This project investigates the moisture barrier properties of bio-based polymers and ways of improving them. The first section addresses the effect of crystallinity on the water permeability of poly(lactic acid) (PLA). The second section investigates PLA/talc composites and PLA/ montmorillonite nanocomposites. The third section is focused on a new polymer, polybutylene succinate (PBS), and its nanocomposites with montmorillonite. In the first section, the water vapour transmission rates (WVTR) through samples of polylactic acid of different crystallinities have been measured. Three different grades of commercial PLA were used with different ratios of L-lactide and D-lactide to give a range of crystallinities from 0 to 50%. Sheets of PLA were prepared by melt compounding followed by compression moulding and annealing at different temperatures and for different times to give the range of crystallinities required. Crystallinity was measured by differential scanning calorimetry (DSC) and the morphology of the samples was observed under crossed polars in a transmitted light microscope. Water vapour transmission rates through the films were measured at 38°C and at a relative humidity of 90%. It was found that the measured values of WVTR decreased linearly with increasing crystallinity of the PLA from 0 to 50%. The results are discussed in terms of the effect of crystallinity on solubility and shown to fit the tortuous path model. The model was also successfully used to explain published data on water permeability of polyethylene terephthalate. In the second section, a series of PLA/talc composites and PLA/ montmorillonite nanocomposites were prepared by melt compounding followed by compression moulding. The morphologies of the composites were investigated using transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) and it was found that the fillers were well dispersed in the polymer matrix. The average aspect ratio of the compounded talc was found to be 8, and that of the nanoclay was found to be 50. Water vapour transmission rates (WVTR) through the films were measured at 38°C and at a relative humidity of 90%. It was found that the measured values of WVTR decreased with increasing filler content and the results gave good agreement with predictions from the Nielsen tortuous path model. In the third section, PBS/ montmorillonite nanocomposites were prepared by melt compounding followed by compression moulding. The melting and crystallisation behaviour of the pure PBS samples were investigated using differential scanning calorimetry (DSC) and cross polarised optical microscopy. A slight decrease of the degree of crystallinity was found in PBS containing 5% nanoclay. The morphology of the composites was investigated using transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) and it was confirmed that that composite structures were intercalated. Water vapour transmission rates (WVTR) through the PBS sheets were measured using a MOCON Permatran-W®398. The measured values of WVTR decreased with increasing nanoclay content. However, the experimental values were all higher than the values predicted by the Nielsen tortuosity model. This result shows that in the case of PBS, which is a highly crystalline polymer, the nanoclay is not as well dispersed and is not as effective in reducing water vapour permeability as in the case of PLA.

A number of leaks of radioactive liquors to ground are known to have occurred from several plant buildings, vaults and disposal trenches within and around the Separation area at the Sellafield nuclear site over the past 50 years1. The most significant of these leaks have occurred from the Magnox Silo, the Caesium Extraction Plant, the Magnox Reprocessing Pump House, the Sludge Storage Tanks, the Burial Pits and the Medium Active Evaporation and Thermal Denitration Plant. The radioactive contamination will be accompanied by other components of spent fuel reprocessing, including inorganic salts from neutralised acids, solvents and other organic compounds along with the typical contaminants commonly associated with large industrial activity such as heavy metals, fuel, oils, degreasing agents etc. The research in this thesis describes the effects of common industrial contaminants on the behaviour of Cs and Sr sorption to bentonite and montmorillonite clay minerals. Batch sorption experiments of Cs and Sr uptake onto bentonite and montmorillonite in a number of complex systems were investigated as follows: 1. Initial batch sorption experiments investigating the normal behaviour of the clay minerals. 2. Introduction of anthropogenic organic ligands EDTA, NTA and picolinic acid into the system and their influence on Sr and Cs uptake. 3. Time dependent studies investigating the effect that residence time of the anthropogenic organic ligands has on the sorption properties of montmorillonite and bentonite. 4. Quaternary systems where simulant Magnox sludge equilibrated water, at a number of concentrations, was introduced to ternary systems containing anthropogenic organic ligands. 5. Time dependent studies investigating the effect of hydrocarbons TCE, toluene and naphthalene on the uptake of Cs and Sr to bentonite and montmorillonite. The batch sorption experiments show that the presence of anthropogenic organic ligands reduces the uptake of Cs and Sr by both montmorillonite and bentonite. It is also shown that the presence of simulant Magnox sludge in quaternary systems can also reduce the uptake of Cs and Sr, with significant reductions in sorption observed for Sr sorption in EDTA quaternary systems. Further, the uptake of Cs and Sr to bentonite and montmorillonite appears to decrease with increasing anthropogenic organic ligand residence time. This suggests that the ligands are altering the surface of the clay minerals reducing the number of available binding sites. The influence of hydrocarbons shows a significant decrease in sorption after 3 months for Cs and Sr sorption to montmorillonite. There were no further significant changes for all other hydrocarbon systems investigated.

Nanocomposites with expandable smectites such as montmorillonite layered silicates (MLS) in polymer matrices have attracted extensive application interest. Numerous MLS concentrations have been used with no particular justification. Here, we investigate the effects of MLS dispersion within the matrix and on mechanical performance. The latter is resolved through a three-prong investigation on rate dependent tensile results, time dependent creep results and the influence of a sharp notch in polypropylene (PP) nanocomposites. A fixed concentration of maleated polypropylene (mPP) was utilized as a compatibilizer between the MLS and non-polar PP. Analysis of transmission electron micrographs and X-ray diffraction patterns on the surface and below the surface of our samples revealed a unique skin-core effect induced by the presence of clay. Differential scanning calorimetric and polarized optical microscopic examination of spherulites sizes showed changes in nucleation and growth resulting from both the maleated PP compatibilizer and the MLS. These structural changes resulted in a tough nanocomposite, a concept not reported before in the PP literature. Nonlinear creep analysis of the materials showed two concentrations 3 and 5 % wt of PP, which reduced the compliance in the base PP. The use of thermal wave imaging allowed the identification of ductile failure among materials, but more important, aided the mapping of the elastic and plastic contributions. These are essential concepts in fracture analysis.

A dissertation submitted to the Faculty of Engineering and the built environment, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the degree of Master of Science in Engineering Johannesburg, October 2017 / An investigation was carried out to determine the effect of the addition of clay on the mechanical properties of a Natural Fibre Composite consisting of a polypropylene matrix with kenaf fibre reinforcement. The kenaf fibres were treated using various chemical treatments to improve the strength of the composites manufactured. Four treatments using different 3-mercaptopropyltrimethoxy silane (MPS) concentrations were investigated to determine which treatment resulted in the best mechanical properties. [Abbreviated Abstract. Open document to view full version] / MT 2018

Visando o desenvolvimento de materiais biodegradáveis para embalagens, blendas de amido/quitosana estruturadas com nanopartículas de montmorilonita (MMT) ou nanofibras de bambu (NFBs) em concentrações de (0,0; 0,5 e 1,0) g de NPs/100 g de polímero foram obtidas pelas técnicas de casting e extrusão. Os bionanocompósitos obtidos das duas técnicas foram caracterizados, bem como foi avaliada a influência da dispersão das nanopartículas sobre as principais propriedades físico-químicas dos bionanocompósitos. Para os filmes produzidos de blendas de amido/quitosana por casting, foram avaliadas as proporções de (5/0; 3,75/0,25; 2,5/2,5; 1,25/0,75 e 0/1) g/100 g base polímero, e a adição dos reforçadores na solução filmogênica. Observou-se uma dispersão assim como uma intercalação satisfatória da MMT nos bionanocompósitos, confirmadas pelas mudanças da cristalinidade devido ao deslocamento do pico característico de 7,2 º para 5,2 º; e os filmes estruturados com NFBs apresentaram variações nas frequências vibracionais dos arranjos moleculares indicando a formação de ligações fortes entre as blendas e os reforçadores. A partir da extrusão da mistura de homo pellets e pellets masterbatch, das blendas de amido/quitosana nas proporções de (100/0; 75/25 e 50/50) g/100 g, foram obtidos compósitos em processo contínuo os quais exibiram propriedades qualitativas satisfatórias assim como mudanças de cristalinidade e interações moleculares. Em relação às propriedades mecânicas, os bionanocompósitos apresentaram um aumento da resposta à tensão assim como da elongação e módulo de elasticidade em relação às concentrações dos reforçadores em cada umas blendas avaliadas. Por outro lado, tanto a formação das blendas como as interações dos reforçadores modificaram significativamente a rede tridimensional dos filmes em relação à taxa de transferência de vapor de água, obtendo-se valores de (155 e 139) g m-2 d-1 para os compósitos obtidos da blenda amido/quitosana 100/0 estruturados com (0,5 e 1,0) g MMT/100 g, respectivamente. Os valores de PVA obtidos são inferiores aos reportados por produtos comerciais como o (PBS) Bionolle™ (330 g m-2 d-1) e (PBAT) Ecoflex® (272 g m-2 d-1). Neste trabalho foi possível desenvolver um material promissor com características diferenciadas e alta aplicabilidade no setor de embalagens biodegradáveis para uso industrial. / Aiming at the development of biodegradable packaging materials, starch/chitosan blends structured with montmorillonite nanoparticles (MMT) or bamboo nanofibers (NFBs) at concentrations of (0.0,0.5 and 1.0) g NPs/100 g of polymer were obtained by the casting and extrusion techniques. The obtained bio-nanocomposites were characterized, as well as, how the dispersion of nanoparticles influenced the main physicochemical properties of the films. For the films from starch/chitosan blends produced by the casting method, the proportions of (5/0, 3.75/0.25, 2.5/2.5, 1.25/0.75 and 0/1) g/100 g based on polymer, were tested and the introducing of the reinforcers into filmogenic solution were evaluated. Satisfactory dispersion and exfoliation of MMT in bio-nanocomposites were confirmed by changes of crystallinity due to displacement of the characteristic peak from 7.2 ° to 5.2 °. In the same way, films structured with NFBs showed variations of the vibrational frequencies of the molecular arrangements indicating strong bonds between the polymer blends and the reinforcers. By the extrusion from the mixture of homo pellets and masterbatch pellets, from starch/chitosan blends at proportions of (100/0, 75/25 and 50/50) g/100 g, the obtained films have exhibited changes of the crystallinity and the molecular interactions. In relation to mechanical properties, the films presented increase of the tension response as well as the elongation and modulus of elasticity in relation to the reinforcer concentration in each evaluated blend. On the other hand, the formation of polymer blends and the interactions of reinforcers with the matrix changed significantly the three-dimensional network and consequently the water vapor transmission (WVT). Films produced from starch/chitosan 100/0, nanostructured with (0.5 and 1.0) g MMT/100 g, exhibited lower values of WVT 155 e 139) gm-2 d -1, respectively, when compared to commercial products such as Bionolle ™ (PBS) 330 g m-2 d-1) and (PBAT) Ecoflex® (272 g m-2 d-1). In this work, it was possible to develop a promising material with desired characteristics in the biodegradable packaging sector with wide application in the industry.

Neste estudo, investigaram-se mudanças nas propriedades coloidais de uma esmectita pilarizada com polihidroxicátion de alumínio. A solução pilarizante foi preparada mediante gotejamento de solução NaOH 0,4 mol L-1 em solução de AlCl3.6H2O 0,2 mol L-1, a qual foi adicionada à suspensão de argila de 1% m/m. Para avaliar mudanças nas propriedades das argilas, recorreu-se às técnicas de titulação potenciométrica descontínua, análise química total, DRX, FTIR, CTC e isotermas de adsorção/dessorção de N2. Além disso, foram realizados ensaios de adsorção de Cu2+ para avaliar a capacidade de remoção do metal de soluções aquosas pelas argilas pilarizadas e gerar informações relacionadas à interação entre adsorvente e adsorbato. Naturalmente, a argila apresentou espaçamento basal de 1,26 nm, ao passo que as pilarizadas apresentaram valores de 1,78 nm (500 oC) e 1,80 nm (350 oC). Dados da análise química total mostraram se tratar de uma montmorillonita com altos teores de Fe3+, e confirmou o aumento nos teores de Al3+ na estrutura da argila após pilarização. Os valores de área superficial específica e volume de microporos foram maiores para as argilas pilarizadas, enquanto que a CTC foi maior para a argila natural. A titulação potenciométrica mostrou modificação nas curvas de titulação com o processo de pilarização, em que nas argilas pilarizadas surgiram novos sítios de reação. Dentre as equações de adsorção aplicadas, Langmuir, Freundlich e Temkin, a primeira apresentou valores de r2 das equações linearizadas maior para todas as argilas e menor desvio médio (?g%) para argila natural, ao passo que a equação de Temkin mostrou valores de ?g(%) menores para as argilas pilarizadas. Parâmetros termodinâmicos confirmaram que a reação de adsorção de Cu2+ é espontânea para todas as argilas, principalmente para as argilas pilarizadas. Além disso, cálculos baseados em equações de Dubinin-Radushkevich evidenciam que a ligação é fraca entre metal e argila, caracterizando reações de fisissorção. / In this study, an Al-pillared smectite was synthesized and changes in its colloidal properties were investigated. The pillaring solution was prepared adding dropwise adequate volume of NaOH 0,4M to AlCl3.6H2O 0,2M solution. Then, the pillaring solution was added to a 1% w/w clay slurry with constant stirring. Potentiometric titration, chemical analysis, XRD, FTIR, CEC and N2 sorption/dessoption isotherms analysis were done to characterize the changes in clay properties. Moreover, adsorption experiments were carried out in order to evaluate the capacity of the pillared clays to remove Cu2+ from aqueous solution and to characterize the interaction between adsorbent and adsorbate. The natural clay has a basal spacing of 1.26 nm whereas the pillared clays reached 1.78 nm (500 oC) and 1.80 nm (350 oC) after calcination. Chemical analysis revealed that the montmorillonite used has high content of Fe3+ and the increase in the Al3+ amount in the structure of the pillared clays after pillaring process. The surface area and micropore volume were higher for the pillared clays and the CEC was higher for the natural clay. The pillaring process changed the potentiometric titration curves, wherein the pillared clays exhibited new reactive site. Experimental data were fit to Langmuir, Freundlich and Temkin adsorption equations, being the the first one the best (highest r2 value) for all the clays and lower standard deviation (?g%) for the natural clay. On the other hand, Temkin equation exhibited ?g% value lower for the pillared clays. Thermodynamics parameters demonstrate that the Cu2+ adsorption process is spontaneous for all the clays, but with higher values for the pillared materials. In addition, application of the Dubinin-Radushkevich equation revealed that the bond between the metal and the clay are weak, characterizing a physisorption.

Este trabalho descreve a síntese de látices poliméricos híbridos contendo a argila natural Montmorilonita (MMT) por meio da polimerização radicalar controlada via mecanismo de transferência reversível de cadeia por adição-fragmentação (RAFT) em emulsão sem adição de surfatante. Primeiramente, copolímeros anfifílicos com diferentes estruturas e composições, foram preparados por meio da polimerização via RAFT em solução e caracterizados por ressonância magnética nuclear de hidrogênio (RMN 1H) e cromatografia por exclusão de tamanho (SEC). A interação entre os copolímeros sintetizados, chamados de macroagentes RAFT, e a superfície da MMT foi estudada por meio de isotermas de adsorção experimentais, as quais foram ajustadas por modelos teóricos. Os macroagentes RAFT à base de ácido acrílico (AA), acrilato de metil éter poli(etileno glicol) (PEGA) e acrilato de n-butila (BA) apresentaram afinidade pela argila como mostraram as isotermas do \"tipo L\" (Langmuir) obtidas. Os látices híbridos preparados utilizando esses macroagentes RAFT foram analisados por microscopia eletrônica de transmissão em temperatura criogênica (cryo-TEM), que revelou lamelas de MMT decoradas com nanopartículas poliméricas. As isotermas de adsorção dos macroagentes RAFT catiônicos à base de metacrilato de 2-(dimetilamino)etila (DMAEMA), PEGA e BA foram do \"tipo H\" (alta afinidade). Esses macroagentes RAFT possibilitaram a preparação de dispersões estáveis de complexos de MMT/macroagente RAFT, o que foi verificado por espalhamento dinâmico de luz (DLS), e sua utilização na síntese de látices híbridos levou à formação de uma camada polimérica em torno das lamelas de MMT. Os filmes poliméricos nanocompósitos obtidos a partir de látices catiônicos estáveis de poli(metacrilato de metila-co-acrilato de n-butila)/MMT apresentaram melhor estabilidade térmica e melhores propriedades mecânicas do que os filmes poliméricos preparados sem adição de argila como mostraram, respectivamente, os resultados de análise termogravimétrica (TG) e de análise termodinâmico-mecânica (DMA) dos materiais. / This work describes the synthesis of hybrid polymer latexes containing natural Montmorillonite clay (MMT) by reversible addition-fragmentation chain transfer (RAFT)-mediated surfactant-free emulsion polymerization. Firstly, amphiphilic copolymers with different structures and compositions were prepared by RAFT polymerization in solution and characterized by hydrogen nuclear magnetic resonance (1H NMR) and size exclusion chromatography (SEC). The interaction between these copolymers (referred to as macroRAFT agents) and the MMT surface was studied by experimental adsorption isotherms, which were adjusted by theoretical adsorption models. MacroRAFT agents based on acrylic acid (AA), poly(ethylene glycol) methyl ether acrylate (PEGA) and n-butyl acrylate (BA) displayed affinity for MMT as shown by the \"L-type\" (Langmuir) isotherms obtained. The hybrid latexes prepared using these macroRAFT agents were analyzed by transmission electron microscopy at cryogenic temperatures (cryo-TEM), which revealed polymer-decorated MMT platelets. The adsorption isotherms of cationic macroRAFT agents based on 2-(dimethylamino)ethyl methacrylate (DMAEMA), PEGA and BA were of the \"H-type\" (high affinity). These RAFT macroRAFT agents allowed the preparation of stable dispersions of MMT/macroRAFT agents complexes, which was verified by dynamic light scattering analysis (DLS), and their use in the synthesis of hybrid latexes led to the formation of a polymer layer surrounding the MMT platelets. Nanocomposite films obtained from stable cationic latexes of poly(methyl methacrylate-co-n-butyl acrylate)/MMT showed better thermal stability and better mechanical properties than polymer films prepared without addition of clay as shown, respectively, by the results of thermogravimetric analysis (TG) and dynamic mechanical analysis (DMA) of the final materials.

Neste trabalho foi realizado um estudo das interações entre os fungicidas (carbendazim e fuberidazole) e as partículas de argilas SWy-1, SHCa-1 e SYn-1 em suspensão aquosa. Foram determinados através de isotermas de adsorção, espectrofometria de absorção no UV, de emissão de fluorescência e difratometria de raios -X. Os resultados experimentais envolvendo a adsorção foram bem ajustados pelas isotermas de Langmuir, Freundlich e Dubinin-Radushkevich os quais indicam haver alta afinidade entre os fungicidas e as argilas. A capacidade de adsorção foi maior na argila SWy-1 comparada às argilas SHCa-1 e SYn-1, sendo estas ultimas com capacidade de adsorção similares. Foi observada a adsorção dos fungicidas carbendazim e fuberidazole à região interlamelar das partículas de argila, onde ocorre a protonação da molécula dos fungicidas, tornando-a mais estável. Medidas espectrofotométricas, na região do UV, foram efetuadas em função do tempo durante 24 horas. Pela análise dos resultados obtidos, foi possível propor um mecanismo geral para explicar as mudanças espectrais que ocorrem durante a adsorção dos fungicidas nas partículas das argilas em suspensão aquosa. Os resultados de espectrofotometria de absorção no UV do fuberidazole adsorvido nas partículas das argilas e as isotermas de adsorção indicaram que existe uma correlação entre a saturação das argilas e a saturação dos sítios ácidos no processo de adsorção. A intensidade de emissão aumentou significativamente quando o carbendazim foi adsorvido nas argilas SHCa-1 e SYn-1. No entanto, com o fuberidazole observou-se uma diminuição da fluorescência. Nenhuma emissão da fluorescência dos fungicidas carbendazim e fuberidazole adsorvidos nas partículas da argila SWy-1 foi observada devido ao alto teor de ferro. A fotodegradação do carbendazim foi significativamente acelerada quando foi adsorvido nas partículas das argilas. Foi possível observar o aparecimento de novas bandas nos espectros de absorção e de emissão dos fotoprodutos formados na argila que não foram reportados na literatura. / In the present work, studies on the interaction between the fungicides (carbendazim and fuberidazole) and clay particles in aqueous suspension. It has been studied by isotherm adsorption, UV spectroscopy, emission of fluorescence and X-Ray. The results were fitted according the Langmuir, Freundlich and Dubinin- Radushkevich isotherms indicating a high affinity between the fungicide and the clay surfaces. The adsorption capacity in the SWy-1 clay was higher than the SHCa-1 and SYn-1 clays, being these last clays with same adsorption capacity between them. The fungicides can be adsorbed as neutral molecules in the external surfaces as well can be protonated in the interlamellar region of the clay particles. Spectrofothometric measurements in the UV region were taken after different time intervals. A mechanism for the adsorption of fungicides molecules on the clay particles was perceived, leading to a better understanding of the adsorption of this compound on clays. The data obtained by the absorption spectrophotometry in the UV region of the fuberidazole adsorbed in the particle clays and its adsorption isotherms indicated the correlation between the saturation of the clays and the saturation of the acid sites in the adsorption process. When carbendazim was adsorbed on the SHCa-1 and SYn-1 clay particles, the emission intensity increased significantly. However with the fuberidazole was decreased. The emission spectra showed bands attributed to both neutral adsorbed and protonated forms of the fungicides. The emission of the fungicides molecules adsorbed on the particles of SWy-1 clays was almost totally quenched due to the high load of iron. The carbendazim photodegradation process was significantly accelerated when carbendazim was adsorbed on the clay particles compared to the aqueous phase. It was possible to determine the absorption and emission spectra of photoproducts formed on the clay particles, which were not detected in other studies reported in the literature.

O entendimento dos mecanismos de degradação que agem sob os nanocompósitos poliméricos frente ao intemperismo (luz UV, calor, oxigênio, chuva ácida, entre outros), é o ponto chave para o desenvolvimento de novos aditivos e novas aplicações. Para este trabalho a síntese do nanocompósito foi realizada no estado fundido, utilizando-se uma extrusora de dupla rosca. A matriz polimérica utilizada foi o HMS-PP (polipropileno com alta resistência do fundido) sintetizado por irradiação gama e a argila Montmorilonita. Para melhor compatibilização entre a matriz e a nanocarga, foi utilizada o agente compatibilizante andrido maléico. Para os ensaios de envelhecimento ambiental e acelerado em estufa, os corpos de prova foram confeccionados por meio de termoprensagem. A caracterização dos efeitos da adição de argila e do envelhecimento nos nanocompósitos, presupôs o emprego das técnicas de ensaios mecânicos, Calorimetria Diferencial Exploratória (DSC), Termogravimetria (TGA), Espectroscopia no Infravermelho por Transformada de Fourier (FT-IR), Espectrometria de Fluorescêcia de Raios X por Dispersão de Comprimento de Onda (WDXRF), Microscopia Eletrônica de Varredura (MEV), Índice de Fluidez (IF), Difração de Raios-X (DRX) e Espectroscopia de Energia Dispersiva (EDS). Foram ensaiadas amostras com 0,1; 1; 3; 5 e 10% de argila. A amostra com porcentagem de 5% de argila demonstrou uma melhor estabilidade frente ao ensaio de envelhecimento ambiental e no envelhecimento acelerado em estufa. Por outro lado na amostra com maior porcentagem de argila (10%) ocorreu o inverso, sob ensaio ambiental houve maior degradação e sob envelhecimento acelerado em estufa, manteve-se resistente até 56 dias de envelhecimento. Nas porcentagens estudas (menor que ≤ 3%) de argila, pode-se constatar um equilíbrio entre o efeito barreira da argila e a ação dos íons metálicos que aceleram o processo degradativo. / The understanding of degradation mechanism action on the polymer nanocomposites in face of weathering (UV light, heat, acid rain, among others), is the key for development of new additives and new applications. In this work the nanocomposite synthesis was carried in molten state, using twin-screw extruder. The polymer matrix was the HMS-PP (high melt polypropylene) synthesized by gamma irradiation and the nanometric inorganic component was the montmorillonite clay. For better compatibilization between the matrix and clay, it were used maleic anhydride as coupling agent. For environment and in oven accelerated aging assays, the dumbbell samples were prepared under hot pressing. The characterization of clay addition effects and aging effects on the nanocomposites, required the use of techiniques of Differential Scanning Calorimetry (DSC), Thermogravimetry (TGA), Fourier Transformed Infrared Spectroscopy (FT-IR), Xray Fluorescence (WDXRF), Scanning Eletron Microscopy (SEM), Energy Dispersive Spetroscopy (EDS) and mechanical properties. Samples with 0.1; 1; 3; 5; 10 % of clay were tested. The sample with 5% of clay showed better stability on the environmental assay and accelerated aging in oven assay. On the other hand, the sample with higher percent of clay (10%), was more degraded under on environmental aging than under accelerated aging in stove. In this case, became more resistant until 56 days of assay. On the studied concentrations (less than ≤ 3%) of clay, it can be seen an equilibrium between barrier effect and metallic ions action accelerating the degradative process.

Uma das alternativas possíveis para substituir os materiais sintéticos na área de embalagem de alimentos é o desenvolvimento de filmes baseados em biopolímeros. Vários estudos têm demostrado o melhoramento nas propriedades de filmes baseados em biopolímeros, devido à utilização de nanopartículas como reforço. No entanto, as melhorias observadas são ainda limitadas e pode-se considerar que isso é devido a problemas de dispersão das nanopartículas em água, especialmente quando se utiliza a técnica tipo casting. Assim, os objetivos deste projeto foram: A) estudar a qualidade da dispersão de nanopartículas de montemorilhonita em água, e B) estudar o efeito dessas dispersões sobre algumas propriedades físicas e funcionais de filmes de gelatina produzidos com elas. As nanopartículas foram dispersas em água na concentração de 1 g MMT/100 g solução, com três dispositivos: homogeneizador mecânico (UT), moinho coloidal (MC) e processador ultrassônico (US). As dispersões foram analisadas para determinação de tamanho das partículas e potencial zeta, e por microscopia eletrônica de varredura e microscopia de força atômica. Os filmes foram produzidos pela técnica de \"casting\", com 5 g de gelatina/100 g de solução filmogênica e 30 g de glicerol/100g de gelatina. A concentração de nanopartículas foi 0, 1, 3, 5 e 7 g de MMT/100g de gelatina. Os filmes de controle e nanocompósitos produzidos com as dispersões de montemorilhonita foram caracterizados para determinação de espessura, umidade, solubilidade, permeabilidade ao vapor de água, propriedades mecânicas por testes de tração e perfuração, cor e opacidade, brilho, microestrutura por microscopia eletrônica de varredura e microscopia de força atômica, transição vítrea por calorimetria diferencial de varredura, difração de raios-X, espectroscopia de infravermelho com transformada de Fourier e ângulo de contato. O potencial zeta e tamanho médio da partícula foi -53, -40, -47 mV e 377, 289, 395 nm, para as dispersões processadas por UT, US e MC, respectivamente. No geral, os filmes reforçados com montemorilhonita, foram 44% menos brilhantes e foram ligeiramente mais hidrofílicos do que os filmes de controle. A tensão na ruptura aumentou de 22 MPa para filmes de controle até 40 MPa, quando a concentração da montemorilhonita foi de até 5 g de MMT/100g de gelatina. A permeabilidade ao vapor de água não variou nos filmes nanocompósitos. O método de dispersão utilizado teve uma forte influência sobre a qualidade das dispersões, afetando o tamanho da partícula e potencial zeta, com efeito evidente sobre as propriedades físicas dos nanocompósitos. A concentração crítica de montemorilhonita como reforço pareceu estar limitada a 5 g de MMT/100 g de gelatina. / One of the possible alternatives to replace synthetic materials in the area of food packaging is the development of films based on biopolymers. Several studies have demonstrated the improvement in properties of films based on biopolymers due to the use of nanoparticles as reinforcement. However, the observed improvements are still limited and it can be considered that this is due to dispersion problems of nanoparticles in water, particularly when using the casting technique. The aim of this project was to study the quality of the dispersion of nanoparticles (montmorillonite) in water, and to analyze the effect of these dispersions on some physical and functional properties of gelatin films. The nanoparticles were dispersed in water (1 g MMT/100 g solution), with three devices: mechanical homogenizer (UT), colloidal mill (MC) and ultrasonic processor (US). The dispersions were analyzed for determination of particle size and zeta potential, and by scanning electron and atomic force microscopies. Films were produced by casting, with 5 g of gelatin/100 g of film-forming solution and 30 g of glycerol/100 g of gelatin. The nanoparticles concentrations were 0, 1, 3, 5 and 7 g of MMT/100g of gelatin. The control and nanocomposite films were characterized for determination of thickness, moisture, water solubility, water vapor permeability, tensile and puncture mechanical properties, color and opacity, brightness, microstructure by scanning electron microscopy and atomic force microscopy, glass transition temperature by differential scanning calorimetry, X-ray diffraction, infrared spectroscopy with Fourier transform and contact angle. The zeta potential and average particle size was -53, -40, -47 mV and 377, 289, 395 nm; for UT, US and MC dispersions, respectively. In general, the films filled with montmorillonite were 44% less glossy and were slightly more hydrophilic than control film. The maximum tensile strength increased from 22 MPa for control film to 40 MPa when the concentration of montmorillonite was up to 5 g of MMT/100g of gelatin. The water vapor permeability did not change in the nanocomposite films. The dispersion method used had a strong influence on the quality of dispersions; it can affect the particle size and zeta potential, with evident effect on the physical properties of nanocomposites. The critical concentration of montmorillonite as reinforcement seemed to be limited to 5 g of MMT/100 g of gelatin maximum tensile strength increased from 22 MPa for control film to 40 MPa when the concentration of montmorillonite was up to 5 g of MMT/100g of gelatin. The water vapor permeability did not change in the nanocomposite films. The dispersion method used had a strong influence on the quality of dispersions; it can affect the particle size and zeta potential, with evident effect on the physical properties of nanocomposites. The critical concentration of montmorillonite as reinforcement seemed to be limited to 5 g of MMT/100 g of gelatin.