Polyethylene/(organo-montmorillonite) composites modified with ethylene/ methacrylic acid copolymer: Morphology and mechanical properties

Several composites based on high-density polyethylene (PE), organically modified montmorillonite (OMMT) and ethylene/methacrylic acid copolymer (EMAA) were prepared by melt compounding. Three Na(+)-montmorillonites (MMT) of different precedence were modified with hexadecyl trimethyl ammonium chloride in order to change their nature from hydrophilic to organophilic. The composites morphology was examined by XRD, SEM and TEM. Mechanical properties were evaluated under static conditions. A slight reinforcement was achieved only when OMMT was added to PE. When EMAA was added to the composites, it negatively interacted with OMMT, diminishing the interlayer distance of OMMT, changing the composite morphology, as if OMMT was not present in composites, and deteriorating their mechanical properties. (C) 2008 Elsevier Ltd. All rights reserved.

Síntese e fotosensibilização de nanotubos de titanatos

Nesta tese é descrita a preparação de nanotubos de titanatos (TNT) via síntese hidrotérmica alcalina, usando uma nova metodologia que evita a utilização de TiO2 cristalino como precursor. Foi estudada a influência da substituição sódio/protão na estrutura, morfologia e propriedades ópticas dos materiais preparados. Os resultados mostraram que a substituição Na+ → H+ resulta numa redução na distância intercamadas dos TNTs, tendo sido medidos valores entre 1.13±0.03 nm e 0.70±0.02 nm para aquele parâmetro. O comportamento óptico dos TNTs foi estudado na região UV-vis, estimando-se um hiato óptico de energia 3.27±0.03 eV para a amostra com maior teor de sódio enquanto que para a amostra protonada foi determinado um valor de 2.81±0.02 eV. Estes valores mostram que a troca iónica Na+ → H+ teve influência no desvio da banda de absorção dos TNTs para a região do visível próximo. A actividade fotocatalítica dos TNTs na degradação do corante rodamina 6G (R6G) foi posteriormente estudada. Verificou-se que, apesar de a amostra com maior teor de sódio ter sido a que exibiu maior capacidade para adsorver o R6G, foi a amostra protonada que apresentou a actividade catalítica mais elevada na fotodegradação deste corante. Numa segunda fase, e com o objectivo de preparar novos materiais nanoestruturados fotosensíveis, procedeu-se à decoração dos TNTs protonados com semicondutores (SC) nanocristalinos usando um método novo. Para o efeito os TNTs foram decorados com nanocristalites de ZnS, CdS e Bi2S3. Foi estudada a influência do tipo de semicondutor na estrutura, morfologia e propriedades ópticas dos SC/TNTs obtidos. Verificou-se que, para qualquer dos semicondutores usados no processo de decoração, a estrutura dos TNTs é preservada e não ocorre segregação do SC. Verificou-se ainda que a morfologia dos nanocompósitos preparados depende fortemente da natureza do semicondutor. No que respeita ao comportamento óptico destes materiais, foram determinados hiatos ópticos de energia 3.67±0.03 eV, 2.47±0.03 eV e 1.35±0.01 eV para as amostras ZnS/TNT, CdS/TNT e Bi2S3/TNT, respectivamente. Estes resultados mostram que através do processo de decoração de TNTs com semicondutores podem ser preparados materiais nanocompósitos inovadores, com propriedades ópticas novas e/ou pré-definidas numa gama alargada do espectro electromagnético.

Síntese e caracterização de alfa-fosfato de zircônio(IV) contendo agregados de cobre metálico

The alpha-zirconium (IV) hydrogenphosphate (alpha-ZrP) has received great attention in the last years due to its properties like ion exchange, intercalation, ionic conductivity and catalytic activity. This work reports a method to produce metallic copper clusters on alpha-ZrP to be used as catalysts in petrochemical processes. It was found that the solids were non-crystalline regardless of the uptake of copper and the reduction. The specific surface area increased as a consequence of the increase of the interlayer distance to accept the copper ions between the layers. During the reduction, big clusters of copper (0,5-11µ) with different sizes and shapes were produced.

Surface geometry of Cu{531}

We present a combined quantitative low-energy electron diffraction (LEED) and density-functional theory (DFT) study of the chiral Cu{531} surface. The surface shows large inward relaxations with respect to the bulk interlayer distance of the first two layers and a large expansion of the distance between the fourth and fifth layers. (The latter is the first layer having the same coordination as the Cu atoms in the bulk.) Additional calculations have been performed to study the likelihood of faceting by comparing surface energies of possible facet terminations. No overall significant reduction in energy with respect to planar {531} could be found for any of the tested combinations of facets, which is in agreement with the experimental findings.

The surface geometries of the medium and high coverage carbon monoxide structures c(2 × 4)–(2CO) and p(root7- x root7)R19°–(4CO) structure

The surface geometries of the p (root7- x root7)R19degrees-(4CO) and c(2 x 4)-(2CO) layers on Ni {111} and the clean Ni {111} surface were determined by low energy electron diffraction structure analysis. For the clean surface small but significant contractions of d(12) and d(23) (both 2.02 Angstrom) were found with respect to the bulk interlayer distance (2.03 Angstrom). In the c(2 x 4)-(2CO) structure these distances are expanded, with values of d(12) = 2.08 Angstrom and d(23) = 2.06 Angstrom and buckling of 0.08 and 0.02 Angstrom, respectively, in the first and second layer. CO resides near hcp and fcc hollow sites with relatively large lateral shifts away from the ideal positions leading to unequal C-Ni bond lengths between 1.76 and 1.99 Angstrom. For the p(root7- x root7-)R19'-(4CO) layer two best fit geometries were found, which agree in most of their atomic positions, except for one out of four CO molecules, which is either near atop or between bridge and atop. The remaining three molecules reside near hcp and fcc sites, again with large lateral deviations from their ideal positions. The average C Ni bond length for these molecules is, however, the same as for CO on hollow sites at low coverage. The average CNi bond length at hollow sites, the interlayer distances, and buckling in the first Ni layer are similar to the c(2 x 4)(2CO) geometry, only the buckling in the second layer (0.08 Angstrom) is significantly larger. Lateral and vertical shifts of the Ni atoms in the first layer lead to unsymmetric environments for the CO molecules, which can be regarded as an imprint of the chiral p(root7- x root7-)R19degrees lattice geometry onto the substrate.

To what extent can mutual shifting of folded carbonaceous walls in slit-like pores affect their adsorption properties?

We have performed systematic Monte Carlo studies on the influence of shifting the walls in slit-like systems constructed from folded graphene sheets on their adsorption properties. Specifically, we have analysed the effect on the mechanism of argon adsorption (T = 87 K) and on adsorption and separation of three binary gas mixtures: CO2/N2, CO2/CH4 and CH4/N2 (T = 298 K). The effects of the changes in interlayer distance were also determined. We show that folding of the walls significantly improves the adsorption and separation properties in comparison to ideal slit-like systems. Moreover, we demonstrate that mutual shift of sheets (for small interlayer distances) causes the appearance of small pores between opposite bulges. This causes an increase in vapour adsorption at low pressures. Due to overlapping of interactions with opposite walls causing an increase in adsorption energy, the mutual shift of sheets is also connected with the rise in efficiency of mixtures separation. The effects connected with sheet orientation vanish as the interlayer distance increases.

Synthesis, structure, and thermal stability of poly(methyl methacrylate)-co- poly(3-tri(methoxysilyil)propyl methacrylate)/ montmorillonite nanocomposites

The structure and the thermodegradation behavior of both poly(methyl methacrylate)-co-poly(3-tri(methoxysilyil)propyl methacrylate) polymer modified with silyl groups and of intercalated poly(methyl methacrylate)-co-poly(3- tri(methoxysilyil)propyl methacrylate)/Cloisite 15A™ nanocomposite have been in situ probed. The structural feature were comparatively studied by Fourier transform infrared spectroscopy (FTIR), 13C and 29Si nuclear magnetic resonance (NMR), and small angle X-ray scattering (SAXS) measurements. The intercalation of polymer in the interlayer galleries was evidenced by the increment of the basal distance from 31 to 45 Å. The variation of this interlayer distance as function of temperature was followed by in situ SAXS. Pristine polymer decomposition pathway depends on the atmosphere, presenting two steps under air and three under N2. The nanocomposites are more stable than polymer, and this thermal improvement is proportional to the clay loading. The experimental results indicate that clay nanoparticles play several different roles in polymer stabilization, among them, diffusion barrier, charring, and suppression of degradation steps by chemical reactions between polymer and clay. Charring is atmosphere dependent, occurring more pronounced under air. © 2012 Society of Plastics Engineers.

Nanocomposites based on LbL films of polyaniline and sodium montmorillonite clay

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The local environment of Co2+ ions intercalated in vanadium oxide/hexadecylamine nanotubes

Vanadium oxide nanotubes constitute promising materials for applications in nanoelectronics as cathode materials, in sensor technology and in catalysis. In this work we present a study on hybrid vanadium oxide/hexadecylamine multiwall nanotubes doped with Co ions using state of the art x-ray diffraction and absorption techniques, to address the issue of the dopant location within the nanotubes' structure. The x-ray absorption near-edge structure analysis shows that the Co ions in the nanotubes are in the 2+ oxidation state, while extended x-ray absorption fine structure spectroscopy reveals the local environment of the Co2+ ions. Results indicate that Co atoms are exchanged at the interface between the vanadium oxide's layers and the hexadecylamines, reducing the amount of amine chains and therefore the interlayer distance, but preserving the tubular shape. The findings in this work are important for describing Co2+ interaction with vanadium oxide nanotubes at the molecular level and will help to improve the understanding of their physicochemical behavior, which is desired in view of their promising applications.

Effect of van der Waals interaction on the properties of SnS2 layered semiconductor

Nowadays, dispersion correction applied on layered semiconductors is a topic of interest. Among the known layered semiconductors, SnS2 polytypes are wide gap semiconductors with a van der Waals interaction between their layers, which could form good materials to be used in photovoltaic applications. The present work gives an approach to the SnS2 geometrical and electronic characterization using an empirical dispersion correction added to the Perdew–Burke–Ernzerhof functional and subsequent actualization of the electronic charge density using the screened hybrid Heyd–Scuseria–Ernzerhof functional using a density functional code. The obtained interlayer distance and band-gap are in good agreement with experimental values when van der Waals dispersion forces are included.

Influence of different organoclays on the curing, morphology, and dynamic mechanical properties of an epoxy adhesive

The thermal, mechanical, and adhesive properties of nanoclay-modified adhesives were investigated. Two organically modified montmorillonites: Cloisite 93A (C93A) and Nanomer I.30E (I.30E) were used as reinforcement of an epoxy adhesive. C93A and I.30E are modified with tertiary and primary alkyl ammonium cations, respectively. The aim was to study the influence of the organoclays on the curing, and on the mechanical and adhesive properties of the nanocomposites. A specific goal was to compare their behavior with that of Cloisite30B/epoxy and Cloisite15A/ epoxy nanocomposites that we have previously studied. Both C30B and C15A are modified with quaternary alkyl ammonium cations. Differential scanning calorimetry results showed that the clays accelerate the curing reaction, an effect that is related to the chemical structure of the ammonium cations. The three Cloisite/nanocomposites showed intercalated clay structures,the interlayer distance was independent of the clay content. The I.30E/epoxy nanocomposites presented exfoliated structure due to the catalytic effect of the organic modifier. Clay-epoxy nanocompo-sites showed lower glass transition temperature (Tg) and higher values of storage modulus than neat epoxy thermoset, with no significant differences between exfoliated or intercalated nanocom-posites. The shear strength of aluminum joints using clay/epoxy adhesives was lower than with the neat epoxy adhesive. The wáter aging was less damaging for joints with I.30E/epoxy adhesive.

Layered silicate nanocomposites based on various high-functionality epoxy resins. Part II: The influence of an organoclay on the rheological behavior of epoxy prepolymers

The effect of an organically surface modified layered silicate on the viscosity of various epoxy resins of different structures and different functionalities was investigated. Steady and dynamic shear viscosities of the epoxy resins containing 0-10 wt% of the organoclay were determined using parallel plate rheology. Viscosity results were compared with those achieved through addition of a commonly used micron-sized CaCO3 filler. It was found that changes in viscosities due to the different fillers were of the same order, since the layered silicate was only dispersed on a micron-sized scale in the monomer (prior to reaction), as indicated by X-ray diffraction measurements. Flow activation energies at a low frequency were determined and did not show any significant changes due to the addition of organoclay or CaCO3. Comparison between dynamic and steady shear experiments showed good agreement for low layered silicate concentrations below 7.5 wt%, i.e. the Cox-Merz rule can be applied. Deviations from the Cox-Merz rule appeared at and above 10 wt%, although such deviations were only slightly above experimental error. Most resin organoclay blends were well predicted by the Power Law model, only concentrations of 10 wt% and above requiring the Herschel-Buckley (yield stress) model to achieve better fits. Wide-angle X-ray measurements have shown that the epoxy resin swells the layered silicate with an increase in the interlayer distance of approximately 15 Angstrom, and that the rheology behavior is due to the lateral, micron-size of these swollen tactoids.

Estudo da intercalação de fontes de potássio em caulinita pura, com tratamento térmico e ativação ácida

The chemical changes in clay minerals has been widely studied in order to improve its properties for use in various applications. However kaolinite has strong hydrogen bonds between their adjacent layers hindering the process changes in its structure. With the objective to facilitate the process of intercalation monobasic potassium phosphate, bibasic potassium phosphate and potassium acetate we was performed on kaolinite heat treatment at 600 °C and activated acidic with phosphoric acid and 5 to 10 mol L-1. The samples they were characterized by energy dispersive spectroscopy (EDS), X-Ray Diffraction (XRD), Infrared Spectroscopy Fourier Transform (FTIR) and Thermogravimetric Analysis (TG) and Differential Thermal Analysis (DTG) and the superficial and textural changes the samples with heat treatment and acid activation they were characterized by scanning electron microscopy (SEM) and Textural Analysis of Adsorption/desorption N2. With the help of the techniques found that, the heat treatment becomes more susceptible to acid activation kaolinite making the samples with two treatments show larger amounts of phosphorus. It was also found that bibasic potassium phosphate binds more strongly the structure of kaolinite by having a structure with two-coordinating oxygens and intercalation with potassium acetate in acid-activated kaolin increases the interlayer distance of the kaolinite and the intercalation occurs with higher response index (RI) for samples with acid activation to 5 mol /L.

Tree structure and richness in an Atlantic Forest fragment: distance from anthropogenic and natural edges

Approximately 7.2% of the Atlantic rainforest remains in Brazil, with only 16% of this forest remaining in the State of Rio de Janeiro, all of it distributed in fragments. This forest fragmentation can produce biotic and abiotic differences between edges and the fragment interior. In this study, we compared the structure and richness of tree communities in three habitats - an anthropogenic edge (AE), a natural edge (NE) and the fragment interior (FI) - of a fragment of Atlantic forest in the State of Rio de Janeiro, Brazil (22°50'S and 42°28'W). One thousand and seventy-six trees with a diameter at breast height > 4.8 cm, belonging to 132 morphospecies and 39 families, were sampled in a total study area of 0.75 ha. NE had the greatest basal area and the trees in this habitat had the greatest diameter:height allometric coefficient, whereas AE had a lower richness and greater variation in the height of the first tree branch. Tree density, diameter, height and the proportion of standing dead trees did not differ among the habitats. There was marked heterogeneity among replicates within each habitat. These results indicate that the forest interior and the fragment edges (natural or anthropogenic) do not differ markedly considering the studied parameters. Other factors, such as the age from the edge, type of matrix and proximity of gaps, may play a more important role in plant community structure than the proximity from edges.

Testes de desempenho aeróbio relacionados a intensidades de corrida em treinamento e competição para fundistas de alto rendimento = : Aerobic performance tests related to training and competition running intensities for high performance distance runners

Universidade Estadual de Campinas . Faculdade de Educação Física