Estudo da mobilidade molecular das blendas aPA/SAN/MMA-MA usando relaxação dielétrica

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Obtenção e caracterização do sistema compósito alginato de sódio-dióxido de titânio em formas de pó e de membrana

The alginates are copolymers of 1→4-linked β-D-mannuronic acid (M) and α-Lguluronic acid (G) residues that are arranjed in a block structure along a linear chain. Titanium dioxide, TiO2, is a ceramic material and can exist in three distinct crystallography forms: anatase, brookite and rutile. composites of organic and inorganic materials have better properties than the components alone. Thus, this study aims to synthesize, characterize and analyze the composite NaAlg-TiO2 in the form of powder and film. The synthesis of composite powders was performed using the sol-gel process and obtain the composite film was performed using the slow evaporation process, then the composites were analyzed by infrared spectroscopy, fluorescence x ray, thermal analysis, attenuated total reflection (ATR), x ray diffraction and impedance spectroscopy. The X ray diffraction patterns of composite powders show that with increasing calcination temperature, there were no complete transition of rutile-anatase crystalline phase, since at all temperatures studied (300, 500, 700, 900 and 1100ºC) were observed peaks of anatase phase. Thermal analysis shows that at 400°C caused the decomposition of sodium alginate in sodium carbonate and above 600°C, we observe an exothermic peak related to the decomposition of sodium carbonate and in the presence of titanium dioxide becomes sodium titanate. The XRD results confirm the formation of sodium carbonate at 700ºC and the formation sodium titanate in the temperature range 900-1100ºC. The sodium titanate influenced the electrical properties of the material, because with increasing temperature there was a decrease in conductivity, probably due to the creation of Ti vacancies, since the sodium can induce the reduction of surface Ti4+ ions into Ti3+ species. The infrared spectra of the composites in the form of powder and film showed a small shift in the bands compared to the spectrum of pure alginate, indicating that these shifts, even small ones, have evidence of miscibility between the polymer and ceramic material

Avaliação das propriedades físico-químicas de sistemas a base de carboximetilcelulose e poli (N-isopropilacrilamida) em soluções aquosas para aplicação na indústria do petróleo

Sustainable development is a major challenge in the oil industry and has aroused growing interest in research to obtain materials from renewable sources. Carboxymethylcellulose (CMC) is a polysaccharide derived from cellulose and becomes attractive because it is water-soluble, renewable, biodegradable and inexpensive, as well as may be chemically modified to gain new properties. Among the derivatives of carboxymethylcellulose, systems have been developed to induce stimuli-responsive properties and extend the applicability of multiple-responsive materials. Although these new materials have been the subject of study, understanding of their physicochemical properties, such as viscosity, solubility and particle size as a function of pH and temperature, is still very limited. This study describes systems of physical blends and copolymers based on carboxymethylcellulose and poly (N-isopropylacrylamide) (PNIPAM), with different feed percentage compositions of the reaction (25CMC, 50CMC e 75CMC), in aqueous solution. The chemical structure of the polymers was investigated by infrared and CHN elementary analysis. The physical blends were analyzed by rheology and the copolymers by UV-visible spectroscopy, small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. CMC and copolymer were assessed as scale inhibitors of calcium carbonate (CaCO3) using dynamic tube blocking tests and chemical compatibility tests, as well as scanning electron microscopy (SEM). Thermothickening behavior was observed for the 50 % CMC_50 % PNIPAM and 25 % CMC_75 % PNIPAM physical blends in aqueous solution at concentrations of 6 and 2 g/L, respectively, depending on polymer concentration and composition. For the copolymers, the increase in temperature and amount of PNIPAM favored polymer-polymer interactions through hydrophobic groups, resulting in increased turbidity of polymer solutions. Particle size decreased with the rise in copolymer PNIPAM content as a function of pH (3-12), at 25 °C. Larger amounts of CMC result in a stronger effect of pH on particle size, indicating pH-responsive behavior. Thus, 25CMC was not affected by the change in pH, exhibiting similar behavior to PNIPAM. In addition, the presence of acidic or basic additives influenced particle size, which was smaller in the presence of the additives than in distilled water. The results of zeta potential also showed greater variation for polymers in distilled water than in the presence of acids and bases. The lower critical solution temperature (LCST) of PNIPAM determined by DLS corroborated the value obtained by UV-visible spectroscopy. SAXS data for PNIPAM and 50CMC indicated phase transition when the temperature increased from 32 to 34 °C. A reduction in or absence of electrostatic properties was observed as a function of increased PNIPAM in copolymer composition. Assessment of samples as scale inhibitors showed that CMC performed better than the copolymers. This was attributed to the higher charge density present in CMC. The SEM micrographs confirmed morphological changes in the CaCO3 crystals, demonstrating the scale inhibiting potential of these polymers

Interaction between Pluronic F127 and Dioctadecyldimethylammonium Bromide (DODAB) Vesicles Studied by Differential Scanning Calorimetry

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

The Interaction Between N-Isopropylacrylamide-Acrylic Acid-Ethyl Methacrylate Thermosensitive Polymers and Cationic Surfactants

The interaction between cationic surfactants and isopropylacrylamide-acrylic acid-ethyl methacrylate (IPA:AA:EMA) terpolymers has been investigated using steady-state fluorescence and spectrophotometric measurements to assess the effect of the polymer composition on the aggregation process and terpolymers' thermosensitivities. Micropolarity studies using pyrene show that the interaction of cationic surfactants with IPA:AA:EMA terpolymers occurs at surfactant concentrations much smaller than that observed for the pure surfactant in aqueous solution. The critical aggregation concentration (CAC) values decrease with both the hydrocarbon length of the surfactant and the content of ethyl methacrylate. These results were interpreted as a manifestation of the increasing contribution of attractive hydrophobic and electrostatic forces between negatively charged polymer chains and positively charged surfactant molecules. The increase of ethyl methacrylate in the copolymers lowers the CAC due to the larger hydrophobic character of the polymer backbone. The cloud point determination reveals that the lower critical solution temperatures (LCST) depend strongly on the copolymer composition and surfactant nature. The binding of surfactants molecules to the polymer chain screens the electrostatic repulsion between the carboxylic groups inducing a conformational transition and the dehydration of the polymer chain.

An investigation of cadmium(II) and nickel(II) adsorption by chitin graft covolymer

Chitin hydrogels of poly(vinylpyrrolidone) (VP) were prepared by means of the hydrogen peroxide graft copolymerization process. The effect of the VP grafted chain on water diffusion through the biopolymer was studied. Fourier transform infrared spectra of the VP-g-Ch showed an increase in the intensities of the hydroxyl and carbonyl stretching bands indicating a reduction in the hydrogen bonding of chitin. An investigation was undertaken regarding the adsorption of nickel(II) and cadmium(II) ions from aqueous solutions by the VP grafted chitin and the effects of the grafting degree on the Cd2+ and Ni2+ sorption were studied. The Cd2+ and Ni2+ adsorption equilibrium data correlate well with the Freundlich equation. The results indicate that the Ch-g-VP graft copolymer under investigation is a potentially powerful chelating material that can be employed for Ni2+ and Cd2+ ion removal from wastewater effluents. (C) 2004 Wiley Periodicals, Inc.

Linear low density polyethylene (LLDPE) from ethylene using Tp(Ms)NiCl (Tp(Ms) = hydridotris(3-mesitylpyrazol-1-yl)) and CP2ZrCl2 as a tandem catalyst system

Linear low density polyethylene (LLDPE) with different branching contents were prepared from ethylene, without the addition of alpha-olefin comonomer, using a combination of catalyst precursors {Tp(Ms)}NiCl (1) (Tp(Ms) = hydridotris(3-mesitylpyrazol-1-yl)) and Cp2ZrCl2 (2) activated with MAO/TMA (1:1) in toluene at 0degreesC and by varying the nickel loading mole fraction (x(Ni)). The polymerization results showed that the turnover frequencies are strongly dependent on the x(Ni) varying from 6.6 x 10(3) to 32.1 x 10(3) mol[C2H4]/mol[Zr] h. The C-13 NMR spectra of the copolymers showed that the branch contents of the polymers increase as the x(Ni) increase in the medium promoting the production of polymers with a wide range of melting point (T-m) (C) 2004 Elsevier B.V. All rights reserved.

MONTE-CARLO SIMULATION OF POLYAMPHOLYTE CHAINS

Polyampholyte copolymers containing both positive and negative monomers regularly dispersed along the chain were studied. The Monte Carlo method was used to simulate chains with charged monomers interacting by screened Coulomb potential. The neutral polyampholyte chains collapse due to the attractive electrostatic interactions. The nonneutral chains are in extended conformations due to the repulsive polyelectrolyte effects that dominate the attractive polyampholyte interactions. The results are in good agreement with experiment.

On the equivalence of the mechanisms governing switching and hysteresis phenomena

The nucleation and growth model, which is usually applied to switching phenomena, is adapted for explaining surface potential measurements on the P(VDF-TrFE) (polyvinylidene fluoride-trifluoroethylene) copolymer obtained in a constant current corona triode. It is shown that the growth is one-dimensional and that the nucleation rate is unimportant, probably because surface potential measurements take much longer than the switching ones. The surface potential data can therefore be accounted for by a growth model in which the velocity of growth varies exponentially with the electric field. Since hysteresis loops can be obtained from surface potential measurements, it is suggested that similar mechanisms can be used when treating switching and hysteresis phenomena, provided that account is taken of the difference in the time scale of the measurements.

Photochemical determination of the interactions between surfactants and polyelectrolytes

The interaction of polyelectrolytes with oppositely charged ionic surfactants was studied at low surfactant concentrations using photochemical bound and free probes. Free probes migrate to initially formed pre-aggregates in systems with high charge- density polyelectrolytes, giving rise to excimer emission. For these systems the initial aggregation process seems to be due to electrostatic interactions. For larger surfactants or copolymers containing larger proportions of neutral monomer that interactions are of hydrophobic nature.

Acrylonitrile-butadiene-styrene toughened nylon 6: The influences of compatibilizer on morphology and impact properties

Polymer alloys have been used as an alternative to obtain polymeric materials with unique physical properties. Generally, the polymer mixture is incompatible, which makes it necessary to use a compatibilizer to improve the interracial adhesion. Nylon 6 (PA6) is an attractive polymer to use in engineering applications, but it has processing instability and relatively low notched impact strength. In this study, the acrylonitrile-butadiene-styrene (ABS) triblock copolymer was used as an impact modifier for PA6. Poly(methyl methacrylate-co-maleic anyhydride) (MMA-MA) and poly(methyl methacrylate-co-maleic methacrylate) (MMA-GMA) were used as compatibilizers for this blend. The morphology and impact strength of the blends were evaluated as a function of blend composition and the presence of compatibilizers. The blends compatibilized with maleated copolymer exhibited an impact strength up to 800 J/m and a morphology with ABS domains more efi8ciently dispersed. Moderate amounts of MA functionality in the compatibilizer (∼5%) and small amounts of compatibilizer in the blend (∼5%) appear sufficient to improve the impact properties and ABS dispersion. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87.

Morphology of Nylon 6/Acrylonitrile-Butadiene-Styrene Blends Compatibilized by a Methyl Methacrylate/Maleic Anhydride Copolymer

The morphologies of nylon 6/acrylonitrile-butadiene-styrene blends compatibilized with a methyl methacrylate/maleic anhydride copolymer, with 3-20 wt % maleic anhydride, were examined by transmission electron microscopy. Some staining techniques were employed for identifying the various phases. The binary blends were immiscible and exhibited poor mechanical properties that stemmed from the unfavorable interactions among their molecular segments. This produced an unstable and coarse phase morphology and weak interfaces among the phases in the solid state. The presence of the copolymer in the blends clearly led to a more efficient dispersion of the acrylonitrile-butadiene-styrene phase and consequently optimized Izod impact properties. © 2003 Wiley Periodicals, Inc.

Effect of compatibilizer in acrylonitrile-butadiene-styrene toughened nylon 6 blends: Ductile-brittle transition temperature

The ductile-brittle transition temperatures were determined for compatibilized nylon 6/acrylonitrile-butadiene-styrene (PA6/ABS) copolymer blends. The compatibilizers used for those blends were methyl methacrylate-co-maleic anhydride (MMA-MAH) and MMA-co-glycidyl methacrylate (MMA-GMA). The ductile-brittle transition temperatures were found to be lower for blends compatibilized through maleate modified acrylic polymers. At room temperature, the PA6/ABS binary blend was essentially brittle whereas the ternary blends with MMA-MAH compatibilizer were supertough and showed a ductile-brittle transition temperature at -10°C. The blends compatibilized with maleated copolymer exhibited impact strengths of up to 800 J/m. However, the blends compatibilized with MMA-GMA showed poor toughness at room temperature and failed in a brittle manner at subambient temperatures.

Thermal properties of nylon6/ABS polymer blends: Compatibilizer effect

Nylon6/ABS binary blends are incompatible and need to be compatibilized to achieve better performance under impact tests. Poly(methyl methacrylate/maleic anhydride) (MMA-MA) is used in this work to compatibilize in situ nylon6/ABS immiscible blends. The MA functional groups, from MMA-MA copolymers, react with NH2 groups giving as products nylon molecules grafted to MMA-MA molecules. Those molecular species locate in the nylon6/ABS blend interfacial region increasing the local adhesion. MMA-MA segments are completely miscible with the SAN rich phase from the ABS. The aim of this work is to study the effects of ABS and compatibilizing agent on the melting and crystallization of nylon6/ABS blends. This effect has been investigated by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). Incorporation of this compatibilizer and ABS showed little effect on the melting behavior of the PA6 crystalline phase, in general. DMTA analysis confirmed the system immiscibility and showed evidence of compatibility between the two phases, nylon6 and ABS, produced by MMA-MA copolymer presence. The nylon6/ABS blend morphology, observed by transmission electron microscopy (TEM), changes significantly by the addition of the MMA-MA compatibilizer. A better dispersion of ABS in the nylon6 phase is observed. © 2004 Kluwer Academic Publishers.

Thermoanalytical study of praziquantel-loaded PLGA nanoparticles

Polymeric nanoparticles have received great attention as potential controlled drug delivery systems. Biodegradable polymers has been extensively used in the development of these drug carriers, and the polyesters such as polylactic acid, polyglycolic acid and their copolymers as poly-lactide-co- glycolide are the most used, considering its biocompatibility and biodegradability. Thermal analysis techniques have been used for pharmaceutical substances for more than 30 years and are routine methods for screening drug-excipient interactions. The aim of this work is to use thermal analysis to characterize PLGA nanoparticles containing a hydrophobic drug, praziquantel. The results show that the drug is in an amorphous state or in disordered crystalline phase of molecular dispersion in the PLGA polymeric matrix and that the microencapsulation process did not interfere with the chemical structure of the polymer, mantaining the structural drug integrity.