Membrane bioreactors (MBRs) show great promise for productivity improvement and energy conservation in conventional bioprocesses for wastewater reclamation. In order to attain high productivity in a bioprocess, it is crucial to retain the microorganisms in the bioreactors by preventing wash out. This enables recycling of the microorganisms, and is consequently saving energy. The main feature of MBRs is their permeable membranes, acting as a limitative interface between the medium and the microorganisms. Permeation of nutrients and metabolites through the membranes is thus dependent on the membrane characteristics, i.e. porosity, hydrophilicity,and polarity. The present thesis introduces membranes for MBRs to be used in a continuous feeding process, designed in the form of robust, durable, and semi-hydrophilic films that constitute an effective barrier for the microorganisms, while permitting passage of nutrients and metabolites. Polyamide 46 (polytetramethylene adipamide), a robust synthetic polymer, holds the desired capabilities, with the exception of porosity and hydrophilicity. In order to achieve adequate porosity and hydrophilicity, bulk functionalization of polyamide 46 with different reagents was performed. These procedures changed the configuration from dense planar to spherical, resulting in increased porosity. Hydroxyethylation of the changed membranes increased the surface tension from 11.2 to 44.6 mJ/m2. The enhanced hydrophilicity of PA 46 resulted in high productivity of biogas formation in a compact MBR, due to diminished biofouling. Copolymerization of hydrophilized polyamide 46 with hydroxymethyl 3,4-ethylenedioxythiophene revealed electroconductivity and hydrophilic properties, adequate for use in MBRs. To find either the maximal pH stability or the surface charge of the membranes having undergone carboxymethylation, polarity and the isoelectric point (pI) of the treated membranes were studied by means of a Zeta analyzer. The hydroxylated PA 46 was finally employed in a multilayer membrane bioreactor and compared with hydrophobic polyamide and PVDF membranes. The resulting biogas production showed that the hydroxylated PA 46 membrane was, after 18 days without regeneration, fully comparable with PVDF membranes.

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A pesquisa avalia comparativamente algumas propriedades físicas e químicas da poliamida 6.6 convencional e biodegradável. Avalia também o tempo de biodegradabilidade da amostra de fio biodegradável e convencional. As propriedades físicas analisadas foram de resistência, alongamento e tenacidade. Já as propriedades químicas foram relativas ao comportamento das amostras quanto ao tingimento e avaliações de solidez posteriores ao tingimento. As amostras avaliadas foram retiradas de malhas produzidas com fio de poliamida 80 dtex f68 x 2, normal e biodegradável, sendo purgadas, alvejadas e tintas. Os resultados das análises físicas, apesar de estatisticamente diferente, possuem os valores das médias muito próximos, o que na prática representam valores aceitáveis dentro do controle estatístico de processo. Ambas as amostras normal e biodegradável apresentaram mesmo comportamento químico, não havendo nenhuma diferença. Com relação ao tempo de biodegradabilidade, sob condições laboratoriais, o dióxido de carbono produzido pelas amostras foi monitorado e medido para determinar a porcentagem de biodegradação de acordo com a norma ASTM D 5511. O fio biodegradável apresenta um tempo de biodegradação 16 vezes mais rápido do que o fio de poliamida normal, tendo 81,7% de biodegradação após 735 dias de teste. Isto representa um ganho muito grande em termos ecológicos, tratando-se de uma fibra sintética / The study evaluates comparatively some physical and chemical properties of conventional and biodegradable polyamide 6.6. It also evaluates the period of biodegradation of the biodegradable and conventional yarn. The physical properties analyzed were strength, elongation and toughness. The chemical properties were related on the behavior of the samples in dyeing and evaluation of subsequent strength dyeing. The evaluated samples were taken from knitwear produced with polyamide yarn 80 dtex f68 x 2, normal and biodegradable, being purged, bleached and dyed. The results of the physical tests, although statistically different, have values very near the average, which in practice represent acceptable values within the statistical control process. Both normal and biodegradable samples had the same chemical behavior, and there is no difference. With respect to biodegradation time under laboratory conditions, the carbon dioxide produced by the samples was monitored and measured to determine the percentage of biodegradation according to ASTM D 5511. The biodegradable yarn has a biodegradation time 16 times faster the yarn normal polyamide, having 81.7% biodegradation after 735 days of testing. This is an expressive gain in ecological terms for a synthetic fiber

A poliamida 6.6 é um dos mais importantes membros da família das poliamidas, principalmente pelas excelentes propriedades de engenharia, como desempenho mecânico e térmico. A sua área de aplicação é ampliada pela adição de cargas inorgânicas. Dentre estas cargas podemos destacar as fibras de vidro, talco, wollastonita e micro esferas de vidro, cargas estas industrialmente conhecidas. Por outro lado, partículas de vidro reciclado provenientes de descarte nunca foram estudadas como reforço de poliamida 6.6, em especial as partículas menores, que são rejeitadas na reciclagem pela indústria do vidro por apresentarem dificuldade de transporte para os fornos, podendo depositar-se nos refratários (fenômeno de arraste), aumentando sua taxa de corrosão, assim reduzindo a vida útil dos fornos. Além disso, essas partículas têm formato irregular. Desse modo, compósitos de poliamida 6.6 reforçados com porcentagens variadas de vidro reciclado e cargas usualmente empregadas pela indústria foram processados em laboratório, com o auxílio de uma extrusora dupla-rosca e as amostras avaliadas foram obtidas por injeção. As seguintes propriedades dos compósitos foram avaliadas: resistência à tração, alongamento na ruptura, módulo na tração, resistência ao impacto Charpy sem entalhe, estabilidade dimensional e microscopia eletrônica de varredura. Os resultados indicam que é possível utilizar-se partículas de vidro reciclado numa matriz de PA-6.6 uma vez que as propriedades do compósito final são compatíveis com aquelas proporcionadas pelas cargas comerciais usualmente empregadas. / Polyamide 6.6 is one of the most important members of the polyamide family, mainly for its excellent engineering properties such as good mechanical and thermal performances. Its application area is enlarged by the addition of inorganic fillers. Among these fillers, glass fibers, talc, wollastonite and glass microspheres could be highlighted, which are industrially known fillers. On the other hand, glass particles from glass cullet have never been studied as a polyamide reinforcement, specially the smaller particles, which are rejected by the glass industry because of the carry-over phenomenon, increasing the cost of the smoke washing, as well as the possibility of increasing refractory corrosion, therefore reducing the useful life of the furnaces. Furthermore, these particles present irregular shapes. In this research, polyamide 6.6 composites, reinforced with different percentages of recycled powder glass and other common fillers used by the industry, were processed in laboratory scale with the help of a double screw extruder. Specimens for testing were obtained by injection, and the following composite properties were evaluated: tensile strength, elongation at rupture, elastic modulus, notchless Charpy impact strength, and dimensional stability. The specimens were also observed in a scanning electron microscope. The results indicated that it is possible to use particles of recycled glass in a PA- 6.6 matrix, once the final composite properties are compatible to the ones of composites containing usual commercial fillers.

Nanocompósitos poliméricos foram preparados por meio da incorporação de 1, 2, 5 e 10% das argilas montmorilonita organofílicas Cloisite 15A e 30B em poliamida-6, pelo método de fusão numa extrusora dupla rosca. Em seguida, foram reprocessados numa extrusora mono-rosca gerando folhas pelo método balão e caracterizados por meio de técnicas espectroscópicas, de análise térmica e difração de raio-X. Os estudos mostraram a formação de nanocompósitos com uma boa dispersão e esfolheamento, principalmente em concentrações de argila inferiores a 5%. Nas amostras com 5 e 10%, nanocompósitos intercalados também foram observados. Portanto, quando a concentração de argila aumenta no nanocompósito, fica cada vez mais difícil obter nanocompósitos totalmente esfoliados. Além disso, verificou-se que a incorporação de 1% da Cloisite 15A ou 30B induzem a cristalização do polímero, predominando a fase γ nos filmes. Entretanto, a medida que a concentração de argila aumenta a fração de fase amorfa tende a aumentar, provavelmente em decorrência da diminuição da velocidade do processo de recristalização em torno de 194 ºC, que gera a fase cristalina γ. Foi demonstrado a presença de um excesso de surfactante em uma das argilas organofílicas, tanto na parte exterior dos tactóides como na região interlamelar, aumentando o espaçamento basal e facilitando o processo de intercalação/esfolheamento. Todavia, o excesso de surfactante interfere nos processos de incorporação pois sofrem decomposição em temperaturas relativamente baixas (200 ºC) enquanto o cátion amônio intercalado se decompõe a 240 ºC. De fato, os estudos realizados comprovam que o surfactante tem influência direta sobre as propriedades das argilas organofílicas e grande importância no processo de incorporação. Melhorias significativas foram observadas nas propriedades de barreira a gases e mecânicas, principalmente com relação a resistência a tração, que aumenta a medida que se aumenta a concentração de argila. As propriedades de perfuração não foram significativamente modificadas, mas também verificou-se um aumento significativo da estabilidade mecânica em função da temperatura. Porém, a absorção de umidade interfere negativamente tanto nas propriedades mecânicas quanto na de barreira a gases, sendo que a Cloisite 15A é menos suscetível que a Cloisite 30B, provavelmente devido ao cátion de amônio quaternário ser mais hidrofóbico. Assim, os filmes de nanocompósitos de poliamida- 6/argila devem ter aplicações diversas na indústria de embalagens / Polymeric nanocomposites were obtained by incorporation of 1, 2, 5 e 10% of the organophilic clays Cloisite 15A e 30B in polyamide-6, using a twin-screw extruder and the melting process. Then, the pellets were reprocessed as films in a single-screw extruder coupled with the blow method, and those materials were characterized by means of spectroscopic, thermal and X-ray difraction techniques. The results were consistent with the formation of nanocomposites with excellent dispersion and exfoliation, especially when the concentration of clay was below 5%. In the samples containing 5 e 10%, the presence of tactoids were observed showing the formation of intercalated nanocomposites as well. Thus, as the concentration of organophillic clay increases, the fraction of completely exfoliated clay decreased. Furthermore, the incorporation of clays (Cloisite 15A or 30B) in concentrations as low as 1% induced the crystallization of polyamide-6, such that it was found in the films predominantly in the γ phase. However, as the concentration of clay increases there is a steady increase of the amorphous phase, probably due to the decrease of the rate of the recrystallization process at 194 ºC, responsible for the formation of the γ phase. Also, the presence of an excess of surfactant was confirmed for both, Clositite 15A and 30B, around the tactoids and in the interlamelar space also, increasing the basal distance and facilitating the intercalation/exfoliation process. However, such an excess interfere in the nanocomposite preparation process since decomposes at relatively low temperatures (200 ºC) while the intercalated quaternary ammonium cation decomposes at 240 ºC. In fact, we showed that the structure of the surfactant directly influences the properties of the organophilic clays, and has strong influence on the nanocomposite preparation process. Significant improvements in the barrier effect to gases and in the mechanical properties were noticed for the nanocomposites, particularly on the resistance to traction and on the mechanical stability as a function of temperature, but the resistance to perforation didnt change significantly as the concentration of clay increased. The absorption of water by the nanocomposites influenced negatively the mechanical properties and the barrier effect as well. However, the nanocomposites prepared with Cloisite 15A were less susceptible than those obtained with Cloisite 30B, probably because the quaternary ammoniun salt in the first one is more hydrophobic and repels more effectively the water molecules

Os polímeros têm sido usados em áreas diferentes, como indústrias automotivas, eletrônicas e de construção civil. A poliamida 6 (PA 6) é um dos principais plásticos de engenharia com aplicações em diversas áreas produtivas, devido as suas propriedades térmicas, mecânicas e a estabilidade dimensional. O objetivo principal deste trabalho foi estudar a potencialidade do uso do dióxido de silício coloidal (SiO2) como carga em substituição ao talco, estudando o efeito da radiação ionizante em suas propriedades. O SiO2 é uma substância amorfa com baixa densidade que tem potencial para ser usado como carga mineral em substituição ao talco na matriz da resina de PA 6. Atualmente o talco é a carga mineral mais utilizada pelas indústrias, por isto vem sofrendo redução de suas reservas ao longo dos anos. Este estudo foi desenvolvido a partir da preparação de um \"masterbeach\" de PA 6 com SiO2. Posteriormente, este \"masterbeach\" foi fracionado em diferentes porcentagens em uma matriz de PA 6. Os corpos de prova das amostras foram processados em uma extrusora dupla rosca, injetados e irradiados no acelerador de elétrons para estudar o efeito da radiação ionizante no compósito de PA 6 com diferentes porcentagens de SiO2. Assim sendo, as propriedades destes compósitos foram analisadas e comparadas com as propriedades das amostras de PA6 com talco. Os resultados mostraram que a utilização do SiO2 como carga para a poliamida 6 é tecnicamente viável, uma vez que suas propriedades foram semelhantes ao compósito de PA 6 com talco. A irradiação dos compósitos estudados apresentou melhorias principalmente nas propriedades térmicas e mecânicas. / Polymers have been used in different fields, such as automotive, civil construction and electronics industries. Polyamide 6 (PA 6) is one of the main engineering plastics with several productive applications areas. By the same token, there was an interest in improving their thermal, mechanical and dimensional stability properties. The main objective of this work was to study the potentiality of colloidal silicon dioxide such as filler. According to literature, SiO2 is an amorphous substance with low density. In addition, this material has the potential to be used as a mineral filler to replace the talc in the PA 6 resin matrix. Therefore, SiO2 load was compared to the mineral filler talc which is currently used by industries. Consequently, their reservations are decreasing all over the years. Indeed, these studies were developed from colloidal silicon dioxide with PA 6 the masterbatch elaboration. In addition, the masterbatch was fractionated in different percentages in a PA 6 matrix. It is important to emphasize that all samples were injected and irradiated by an electrons accelerator. Furthermore, the effect of ionizing radiation on the PA 6 composite in different SiO2 percentages was studied. In short, radiation interacts with the polymer by transferring energy to a polymer chain causing modifications that are interfering with its properties. Thus, the mechanical and thermal properties of these composites were measured. In this manner, the irradiation composite studied in that research brought improvements in the thermal and mechanical properties evaluated. In conclusion, results have shown that the use of colloidal silicon dioxide in polyamide 6 composite is technically feasible load to replace talc.

Graphene Nanoplatelets (GNP) was incorporated into polyamide 6 (PA6) matrix by melt compounding method and the enhancements in the properties of the nanocomposites were studied. Response Surface Methodology (RSM) was employed to assist in the study of processing conditions in melt compounding. RSM analysis revealed that the GNP concentrations to be the most significant term to affect the tensile modulus and crystallinity followed by the screw speed whereas the residence time was found to be non-significant. GNP with 5 Î1⁄4m (G5) and 25 Î1⁄4m (G25) were used in the GNP aspect ratio study. The average flake size of G5 and G25 to was measured to be 5.07 Î1⁄4m and 22.0 Î1⁄4m, respectively with the G5 distributed narrowly whereas the G25 exhibit broad distribution. TGA analysis shown that HT25 is more thermally stable compared to G25 due to some remnants lost during thermal treatment and this was confirmed by EDX and CHNS analysis. XRD profiles of the PA6-G-NC illustrate typical peaks of PA6 crystals phase as well as pure graphite characteristic peak. PA6-G25-NC observed to exhibit slightly higher peak intensity compared to PA6-G5-NC suggesting more formation of PA6 crystals. Similar improvement was observed on PA6-HT25-NC compared to PA6-G25-NC indicating more formation of PA6 crystals due improved dispersion of HT25. DSC on PA6-G25-NC showed higher cooling temperature and crystallinity compared to PA6-G5-NC due to larger surface area of the G25. Similarly, PA6-HT25 showed better improvement in crystallinity over PA6-G25-NC due to increase nucleation sites by the HT25. The thermal conductivity of PA6-G25-NC is slightly higher than the thermal conductivity of PA6-G5-NC but not significant considering the G25 is 5 times larger than G5. Instead, no significant difference was observed between PA6-HT25-NC and PA6-G25-NC. Addition of GNP increased the thermal stability of the PA6-G-NC systems under both nitrogen and air atmospheres regardless of the GNP aspect ratio. The viscoelastic properties showed insignificant difference between PA6-G5-NC and PA6-G25-NC. The inefficient improvement by G25 might be due to agglomeration formed during processing. The storage modulus and tan Î ́ of PA6-HT25-NC decreased but the Tg significantly improved compared to PA6-G25-NC. This was assumed to be because of improved dispersion of HT25 but reduced interfacial interaction after the heat treatment. The shear storage modulus, G’ and complex viscosity, |η*| were observed to increase with increasing GNP content with more pronounced improvement seen on PA6-G25-NC compared to PA6-G5-NC. However, no network percolation threshold was observed until 20 wt.% of GNP. The poor interfacial interaction of HT25 resulted in lower G’ and |η*| compared to G25. Tensile test results showed typical improvement with PA6-G25-NC having higher tensile modulus compared to PA6-G5-NC. Further enhancement was obtained with PA6-HT25-NC suggesting improved dispersion and volume of constrained chains mobility despite the poor surface interaction. Comparison with Halphin-Tsai modulus revealed that the effective modulus to be 150 GPa for G5 and 200 GPa for G25. The water uptake measurement results showed that GNP reduced the water uptake percentage and diffusion coefficient especially with G25. The test conducted on saturated PA6-G-NC results in improved thermal conductivity due to the high thermal conductivity of water but the viscoelastic and tensile properties severely reduced due to plasticisation effect.

Nanocompósitos poliméricos foram preparados por meio da incorporação de 1, 2, 5 e 10% das argilas montmorilonita organofílicas Cloisite 15A e 30B em poliamida-6, pelo método de fusão numa extrusora dupla rosca. Em seguida, foram reprocessados numa extrusora mono-rosca gerando folhas pelo método balão e caracterizados por meio de técnicas espectroscópicas, de análise térmica e difração de raio-X. Os estudos mostraram a formação de nanocompósitos com uma boa dispersão e esfolheamento, principalmente em concentrações de argila inferiores a 5%. Nas amostras com 5 e 10%, nanocompósitos intercalados também foram observados. Portanto, quando a concentração de argila aumenta no nanocompósito, fica cada vez mais difícil obter nanocompósitos totalmente esfoliados. Além disso, verificou-se que a incorporação de 1% da Cloisite 15A ou 30B induzem a cristalização do polímero, predominando a fase γ nos filmes. Entretanto, a medida que a concentração de argila aumenta a fração de fase amorfa tende a aumentar, provavelmente em decorrência da diminuição da velocidade do processo de recristalização em torno de 194 ºC, que gera a fase cristalina γ. Foi demonstrado a presença de um excesso de surfactante em uma das argilas organofílicas, tanto na parte exterior dos tactóides como na região interlamelar, aumentando o espaçamento basal e facilitando o processo de intercalação/esfolheamento. Todavia, o excesso de surfactante interfere nos processos de incorporação pois sofrem decomposição em temperaturas relativamente baixas (200 ºC) enquanto o cátion amônio intercalado se decompõe a 240 ºC. De fato, os estudos realizados comprovam que o surfactante tem influência direta sobre as propriedades das argilas organofílicas e grande importância no processo de incorporação. Melhorias significativas foram observadas nas propriedades de barreira a gases e mecânicas, principalmente com relação a resistência a tração, que aumenta a medida que se aumenta a concentração de argila. As propriedades de perfuração não foram significativamente modificadas, mas também verificou-se um aumento significativo da estabilidade mecânica em função da temperatura. Porém, a absorção de umidade interfere negativamente tanto nas propriedades mecânicas quanto na de barreira a gases, sendo que a Cloisite 15A é menos suscetível que a Cloisite 30B, provavelmente devido ao cátion de amônio quaternário ser mais hidrofóbico. Assim, os filmes de nanocompósitos de poliamida- 6/argila devem ter aplicações diversas na indústria de embalagens / Polymeric nanocomposites were obtained by incorporation of 1, 2, 5 e 10% of the organophilic clays Cloisite 15A e 30B in polyamide-6, using a twin-screw extruder and the melting process. Then, the pellets were reprocessed as films in a single-screw extruder coupled with the blow method, and those materials were characterized by means of spectroscopic, thermal and X-ray difraction techniques. The results were consistent with the formation of nanocomposites with excellent dispersion and exfoliation, especially when the concentration of clay was below 5%. In the samples containing 5 e 10%, the presence of tactoids were observed showing the formation of intercalated nanocomposites as well. Thus, as the concentration of organophillic clay increases, the fraction of completely exfoliated clay decreased. Furthermore, the incorporation of clays (Cloisite 15A or 30B) in concentrations as low as 1% induced the crystallization of polyamide-6, such that it was found in the films predominantly in the γ phase. However, as the concentration of clay increases there is a steady increase of the amorphous phase, probably due to the decrease of the rate of the recrystallization process at 194 ºC, responsible for the formation of the γ phase. Also, the presence of an excess of surfactant was confirmed for both, Clositite 15A and 30B, around the tactoids and in the interlamelar space also, increasing the basal distance and facilitating the intercalation/exfoliation process. However, such an excess interfere in the nanocomposite preparation process since decomposes at relatively low temperatures (200 ºC) while the intercalated quaternary ammonium cation decomposes at 240 ºC. In fact, we showed that the structure of the surfactant directly influences the properties of the organophilic clays, and has strong influence on the nanocomposite preparation process. Significant improvements in the barrier effect to gases and in the mechanical properties were noticed for the nanocomposites, particularly on the resistance to traction and on the mechanical stability as a function of temperature, but the resistance to perforation didnt change significantly as the concentration of clay increased. The absorption of water by the nanocomposites influenced negatively the mechanical properties and the barrier effect as well. However, the nanocomposites prepared with Cloisite 15A were less susceptible than those obtained with Cloisite 30B, probably because the quaternary ammoniun salt in the first one is more hydrophobic and repels more effectively the water molecules

A poliamida 6.6 é um dos mais importantes membros da família das poliamidas, principalmente pelas excelentes propriedades de engenharia, como desempenho mecânico e térmico. A sua área de aplicação é ampliada pela adição de cargas inorgânicas. Dentre estas cargas podemos destacar as fibras de vidro, talco, wollastonita e micro esferas de vidro, cargas estas industrialmente conhecidas. Por outro lado, partículas de vidro reciclado provenientes de descarte nunca foram estudadas como reforço de poliamida 6.6, em especial as partículas menores, que são rejeitadas na reciclagem pela indústria do vidro por apresentarem dificuldade de transporte para os fornos, podendo depositar-se nos refratários (fenômeno de arraste), aumentando sua taxa de corrosão, assim reduzindo a vida útil dos fornos. Além disso, essas partículas têm formato irregular. Desse modo, compósitos de poliamida 6.6 reforçados com porcentagens variadas de vidro reciclado e cargas usualmente empregadas pela indústria foram processados em laboratório, com o auxílio de uma extrusora dupla-rosca e as amostras avaliadas foram obtidas por injeção. As seguintes propriedades dos compósitos foram avaliadas: resistência à tração, alongamento na ruptura, módulo na tração, resistência ao impacto Charpy sem entalhe, estabilidade dimensional e microscopia eletrônica de varredura. Os resultados indicam que é possível utilizar-se partículas de vidro reciclado numa matriz de PA-6.6 uma vez que as propriedades do compósito final são compatíveis com aquelas proporcionadas pelas cargas comerciais usualmente empregadas. / Polyamide 6.6 is one of the most important members of the polyamide family, mainly for its excellent engineering properties such as good mechanical and thermal performances. Its application area is enlarged by the addition of inorganic fillers. Among these fillers, glass fibers, talc, wollastonite and glass microspheres could be highlighted, which are industrially known fillers. On the other hand, glass particles from glass cullet have never been studied as a polyamide reinforcement, specially the smaller particles, which are rejected by the glass industry because of the carry-over phenomenon, increasing the cost of the smoke washing, as well as the possibility of increasing refractory corrosion, therefore reducing the useful life of the furnaces. Furthermore, these particles present irregular shapes. In this research, polyamide 6.6 composites, reinforced with different percentages of recycled powder glass and other common fillers used by the industry, were processed in laboratory scale with the help of a double screw extruder. Specimens for testing were obtained by injection, and the following composite properties were evaluated: tensile strength, elongation at rupture, elastic modulus, notchless Charpy impact strength, and dimensional stability. The specimens were also observed in a scanning electron microscope. The results indicated that it is possible to use particles of recycled glass in a PA- 6.6 matrix, once the final composite properties are compatible to the ones of composites containing usual commercial fillers.

Synthetic netropsin analogs of the thiophene and pyridine, induce the netropsin analogs binding DNA from A-T base pair change to G-C base pair. Moreover, dendritic electrostatic groups have bulky conformation, which induce the netropsin analogs binding DNA to major groove.