NMR study of ion-conducting organic-inorganic nanocomposites poly(ethylene glycol) - Silica - LiClO4

Hybrid organic-inorganic ionic conductors, also called ormolytes, were obtained by dissolution of LiClO4 into silica/poly(ethylene glycol) matrices. Solid-state nuclear magnetic resonance (NMR) was used to probe the inorganic phase structure (Si-29) and the effects of the temperature and composition on the dynamic behavior of the ionic species (Li-7) and the polymer chains (H-1 and C-13). The NMR results between -100 and +90 degrees C show a strong correlation with ionic conductivity and differential scanning calorimetry experiments. The results also demonstrate that the cation mobility is assisted by segmental motion of the polymer, which is in agreement with the results previously reported for pure poly(ethylene oxide), PEG, electrolytes.

Gelation of siloxane-poly(oxypropylene) composites

The viscoelastic properties of siloxane-poly(oxypropylene) (PPO) nanocomposites prepared by the sol-gel process has been analyzed during gelation by dynamic rheological measurements. The changes of storage and loss moduli, complex viscosity and phase angle has been measured as a function of time showing the newtonian viscosity of the sol in the initial step of gelation, and its progressive transformation to a viscoelastic gel. The rheologic properties have been correlated to mass fractal, nearly linear growth models and percolation theory. This study, completed by quasi-elastic light scattering and Si-29 solid state nuclear magnetic resonance measurements, shows that the mechanisms of gelation of siloxane-PPO hybrids depend on the molecular weight of the polymer and on the pH of the hybrid sol. For hybrids prepared in acid medium, a polymerization involving silicon reactive species located at the extremity of the polymer chains and presenting a functionality f = 2 occurs, forming a fractal structure during the first stage of sol-gel transition. For samples prepared under neutral pH, the fractal growth is only observed for hybrids containing short polymer chains (M-w similar to 130 gmol(-1)). The fractal dimensionality determined from the change in the rheological properties, indicates that the fractal growth mechanism changes from reaction-limited to diffusion-limited aggregation when the molecular weight of the PPO increases from 130 to 4000 gmol(-1) and as catalyst conditions change from acidic to neutral. Near the gel point, these hybrid gels have the typical scaling behavior expected from percolation theory. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Effect of cold plasma treatment on mechanical properties of PET/PMMA composites

Mechanical strength of polyethylene terephthalate (PET) fibres and polymethyl methacrylate (PMMA) matrix composites were studied with particular interest on the effects of oxygen and argon plasma treated fibres. PET. fibres were treated in a radio frequency plasma reactor using argon or oxygen for different treatment times to increase the interface adhesion. Fibre volume fraction was measured through digital image analysis. Elastic moduli resulted between 3 GPa for untreated to 6 GPa for treated composites. Tensile tests on PET fibres showed that plasma treatment caused a decrease in average tensile strength compared to untreated fibres. Fracture analysis confirmed the increase in interfacial adhesion due to plasma treatment. (c) 2004 Elsevier Ltd. All rights reserved.

Development of alpha-SiAlON-SiC ceramic composites by liquid phase sintering

In this work, in situ alpha-SiAlON-SiC ceramic composites were obtained,by, liquid phase sintering, using SiC as reinforcement. Different beta-SiC powder contents (0-20 wt.%), were added to Si3N4-AlN-RE2O3. powder mixtures, and compacted by cold isostatic pressing. The samples were sintered at 1950 degrees C for 1 h, in N-2 atmosphere. Sintered: samples were characterized by relative density, weight loss, X-ray diffraction and scanning electron microscopy. Furthermore, mechanical properties such as hardness and fracture toughness were determined by Vickers indentation method. Lattice parameters of the alpha' phase did not considerably change with increase of SiC content. However, morphology, average grain size and aspect ratio of the alpha' phase were considerably changed with increase of the SiC content. These behavior influences significantly the mechanical properties of this hard ceramic composite. (C) 2006 Elsevier Ltd. All rights reserved.

Structural study of composites of aerosil fumed silica and tetraethoxysilane-derived sonogels

Composites of aerosil fumed silica and tetraethoxysilane-derived sonogel were prepared by changing the aerosil content between 0 and 30wt% with respect to the silica content in the original tetraethoxysilane (TEOS). The structural characteristics were studied by density and Vickers microhardness measurements and analyzed by means of small-angle X-ray scattering (SAXS). The structure of the composite aerosil/TEOS-derived sonogel can be described as inclusions of the aerosil particles embedded in the matrix of the TEOS-derived sonogel, forming an aerosil/matrix interfacial surface inside the composite. The weakening of the bonding of aerosil/matrix interface, as suggested by the reported decrease in microhardness, increases the fracture toughness of the composite. The additive effect of the aerosil particles on the structure of the sonogel accounts for the increase of the bulk density and reduction of the specific surface of the composite. Some internal structure associated with the microclusters making up the sonogels is apparent from systematic deviations from Porod's law found in the system with small aerosil contents. (c) 2005 Elsevier B.V. All rights reserved.

Oxygen plasma treatment of sisal fibers and polypropylene: Effects on mechanical properties of composites

Polypropylene powder and sisal fibers were oxygen plasma treated, and the mechanical properties of their composites were tested. Two main effects were investigated: the incorporation of oxygen polar groups in the polypropylene surface and the surface degradation and chain scission of both polypropylene and sisal fibers. Prior to these treatments, three reactor configurations were tested to investigate the best condition for both effects to occur in PP film. Results showed that polypropylene-cellulose adhesion forces are about an order of magnitude higher for PP film treatments at 13.56 MHz than at 40 kHz owing to much higher chain scission at lower frequencies, although it probably also occurs at high frequency and high power. Polypropylene powder treated with oxygen plasma in optimum conditions for polar group incorporation did not result in improvement in any composite mechanical property, probably owing to the polymer melting. Sisal fibers and PP powder treated In conditions of surface degradation did not improve flexural or tensile properties but resulted in higher impact resistance, comparable to the improvement obtained with the addition of compatibilizer.

Structure, microstructure and dielectric properties of 100-x(Bi0.5Na0.5)TiO3-x[SrTiO3] composites ceramics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electrical relaxation in proton conductor composites based on (NH4)H2PO4/TiO2

We report on electrical relaxation measurements of (1-x)NH4H2PO4-xTiO(2) (x = 0.1) composites by admittance spectroscopy, in the 40-Hz-5-MHz frequency range and at temperatures between 303 and 563 K. Simultaneous thermal and electrical measurements on the composites identify a stable crystalline phase between 373 and 463 K. The real part of the conductivity, sigma', shows a power-law frequency dependence below 523 K, which is well described by Jonscher's expression sigma' = sigma(0)(1 + (omega/omega(p))(n)), where sigma(0) is the dc conductivity, omega(p)/2 pi = f(p) is a characteristic relaxation frequency, and n is a fractional exponent between 0 and 1. Both sigma(0) and f(p) are thermally activated with nearly the same activation energy in the II region, indicating that the dispersive conductivity originates from the migration of protons. However, activation energies decrease from 0.55 to 0.35 eV and n increases toward 1.0, as the concentration of TiO2 nanoparticles increases, thus, enhancing cooperative correlation among moving ions. The highest dc conductivity is obtained for the composite x = 0.05 concentration, with values above room temperature about three orders of magnitude higher than that of crystalline NH4H2PO4 (ADP), reaching values on the order of 0.1 (Omega cm)(-1) above 543 K.

The ferromagnetic behaviour of conducting polymers revisited

The magnetic properties of doped pellets of poly(3-methylthiophene) showing room temperature ferromagnetic behaviour have been discussed in a previous article. The magnetic behaviour was attributed to a weak ferromagnetic phase, due to the superexchange interaction of polarons via the dopant anions. The Dzialoshinsky-Morya interaction among canted spins was proposed to explain the ferromagnetism. In this article the main conclusions of that work concerning the magnetic behaviour are revised. The basic assumption now is that the magnetic moments are spin 1/2 polarons that can interact antiferromagnetically and/or ferromagnetically. In the small crystalline regions of the polymer, which are identified with the polymer portion that remains ferromagnetic at room temperature, the interaction gives rise to S = 0 and 1 bipolarons and the S = 1 triplet state is lower in energy. In the disordered region, disorder will prevent the complete S = 1 and 0 coupling and bands of polarons ferromagnetically and antiferromagnetically coupled will appear. Using this approach, all the magnetization data can be qualitatively explained, as well as the electron spin resonance data.

New strategies in the preparation of exfoliated thermoplastic starch-montmorillonite nanocomposites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Alternatives Panels from Waste Plastics Reinforced With Fibers of Pupunha Palm for Use in Civil Construction and Furniture Industry

In order to cooperate in minimizing the problems of the current and growing volume of waste, this work aims at the production of panels made from industrial waste -thermoplastic (Polypropylene - PP; Polyethylene - PE and Acrylonitrile Butadiene Styrene - ABS) reinforced with agro-industrial waste - pupunha palm waste (shells and sheaths). The properties of the panels were evaluated: density, thickness swelling, water absorption and moisture content. It was used the ASTM D1037; EN 317; and ANSI A208.1 standards regarding particle boards. The best results in physical tests were treatments 1 (100% waste plastic), 6 (60% plastic waste and 40% waste of pupunha) and 7 (70% waste plastic and 30% waste of pupunha). The best results in the mechanical tests were treatments 3 (30% de residuos plasticos e 70% de residuos da pupunha), 4 (40% de residuos plasticos c 60% de residuos da pupunha) and 5 (50% de residuos plasticos e 50% de residuos da pupunha). For mechanical tests it was concluded that the results of modulus of rupture and of modulus of elasticity the best treatments were those with more fibers. In the tensile tests perpendicular to the surface, it is clear that using more waste plastics leads to the best results. It was concluded that the waste can be used as raw material for the production of alternative materials mainly in civil construction and furniture industries, and it can be employed in urban or rural environment, given the concept of eco-efficient products.

Magnetic field dependent magnetization of a conducting plasticized poly(aniline) film

We report magnetic data of free standing films of poly( aniline) (PANI) protonated with a plasticizing di-ester of succinic acid. The data have been obtained using the electron spin resonance (ESR) technique at two different frequencies, X-band (9.4 GHz) and Q-band ( 34 GHz), on one hand, and by magnetization measurements in broad ranges of temperatures and magnetic fields on the other hand. All the data can be explained assuming a transition as a function of temperature from delocalized magnetic moments in the valence band to localized positive polarons in several antiferromagnetically correlated bands. By increasing the magnetic field, the magnetic properties are affected in several ways. An intra-band admixture of states occurs; it contributes to increase the spins' localization and finally promotes an antiferromagnetic-metamagnetic transition.

Luminescent nano-composites generated from a spray

The spray-pyrolysis (SP) synthesis technique has been employed to obtain SiO2:Eu3+ and gamma-AlOOH:Eu3+, It was possible to obtain sub-micrometric spherical particles of SiO2 with luminescent Eu3+ ions bonded to the silica surface or embedded in amorphous silica beads, by controlling the synthesis and annealing process. Boehmite y-AlOOH doped with Eu3+ nanoparticles were synthesized by SP at moderate temperature (200 degrees C) with Eu3+ ions bonded to the surface hydroxyls of the boehmite nanocrystals. Luminescent nanocomposites were obtained by controlled reaction of gamma-AlOOH:Eu3+ nanocrystals with ASN (asparagine). In these nano-composites, the Eu3+ are held at the surface of the boehmite nanocrystals and partially shielded from interactions with additional luminescence quenchers (hydroxyl groups, water molecules). (C) 2008 Elsevier B.V. All rights reserved.