Clay minerals have historically played a consequential role in human health. While the beginnings were rooted in geophagy, a primitive act of consuming earth, the health-related uses of clay minerals have evolved and diversified over time. As excipients in pharmaceutical formulations, clay minerals can attribute novel properties onto intercalated compounds. Intercalating oxybenzone, a UV filter, within the interlamellar space of montmorillonite is desirable in order to minimize direct contact with skin. Intercalating resveratrol, a compound known for attributing beneficial effects onto human health, may be advantageous since this compound is susceptible to cis-trans isomerisation. The strategy of using alkylammonium–modified clay was undertaken and proved successful for the intercalation of oxybenzone. The field of biopolymer/layered silicate nanocomposites is heavily researched for use in a multitude of applications. Novel montmorillonite nanocomposites were prepared with neutral guar gum and cationic guar gum, using an environmentally friendly process and are fully characterized.

Engineered organoclays are 2:1 phyllosilicate soils that have been synthesized with a controlled interlayer organic phase to exhibit enhanced strength, lower compressibility, and stronger retention of organic compounds. Engineered organoclays are highly sorptive, and have a variety of potential engineering applications as sorbents or amendments in engineered earthen barrier systems. Previous studies examined the impact of the organic coating on a soil's physical properties; however, the geochemical behaviors of organoclays, especially their interaction with organic compounds at the micro-scale, remained relatively unquantified. This study investigated the engineering behavior of montmorillonite modified with a variety of quaternary ammonium cations (QAC clays) with controlled structure and density of loading. Molecular dynamics simulations were used to model the surfactant arrangement, geochemical processes in the QAC-clay interlayer, including organic compound sorption and mass transport, as well as the surface electrokinetics of suspended QAC-clay particles. All simulations were carried out based on the combined force field of ClayFF and the Consistent-Valence Force Field to ensure the accuracy of the simulation results, and results yielded insight into the prediction of synthesized QAC-clay behaviors as sorptive material for non-polar organic compounds.

The effects of polyethylene, (PE), type, compatibilizer type and organoclay type on the morphology, rheological, thermal, and mechanical properties of ternary low density polyethylene (LDPE), high density polyethylene (HDPE), and linear low density polyethylene (LLDPE), matrix nanocomposites were investigated in this study. Ethylene &ndash / Methyl acrylate &ndash / Glycidyl methacrylate terpolymer (E-MAGMA) and Ethylene &ndash / Butyl acrylate- Maleic anhydrate terpolymer (E-BA-MAH) were used as the compatibilizers. The organoclays selected for the study were Cloisite 30B and Nanofil 8. Nanocomposites were prepared by means of melt blending via co-rotating twin screw extrusion process. Extruded samples were injection molded to be used for material characterization tests. Optimum amounts of ingredients of ternary nanocomposites were determined based on to the mechanical test results of binary blends of PE/Compatibilizer and binary nanocomposites of PE/Organoclay. Based on the tensile test results, the optimum contents of compatibilizer and organoclay were determined as 5 wt % and 2 wt %, respectively. XRD and TEM analysis results indicated that intercalated and partially exfoliated structures were obtained in the ternary nanocomposites. In these nanocomposites E-MA-GMA compatibilizer produced higher d-spacing in comparison to E-BA-MAH, owing to its higher reactivity. HDPE exhibited the highest basal spacing among all the nanocomposite types with E-MA-GMA/30B system. Considering the polymer type, better dispersion was achieved in the order of LDPE&lt / LLDPE&lt / HDPE, owing to the linearity of HDPE, and short branches of LLDPE. MFI values were decreased by the addition of compatibilizer and organoclay to the matrix polymers. Compatibilizers imparted the effect of sticking the polymer blends on the walls of test apparatus, and addition of organoclay showed the filler effect and increased the viscosity. DSC analysis showed that addition of compatibilizer or organoclay did not significantly affect the melting behavior of the nanocomposites. Degree of crystallinity of polyethylene matrices decreased with organoclay addition. Nanoscale organoclays prevented the alignment of polyethylene chains and reduced the degree of crystallinity. Ternary nanocomposites had improved tensile properties. Effect of compatibilizer on property enhancement was observed in mechanical results. Tensile strength and Young&rsquo / s modulus of nanocomposites increased significantly in the presence of compatibilizers.

Clay minerals have historically played a consequential role in human health. While the beginnings were rooted in geophagy, a primitive act of consuming earth, the health-related uses of clay minerals have evolved and diversified over time. As excipients in pharmaceutical formulations, clay minerals can attribute novel properties onto intercalated compounds. Intercalating oxybenzone, a UV filter, within the interlamellar space of montmorillonite is desirable in order to minimize direct contact with skin. Intercalating resveratrol, a compound known for attributing beneficial effects onto human health, may be advantageous since this compound is susceptible to cis-trans isomerisation. The strategy of using alkylammonium–modified clay was undertaken and proved successful for the intercalation of oxybenzone. The field of biopolymer/layered silicate nanocomposites is heavily researched for use in a multitude of applications. Novel montmorillonite nanocomposites were prepared with neutral guar gum and cationic guar gum, using an environmentally friendly process and are fully characterized.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho foram preparados nanocompósitos de elastômeros termoplásticos à base de PP/EPDM/argila organofílica. Foram utilizados como agentes interfaciais polipropileno e terpolímero de etileno-propileno-dieno ambos modificados com grupos anidrido maleico, PP-MA e EPDM-MA, respectivamente. Dois tipos de argila organofílica, que se diferenciam pela estrutura química do surfactante e conseqüentemente pela estabilidade térmica, foram empregados como carga inorgânica. Os nanocompósitos foram preparados pela técnica de intercalação por fusão em câmara interna de mistura e a incorporação da argila foi feita pela adição de masterbatches previamente preparados. Foram investigadas as propriedades de tração, reométricas e ainda a morfologia (cristalinidade e estrutura obtida) dos nanocompósitos a fim de estabelecer a influência do tipo e quantidade de argila organofílica e agente interfacial. Os resultados mostraram que a adição de agente interfacial melhorou a dispersão da argila organofílica na matriz de PP/EPDM, particularmente o PP-MA. Foram obtidos nanocompósitos com estruturas mistas intercaladas e esfoliadas, que resultaram em maiores valores de módulo de elasticidade e manutenção dos valores de deformação. As propriedades reométricas confirmaram o maior grau de dispersão da argila organofílica em nanocompósitos contendo PP-MA. Teores crescentes de argila reduziram a cristalinidade dos nanocompósitos, os quais quando reprocessados, mantiveram as características inerentes ao TPE de origem. Por fim, a estrutura do surfactante presente / In this work it was prepared nanocomposites based in PP/EPDM thermoplastic elastomer and organoclay. Maleinized polypropylene and ethylene-propylene-diene rubber, PP-MA and EPDM-MA, respectively, were employed as interfacial agents. Also two kinds of organoclays, differing about surfactant chemical structure and as consequence thermal stability, were investigated as inorganic filler. Nanocomposites were prepared by melt intercalation in an internal chamber mix and organoclay was incorporated by masterbatches addition, which ones were previously made. It was investigated the influence of amount and kind of organoclay and interfacial agent on tensile properties, rheology and morphology (crystallinity and structure type) of nanocomposites obtained. The results showed that interfacial agents addition promoted a better dispersion degree of organoclay platelets in PP/EPDM matrix, mainly PP-MA. Nanocomposites with both intercalated and exfoliated structures were obtained. These exhibited higher Young modulus and kept their elongation values. The better dispersion degree of clay platelets in nanocomposites containing PP-MA was confirmed by rheology measurements. Increasing amounts of organoclay lowered the crystallinity degree of nanocomposites but the reprocessability was maintained similar to that of pure TPE. Finally, the chemical structure of surfactants did not change the intercalation/exfoliation process due to the similarity of organoclay basal spacing and moderated TPE processing temperature.

Clay minerals have historically played a consequential role in human health. While the beginnings were rooted in geophagy, a primitive act of consuming earth, the health-related uses of clay minerals have evolved and diversified over time. As excipients in pharmaceutical formulations, clay minerals can attribute novel properties onto intercalated compounds. Intercalating oxybenzone, a UV filter, within the interlamellar space of montmorillonite is desirable in order to minimize direct contact with skin. Intercalating resveratrol, a compound known for attributing beneficial effects onto human health, may be advantageous since this compound is susceptible to cis-trans isomerisation. The strategy of using alkylammonium–modified clay was undertaken and proved successful for the intercalation of oxybenzone. The field of biopolymer/layered silicate nanocomposites is heavily researched for use in a multitude of applications. Novel montmorillonite nanocomposites were prepared with neutral guar gum and cationic guar gum, using an environmentally friendly process and are fully characterized.

As nanocomposites provide considerable improvements in material properties, scientists and engineers are focussing on biodegradable nanocomposites having superior material properties as well as degradability. This thesis has investigated the properties of biodegradable nanocomposites of the aliphatic thermoplastic polyester, poly (lactide acid) (PLA) and the synthetic biodegradable polyester, poly (butylene succinate) (PBS). To enhance the properties of this blend, nanometer-sized clay particles, have been added to produce tertiary nanocomposite. High aspect ratio and surface area of clay provide significant improvement in structural, mechanical, thermal and barrier properties in comparison to the base polymer. In this study, a series of PLA/PBS/layered silicate nanocomposites were produced by using a simple twin-screw extruder. PLA/PBS/Cloisite 30BX nanocomposites were prepared containing 1, 3, 5, 7 and 10 wt% of C30BX clay, while PLA and PBS polymers compositions were fixed at a ratio of 80 to 20. This study also included the validation of a gas barrier model for these biodegradable nanocomposites. WAXD indicated an exfoliated structure for nanocomposites having 1 and 3 wt% of clay, while predominantly development of intercalated structures was noticed for nanocomposites higher than 5 wt% of clay. However, TEM images confirmed a mixed morphology of intercalated and exfoliated structure for nanocomposite having 1 wt% of clay, while some clusters or agglomerated tactoids were detected for nanocomposites having more than 3 wt% of clay contents. The percolation threshold region for these nanocomposites lied between 3-5 wt% of clay loadings. Liquid-like behaviour of PLA/PBS blends gradually changed to solid-like behaviour with the increase in concentration of clay. Shear viscosity for the nanocomposites decreased as shear rate increased, exhibiting shear thinning non-Newtonian behaviour. Tensile strength and Young's modulus initially increased for nanocomposites of up to 3 wt% of clay but then decreased with the introduction of more clay. At high clay content (more than 3 wt%), clay particles tend to aggregate which causes microcracks at the interface of clay-polymer by lowering the polymer-clay interaction. Percentage elongation at break did not show any improvement with the addition of clay. PLA/PBS blends were considered as immiscible with each other as two separate glass transition and melting temperatures were observed in modulated differential scanning calorimetry (MDSC) thermograms. MDSC showed that crystallinity of the nanocomposites was not much affected by the addition of clay and hence some compatibilizer is required. Thermogravimetric analysis showed that the nanocomposite containing 3 wt% of clay demonstrated highest thermal stability compared to other nanocomposites. Decrease in thermal stability was noticed above 3 wt% clay; however the initial degradation temperature of nanocomposites with 5, 7 and 10 wt% of clay was higher than that of PLA/PBS blend alone. Gas barrier property measurements were undertaken to investigate the transmission of oxygen gas and water vapours. Oxygen barrier properties showed significant improvement with these nanocomposites, while that for water vapour modest improvement was observed. By comparing the relative permeabilities obtained from the experiments and the model, it was concluded that PLA/PBS/clay nanocomposites validated the Bharadwaj model for up to 3 wt% of clay concentration.

Organic materials are ubiquitous in the geologic environment, and can exert significant influence over the interfacial properties of minerals. However, due to the complexity in their structure and interaction with soil solids, their impact has remained relatively unquantified. This study investigated the engineering behaviors of organoclays, which were synthesized in the laboratory using naturally occurring clay minerals and quaternary ammonium compounds of controlled structure and density of loading. Organic cations were chosen to study the effects of functional group structure and size. The laboratory investigation showed that the presence of the organic cations on the mineral surfaces led to increased hydrophobicity of all clays tested. Conduction studies on the electrical, hydraulic, and thermal properties of the organoclay composites suggested that increasing the total organic carbon content resulted in decreased electrical and thermal conductivity, but increased hydraulic conductivity, due to the reduced swelling of the base clay mineral phase. Electrokinetic properties of the organoclays illustrated that compared with the clay's naturally occurring inorganic cations, exchanged quaternary ammonium cations were more likely bound within a particle's shear plane. Consequently, organoclays had less negative zeta potential than that of unmodified bentonite. Increasing the length of one carbon tail was more effective at binding organic cations within the shear plane than increasing the size of the cation, when compared on the basis of total organic carbon content. In terms of large strain strength, the modified organic clays exhibited increased shear strength, in part owing to the reduction in water content caused by the presence of the hydrophobic organic layering. Shear strength increased with single carbon tail length or with cation size, although the latter effect tended to reach a plateau as the length of the four short cation tails increased from 2 to 4. In terms of small strain behavior, the shear modulus was shown to be a function of the total organic carbon content. It is believed that number of particle contacts increased as the organic carbon content increased. Stiffness increased as either the size of the cation or the total organic carbon content was increased. Damping also increased as the organic loading was increased, with the organic phase acting as an energy dissipation mechanism.

Made available in DSpace on 2016-12-08T17:19:17Z (GMT). No. of bitstreams: 1 Tarcisio Sanson Sene.pdf: 3938998 bytes, checksum: 4f0f85a51934cd08bc44991295bfcef1 (MD5) Previous issue date: 2012-06-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Interesting changes in mechanical and electrical conductivity properties of polymeric matrixes are provided by dispersing carbon nanotubes, obtaining a nanocomposite. Current researches showed an effect of assisted dispersion of carbon nanotubes (CNT) by montmorilonite clay in an epoxy matrix, in a way that increments of clay provided better dispersion of CNT in the matrix, increasing the nanocomposite electrical conductivity when the same fraction of CNT was kept. This work intended to assess the effect of the simultaneous dispersion of a montmorillonite clay and CNT on a diglycidyl ether of bisphenol-A (DGEBA) epoxy matrix. Further, the assisted dispersion of CNT was assessed by two different montmorillonite clays: as natural (MMT-Na) and an organoclay (MMT-30B). The nanocomposites were fabricated by in situ polymerization method, using high energy sonication as the dispersion method, without the aid of solvents in the medium. The nanocomposites were molded by casting or by resin transfer molding (RTM), adding 27% v/v of glass-fibers in the latter molding method, obtaining a hybrid micro/nanocomposite. The glass transition temperature (Tg) of the nanocomposites was increased until 10ºC for the samples containing MMT-30B clay, however it practically did not change with the dispersion of MMT-Na clay, when compared to the Tg of the neat epoxy matrix. In the other hand, the simultaneous dispersion of CNT with each one of the clays provided two different Tg behaviors, with the same 10ºC increasing in Tg when the CNT were added with MMT-30B, and a lower increase of 3ºC in the Tg when the MMT-Na and CNT were added, also comparing to the neat sample. The casted samples did not show a significant change in the flexural modulus, though the flexural strength was reduced in the samples containing any of the clays, being this reduction proportional to the agglomerated feature of the nanocomposite. Regarding to the CNT percolation threshold in the epoxy matrix, it was verified to be between 0,04 and 0,10% v/v of CNT. The simultaneous dispersion of CNT with the clays just produced distinct dielectric behaviors when the fraction of CNT was higher than the percolation threshold. Both clays affected the continuity of the CNT percolated network, considering the clay fraction used. The simultaneous adding of MMT-30B clay with CNT was the condition that most reduced the conductivity of the samples, among those containing the same CNT fraction. The MMT-Na clay did not reduce the number of percolated ways of CNT as the MMT-30B, and, above a critical frequency of electrical current, the simultaneous dispersion of MMT-Na and CNT exhibited higher conductivity than the sample containing just the same CNT fraction, suggesting that more polarizable interfaces are being produced at this condition. Regarding to the hybrid micro/nanocomposites produced by RTM, there is a suspect that the low fraction of nanoparticles did not favor the increasing in the flexural modulus of the hybrid composite. The high viscosity of the samples containing any one of the clays caused low impregnation in the glass-fibers, obtaining regions of the composite without fibers dispersed. The MMT-Na clay was filtered though the porous medium during the resin infusion, probably due to its hydrophilic nature, showing lower compatibility with the epoxy matrix. / Nanotubos de carbono dispersos em matrizes poliméricas podem proporcionar interessantes alterações em propriedades mecânicas e de condutividade elétrica no material nanocompósito resultante. Trabalhos atuais demonstram um possível efeito de dispersão de nanotubos de carbono (NTC) assistida pela dispersão simultânea com argila montmorilonita natural em uma matriz epoxídica, de modo que incrementos de argila proporcionariam melhor dispersão dos NTC na matriz, elevando a condutividade elétrica quando mantido constante o teor de NTC. Este trabalho intencionou avaliar o efeito da dispersão simultânea de argila montmorilonita e NTC nas propriedades mecânicas, térmicas e dielétricas de uma matriz de epóxi do diglicidil éter do bisfenol-A (DGEBA). Ainda, foi avaliado o efeito de dispersão de NTC assistido por duas diferentes argilas montmorilonita: natural (MMT-Na) e uma organoargila (MMT-30B). Os nanocompósitos foram fabricados pelo método de polimerização in situ, utilizando sonicação de alta energia como fonte de dispersão e sem a utilização de solventes. Os nanocompósitos foram moldados por casting e por moldagem por transferência de resina (RTM resin transfer molding), neste último método sendo utilizados 27% v/v de fibras-de-vidro, obtendo-se um híbrido micro/nanocompósito. A temperatura de transição vítrea (Tg) dos nanocompósitos foi elevada em até 10ºC para os nanocompósitos contendo argila MMT-30B, porém praticamente não se alterou com a dispersão argila MMT-Na, quando comparado com a Tg da matriz sem as nanopartículas. Já a dispersão simultânea de NTC com cada uma das duas argilas promoveu diferentes alterações na Tg, não alterando em relação à Tg do nanocompósito que possuía somente argila MMT-30B e elevando a Tg da amostra que possuía argila MMT-Na em 3ºC em relação à amostra pura. As amostras preparadas por casting não apresentaram significante alteração de módulo de elasticidade, porém, quando presente alguma das argilas na composição da amostra, a resistência à flexão foi reduzida proporcionalmente ao caráter aglomerado das nanopartículas. Com relação ao limiar de percolação de NTC, foi verificado estar situado entre teores 0,04 e 0,10% v/v. A dispersão simultânea de cada argila com NTC somente gerou comportamentos distintos de condutividade quando utilizado teor de NTC acima da ocorrência de percolação. Nos teores utilizados, ambas as argilas afetaram a continuidade da rede percolada de NTC, porém a argila MMT-30B foi a que mais reduziu a condutividade em freqüências abaixo de 100 Hz. A argila MMT-Na já não reduziu o número de caminhos percolados de NTC como no caso da argila MMT-30B, e acima de determinada frequência de corrente elétrica, a dispersão simultânea de argila MMT-Na com NTC exibe maior condutividade do que a amostra contendo somente o mesmo teor de NTC, sugerindo que estão sendo geradas interfaces mais polarizáveis quando dispersos simultaneamente a argila MMT-Na e NTC. Em relação aos híbridos micro/nanocompósitos produzidos por RTM, suspeita-se que o baixo teor de nanopartículas não favoreceu o aumento de módulo de elasticidade do material híbrido. A alta viscosidade das amostras que possuíam alguma argila em sua composição gerou baixa impregnação de fibras e formação de regiões sem fibras-de-vidro no volume do compósito. A argila MMT-Na foi filtrada pelo meio poroso durante a infusão, provavelmente devido à sua natureza hidrofílica, possuindo menor compatibilidade com a matriz epoxídica.

Aminoclay belongs to a large group of organic modified materials based on clays. These materials could find many potential practical applications and, in particular, may be used as a matrix with the ability of the organisation and stabilisation of incorporated substances. The utilisation of aminoclay in the field of medical applications seems highly prospective, but there is the need to visualise the clay system and the processes within it. This essay deals with the issue of aminoclay visualisation by means of fluorescent spectroscopy. Through fluorescent spectroscopy, aminoclay was discovered to be autofluorescent. The autofluorescence of aminoclay is not usable in practical applications because of the low fluorescence intensity. This is the reason for the research into other possibilities for modifications of the internal structure of aminoclay by europium ions. These ions in chelated form are able to be fluorescent and modifications of the external structure are possible by electrostatic implementation of fluorescent dyes. Characterisation of the prepared complexes was provided by spectrofluorimetry and fluorescent microscopy for the purpose of evaluation of the practical application of aminoclay.