has been shown to induce obesity, insulin resistance and glucose intolerance in wildtype mice. Whereas Pabp4-/- mice were only distinguishable from wild-type in terms of female lean mass on normal diet, pronounced sexually dimorphic differences were observed in HFD fed mice. Male Pabp4-/- mice appeared to be partially protected from the negative effects of an 8 week HFD regimen, with a 44% decrease in adipose mass gain compared to wildtype despite equal lean mass. Pabp4-/- male mice also had significantly reduced ectopic lipid stores, with an 81% decrease in hepatic triglyceride concentration compared to wildtype, meaning that NAFLD has not developed. Furthermore, Pabp4- /- male mice did not develop hyperinsulinemia on HFD and retained insulin sensitisation (assessed via glucose tolerance test (GTT) and insulin tolerance test (ITT)), although they displayed wildtype-like elevated plasma glucose concentrations (compared to ND). Western blotting had detected high PABP4 levels in the pancreas, indicating a possible pancreatic origin of these alterations. However, immunofluorescence revealed that PABP4 was confined to the exocrine portion of the pancreas, and was undetectable in the insulin producing pancreatic beta cells, suggesting this phenotype may not be beta cell in origin. This is consistent with the fact that the Pabp4-/- male mice retained an appropriate glucose-induced burst of insulin secretion, and therefore insulin production appears unimpaired. Thus, the primary defect may reside in the exocrine pancreas, which aids digestion, or in other key metabolism related tissues (e.g. muscle, liver, adipose and brain), or a combination thereof. In HFD fed wildtype mice, insulin resistance is caused by increased adiposity and ectopic lipid depots, which blunt insulin stimulated signalling cascades, meaning that the normal responses to insulin (e.g. cellular up take of glucose in muscle and arrested glucose production in liver, to decrease plasma glucose concentrations), are impaired. Therefore, the absence of insulin resistance in HFD fed Pabp4-/- male mice may be a consequence of the reduced increase in adipose mass and ectopic lipid deposits detected in these mice, and their consequent lack of inhibition on insulin signalling pathways. The reduced adiposity was not a result of reduced food intake or dietary fat absorption as male Pabp4-/- mice did not eat less nor exhibit apparent steatorrhea (fatty stools). These results highlight that the Pabp4-/- male mice appear to have an alteration in energy use/storage, and the investigation of this will form the basis of future work. When fed HFD, female Pabp4-/- mice revealed a divergent phenotype to that of wildtype female mice and Pabp4-/- male mice. HFD fed Pabp4-/- female mice showed no difference to HFD-fed wildtype mice in terms of weight, but still exhibited the reduction in lean mass seen on ND, but now with a 22.8% increase in volume of adipose tissue. Together, this means that HFD fed Pabp4-/- females have a higher body fat percentage (32.6% compared to 25.9 % for wildtype females). In contrast to the males, there was no difference in terms of hepatic triglycerides in HFD fed Pabp4-/- female mice and they showed greater hyperglycaemia than wildtype (GTT), although like males they retained insulin sensitisation (ITT). These potentially conflicting results in terms of insulin sensitivity and plasma glucose concentrations may result from the alterations in body composition, which can confound results when lean mass is altered and total body weight is used for calculating doses for GTT/ITT. Interestingly, adiponectin, an adipokine normally found in inverse proportion to adipose mass, was increased in plasma from HFD fed Pabp4-/- female mice (21% increase from HFD fed wildtype mice). Whilst surprising given the increase fat mass of Pabp4-/- females, the insulin sensitising properties of adiponectin may help to explain the retained insulin sensitivity detected in the female Pabp4-/- mice. / The finding that HFD revealed metabolic differences in the Pabp4-/- mice lead to the question of whether Pabp4-/- mice have issues adapting to other situations which require modulation of energy storage and glucose homeostasis. One such event is pregnancy, when maternal regulation of insulin resistance is tightly modulated throughout gestation. We therefore characterised the maternal Pabp4-/- environment in late pregnancy (E18.5), when insulin sensitivity decreases to 40-60% lower than pre-pregnancy which results reduced maternal glucose uptake, freeing the glucose up for the rapidly developing foetus. Pregnant Pabp4-/- mice had elevated plasma insulin concentration post fasting (63.7% increase), however glucose homeostasis was wildtype-like, both in terms of plasma glucose and insulin concentrations, throughout a GTT. However, plasma glucose and insulin concentrations in E18.5 Pabp4-/- foetuses were significantly decreased (9% and 44.3% respectively). Pabp4-/- foetuses also had reduced foetal and placental weight/length parameters. This establishes that the differences in weight observed at birth were present by late gestation and secondly, that the reductions in both foetal glucose and insulin concentrations which may contribute to or underlie the reduced growth. It also suggests that the differences seen in adulthood on HFD may be a consequence of metabolic differences present during pregnancy. Taken together, these data support the hypothesis that PABP4 plays a key role in the regulation of mRNAs which are important in growth, post-natal survival and metabolic adaption to high fat diet.

Este trabalho apresenta estudos sobre a síntese química do PEDOT com o objetivo de desenvolver diferentes arquiteturas e propriedades para melhorar a taxa de degradabilidade deste polímero. As estratégias foram as preparações de uma blenda, um copolímero e um nanocompósito. O estudo foi iniciado pela síntese química oxidativa do PEDOT (poli (3,4- etilenodioxitiofeno)) em microestruturas utilizando condições brandas e ambientalmente amigáveis, porém o material obtido não apresentou solubilidade e boas condições de se produzir um filme. Então foi sintetizado quimicamente o PEDOT dopado com PSS (poli estireno sulfonado) (PEDOT:PSS), o mesmo foi usado para preparar blendas com o PLGA (poli (ácido láctico-co-glicólico), para melhorar sua degradabilidade. Foi possível produzir um filme fino e nanoestruturado através de deposição eletrostática camada por camada (LBL) que pode ser utilizado para modificação de eletrodos ou de suportes tridimensionais para engenharia celular. Para garantir a degradabilidade do material, foi realizada a síntese de copolímeros de PEDOT e PLLA (poli(lactídeo)) em que foi variada a proporção de PEDOT na cadeia polimérica. Os copolímeros foram caracterizados por IV, RMN, UV, análises térmicas e submetidos a testes de degradabilidade e de viabilidade celular, apresentando excelentes resultados. Foi possível a obtenção de microfibras deste material. A outra alternativa estudada foi a síntese de um nanocompósito, preparado através da síntese química do PEDOT, partindo do monômero EDOT (3,4- etilenodioxitiofeno)usando HAuCl4 como oxidante e NaPSS como dopante e dispersante. O nanocompósito obtido foi caracterizado apresentando diâmetros médio próximos de 4 nm e com uma estrutura caroço-casca, apresentando nanopartícula de ouro como caroço e o polímero PEDOT:PSS como casca. Foram obtidos filmes deste material por deposição por evaporação de solvente, LBL, utilizando como policátion o PDDA (cloreto de poli (dialil dimetil amônio)) e quitosana, e por deposição eletroforética, que apresentou excelentes propriedades eletrocrômicas como rápidos tempos de respostas com bons contrastes ópticos / This work presents studies about the chemical synthesis of PEDOT (Poly(3,4-ethylenedioxythiophene)) with the aim of preparing different architectures and properties to improvement the degradability rate of this polymer. The strategies used to achieve this pupose were the preparation of polymer blends, copolymers and nanocomposites. The study was started by the chemical synthesis of microstructures PEDOT in mild and environment friendly conditions, but the material did not show solubility which enable film formation. Then, PEDOT was synthetized by chemical synthesis doped with PSS (poly(styrene sulfonic acid)), (PEDOT:PSS) to prepare blends with PLGA (poly(lactic-co-glycolic acid)) to improve its degradability. It was possible to prepare a thin and nanostructured film, by electrostatic layer-by-layer deposition (LBL), which could be used for electrodes or scaffold surface modification. In order to ensure the material\'s degradability, PEDOT and PLLA (poly(lactide)) copolymers were prepared, changing PEDOT proportion in the polymeric structure. The copolymers were characterized by, IR, NMR, UV, thermal analysis and then degradability and cell viability tests, which shown important results. Fibers were able to be obtained with these materials. The next strategy was the preparation of a nanocomposite by one-spot chemical synthesis, initiated by the monomer EDOT (3,4- ethylenedioxythiophene) using HAuCl4 as oxidant and NaPSS as both dopant and dispersant. The nanocomposite obtained was characterized showing diameter of around 4nm and a core-shell structure, with gold nanoparticle as core and PEDOT:PSS as the shell. Films were obtained by this material by casting, by LBL, using PDDA (Poly(diallyldimethylammonium) chloride) and chitosan as polycations, and by electrophoretic deposition. The latter method shows excellent characteristics as fast response time with a good optical contrast

Na montagem de um farol automobilístico são utilizados diversos materiais, tais como insertos metálicos nas fixações, vidros nas lâmpadas, materiais poliméricos nas lentes, carcaças, molduras, vedações e refletores, além de vernizes, tintas, película de metal para reflexão do feixe luminoso. Há cerca de quatro décadas foi iniciada a confecção dos refletores utilizando o BMC (bulk moulding compound), sigla em inglês para composto para moldagem em forma de massa, que é um compósito polimérico termofixo. Este material apresenta inúmeras vantagens sobre o metal, tal como forma e geometria que podem se integrar facilmente ao desenho do carro, elevada produtividade, baixo custo e da elevada resistência térmica. Contudo, apresentam o inconveniente de não poderem ser reciclados. Uma opção ao BMC tem sido o PEI [poli (éter imida)], que é um material polimérico termoplástico de alto desempenho que apresenta propriedades atrativas para essa utilização. Oferece também elevada produtividade, porém com um custo elevado se comparado ao BMC. Tem a vantagem de pode ser reciclado. De modo a analisar o potencial dos dois materiais e extrair deles suas vantagens competitivas, bem como determinar suas possíveis limitações, o presente trabalho apresenta os resultados de caracterização mecânica, análise térmica, ensaios de impacto, ensaios de temperatura de deflexão térmica (HDT) e reaproveitamento de resíduos de BMC, incorporando-o ao PVC [poli (cloreto de vinila)], resultando uma nova blenda polimérica. O estudo conclui que ambos os materiais podem ser utilizados para fabricação de refletores automobilísticos. No entanto, o preço do PEI é maior que o do BMC, o que desestimula sua utilização em produtos de alta escala de produção, como, por exemplo, o produto do presente trabalho. O BMC por sua vez não pode ser reciclado, exigindo um custo adicional para seu reaproveitamento de maneira a evitar seu descarte em aterro sanitário. / For assembly of an automobile headlight a lot of materials are used such as metallic inserts anchors, glass in the lamps, lens of polymeric materials, bezels, frames, fences and reflectors as well as paints, metallic sheet for reflection of the luminous beam. About four decades ago begun the manufacturing of BMC reflectors, which is a thermoset composite material. This material presents countless advantages on the metal, such as shape and geometry that can easily integrate the designing of cars, high productivity, low cost and high heat resistance. However, they have the disadvantage of not being able to be recycled. An option to the BMC has been the PEI [poly (ether imide)], which is a high performance polymeric thermoplastic material which brings attractive properties for the production of reflectors. It also offers high productivity, however with a high cost compared to BMC. It also has the advantage of being recycled. In order to analyze the potential of both materials and extract their competitive advantages, as well as determine their possible limitations, this study presents the results of mechanical characterization, thermal analysis, impact tests, tests on heat deflection temperature (HDT) and the reuse of BMC waste, incorporating it to PVC [poly (vinyl chloride)], resulting in a new polymeric blend. The study concludes that both materials can be used for manufacturing automobile reflectors. However, the price of PEI is higher than the one of BMC, which discourages their use in high-scale production products, as the one of this work. The BMC for your time can not be recycled, demanding an extra cost for their reuse, avoiding its disposal in landfill.

Para a produção de compósitos multifuncionais crescente atenção tem sido dada a uma homogeneização eficaz de hidroxiapatitas em matrizes poliméricas, buscando uma sintonia fina da concentração entre polímeros biodegradáveis e biocerâmicas. Este trabalho dedicou-se a síntese, caracterização e estudo das propriedades biológicas do híbrido hidroxiapatita / poli(ε-aprolactona) estrela. A hidroxiapatita nanométrica (HAPN) foi revestida com o polímero biodegradável poli(ε -caprolactona) de topologia em estrela de três braços (PCLE). O uso de um polímero com topologia ramificada visa alterar algumas de suas propriedades mecânicas, a adesão interfacial à cerâmica, a sua viscosidade, o volume hidrodinâmico e sua cinética de degradação. O desempenho do híbrido HAPN/PCLE foi comparado com os materiais: HAP com partículas micrométricas (HAP-91 material comercial), o seu compósito revestido com PCLE (HAP-91/PCLE) e uma cerâmica nanométrica bifásica hidroxiapatita/β-TCP (HAP-8). Os materiais foram caracterizados por avaliações físico-químicas e biológicas realizadas por estudos de citotoxicidade, adsorção de proteínas, proliferação celular, atividade de fosfatase alcalina. A síntese de PCLE foi verificada por análise espectroscópica (espectroscopia no infravermelho-FTIR; ressonância magnética nuclear de prótons- 1H-RMN e carbono- 13C-RMN; a matriz assistida por desorção a laser / ionização; MALDI-TOF; e cromatografia de permeação em gel (GPC). O revestimento das biocerâmicas por PCLE foi confirmado por técnicas de microscopia eletrônica de transmissão (MET) e de varredura (MEV). Os compósitos mostraram uma melhor trababilidade em relação à cerâmica pura e são menos quebradiços, possivelmente devido à presença do PCLE na interface da biocerâmica. A análise de MEV e MET mostrou um aspecto de continuidade no contorno das partículas de cerâmica, em micro e nano-escala. Os compósitos apresentam comportamento não citototóxico e propiciaram um crescimento de células de mamíferos. A proliferação de células osteoblásticas (MG -63) foi significativamente mais elevada para o compósito HAPN/PCLE em comparação com outros biomateriais, sugerindo influência da área de superfície na adesão e proliferação de células. O estudo do ângulo de contato indicou que o revestimento com PCLE faz com que a superfície da biocerâmica seja mais hidrofóbica. O estudo com radioisótopos indicou que o revestimento da biocerâmica com PCLE altera significativamente a adsorção das proteínas do sangue fibrinogênio e albumina. O processo de regeneração do tecido ósseo foi estudado em condições in vivo com a implantação de pastilhas dos materiais estudados em tíbias de coelho. Os resultados mostraram que os compósitos podem ser utilizados como biomaterial, pois houve neoformação óssea ao redor dos implantes. / For the production of multifunctional composites in the combination of biodegradable polymers and bioceramics, increasing attention has been paid to an effective homogenization of hydroxyapatite within polymer matrices and a fine tuning of the concentration. This work was dedicated to the synthesis, characterization and study of the biological properties of the hybrid star poly(ε-caprolactone)/hydroxyapatite composites. A nanometer hydroxyapatite (HAPN) was coated with the biodegradable polymer poly (ε-caprolactone) with three arms star topology (PCLE). The use of polymer branched topology aims to change some of its mechanical properties, the interfacial adhesion to ceramic, its viscosity, the hydrodynamic volume and its degradation kinetics. The performance of the hybrid HAPN/PCLE was compared with the other three materials: HAP commercial micrometric particles (HAP-91), their composite coated with PCLE (HAP-91/PCLE) and a biphasic ceramic nanohydroxyapatite/β-TCP (HAP-8). All materials were characterized by different physico-chemical and biological evaluations performed by cytotoxicity studies, protein adsorption, cell proliferation, alkaline phosphatase activity and an in vivo studies. The synthesis of PCLE was verified by spectroscopic analysis (Fourier-Transform infrared-FTIR and nuclear magnetic resonance-1H-NMR/13C-NMR), matrix-assisted laser desorption/ionization (MALDI-TOF) and gel permeation chromatography (GPC). The coating of the bioceramics by PCLE was confirmed by microscopy techniques transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The composites showed better easy handling in relation to pure ceramic and are less brittle, possibly due to the presence of PCLE at bioceramic interface. The SEM and TEM analysis showed an aspect of continuity in the contour of the ceramic particles, both in micro and nanoscale. The composites exhibit non cytotoxicity behavior and propitiated mammalian cell growth. The proliferation of osteoblastic cells (MG-63) was significantly higher for the composite HAPN/PCLE compared to other biomaterials, suggesting influences of the surface area on the cell adhesion and proliferation. The study of contact angle indicated that the PCLE coating makes the bioceramic surfaces more hydrophobic. The radioisotopic studies indicates that the coating of bioceramics with PCLE significantly alter the adsorption of blood proteins fibrinogen and albumin. The process of regeneration of bone tissue was studied in in vivo conditions after implantation of implants manufactured from composites in rabbit´s tibias. The results showed that composites can be used as biomaterial since the newly bone grew around the implants.

Este trabalho apresenta o estudo da incorporação de fibra de vidro curta em composto rígido de poli(cloreto de vinila) - PVC - por meio de equipamentos e técnicas de processamento convencionais da indústria brasileira. Foram avaliadas as influências de: a) tamanho de fibra de vidro (tipo E), b) dosagem de fibra de vidro, c) dosagem de dióxido de titânio (TiO2) e d) a temperatura de processamento nas propriedades físicas, térmicas, mecânicas e na adesão entre matriz polimérica e fibra de vidro (analisada por Microscopia Eletrônica de Varredura). O custo-benefício dos compósitos foi calculado por meio de Índices de Mérito para os modos de carregamento mecânico encontrados nos tubos pressurizados para água fria (Cilindro com Pressão Interna) e perfis rígidos utilizados em construção civil (Barra em Flexão), dado o grande uso de PVC nestas aplicações. Entre os resultados obtidos, destaca-se o aumento de 45% no módulo de elasticidade para os compósitos com 20% de fibra de vidro moída que, para algumas aplicações, pode apresentar uma relação custo-benefício bastante favorável. / This work presents the impact of the short glass fiber incorporation in rigid PVC compound through conventional processing techniques currently employed in the Brazilian industry. It were studied the influences of a) glass fiber geometry (E type), b) glass fiber content, c) titanium dioxide content and d) processing temperature in the physical, mechanical and thermal properties. The adhesion conditions between polymeric matrix and glass fiber was analyzed by scanning electron microscopy (SEM). Cost-benefit relation of composites was evaluated using materials index technique for mechanical conditions found in pressurized water pipes (cylinder with internal pressure) and in building construction profiles (beam loaded in bending). The results attained suggested that, in some cases, the mechanical properties enhancement (such as the increase of 45% in the modulus of elasticity for composites containing 20% of glass fiber) and the processing techniques required to produce it can present an interesting cost-benefit relation.

O presente trabalho descreve o preparo, a caracterização e o uso de eletrodo modificado com polímero de azul de metileno (PMB) imobilizado sobre a superfície de eletrodo de carbono vítreo (GCE-PMB) na análise do herbicida glifosato. O método utilizado para a preparação dos filmes do PMB foi a eletropolimerização. Os filmes preparados por este método apresentam características diferenciadas tais como robustez, estabilidade e propriedade redox satisfatória. As condições experimentais otimizadas foram a velocidade de varredura (50 mV s-1), o intervalo de potencial (-0,4 a +1,2 V), o número de ciclos (30) e o pH da solução do eletrólito suporte (pH 8). A solução de eletrólito suporte foi preparada a partir das soluções de tampão fosfato (0,05 mol L-1) e NaNO3 (0,1 mol L-1), pH 8. A mesma foi utilizada no preparo da solução de azul de metileno (MB) (0,25 x 10-3 mol L-1), no pré-tratamento do eletrodo de carbono vítreo (GC) por voltametria cíclica (CV) e no preparo de soluções para os estudos iniciais com o GCE-PMB. O pré-tratamento da superfície do eletrodo de GC foi realizado aplicando + 0,9 V por 240 s seguido de várias varreduras cíclicas de -0,4 a +1,0 V com velocidade de varredura de 50 mV s-1 até obter um perfil estável do voltamograma do eletrodo. Após o preparo do GCE-PMB, a atividade eletrocatalítica do eletrodo foi investigada para o Ácido Ascórbico (AA) e a L-Cisteína (L-Cys) por CV de -0,4 a +0,6. Foi observado aumento da corrente de pico e diminuição do sobrepotencial em relação ao eletrodo de GC. Nos estudos na presença do glifosato, o GCE-PMB apresentou resposta eletroquímica direta, por voltametria cíclica, para o glifosato (1,0 x 10-3 mol L-1) em solução de KCl 0,1 mol L-1 (pH 5,3) de -0,4 a +0,6 V e velocidade de varredura 50 mV s-1. A resposta voltamétrica apresentou picos anódico e catódico em 0,2 e 0, respectivamente. Para os estudos realizados por meio da técnica de voltametria de onda quadrada (SWV), os parâmetros freqüência, amplitude e incremento de varredura foram otimizados. A partir desses estudos foi possível obter informações relevantes sobre a interação do GCE-PMB com o glifosato. Os resultados mostraram que é possível observar a eletroatividade do herbicida glifosato sobre uma superfície eletródica sem a presença de metais como agentes complexantes. / This work describes the preparation, characterization and the use of the modified electrode with methylene blue polymer (PMB) immobilized onto the surface of glassy carbon electrode (GCE-PMB) in the analysis of the herbicide glyphosate. Concerning the methodology aspects, the method used for the preparation of the films PMB was the electropolymerization. The films prepared by this method present a differentiated characteristic such as robustness, stability and good redox properties. The optimized experimental conditions are the scan rate (50 mV s-1), the potential range (-0.4 to +1.2 V), the number of cycles (30) and the pH of the supporting electrolyte (pH 8). The supporting electrolyte solution was prepared from phosphate buffer solutions (0.05 mol L-1) and NaNO3 (0.1 mol L-1), pH 8. The same solution was used to prepare the solution of methylene blue (MB) (0.25 x 10-3 mol L-1), the pretreatment of the GC electrode by cyclic voltammetry (CV). It was also utilized in preparing solutions for the initial studies with GCE-PMB. The pre-treatment of the electrode surface of GC was performed, considering 0.9 V during 240 s, followed by several cyclic scans from -0.4 to 1.0 V (with scan rate of 50 mV s-1) until a stable profile of the voltammogram. After preparing the GCE-PMB, electrocatalytic activity it was investigated for Ascorbic Acid (AA) and L-Cysteine (L-Cys) by CV from -0.4 to +0.6 V. It was observed increase in peak current and decrease the overpotential comparing to glassy carbon electrodes. The GCE-PMB presented direct electrochemical response, for glyphosate (1 x 10-3 mol L-1) in KCl 0.1 mol L-1 (pH 5.3) from -0.4 to +0.6 V and scan rate 50 mV s-1. The voltammetric response showed anodic and cathodic peaks in 0.2 and 0, respectively. Using the square wave voltammetry (SWV), the parameters frequency, amplitude and scan increment were optimized. It was possible to find relevant information about the interaction between GCE-PMB and glyphosate. These results showed that is possible observe the electroactivity of glyphosate on a modified electrodic surface in absence of metals or complexing agents.