Dielectric behavior of PVDF/POMA blends that have a low doped POMA content

The real (ε′) and imaginary (ε″) components of the complex permittivity of blends of PVDF [poly(vinylidene fluoride)] with POMA [poly(o‐methoxyaniline)] doped with toluenosulfonic acid (TSA) containing 1, 2.5, and 5 wt % POMA–TSA were determined in the frequency interval between 10² and 3 × 10⁶ Hz and in the temperature range from ?120 up to 120°C. It was observed that the values of ε′ and ε″ had a greater increase with the POMA–TSA content and with a temperature in the region of frequencies below 10 kHz. This effect decreased with frequency and it was attributed to interfacial polarization. This polarization was caused by the blend heterogeneity, formed by conductive POMA–TSA agglomerates dispersed in an insulating matrix of PVDF. The equation of Maxwell–Garnett, modified by Cohen, was used to evaluate the permittivity and conductivity behavior of POMA–TSA in the blends. A strong decrease was observed in POMA–TSA conductivity in the blend, which was bigger the lower the POMA–TSA content in the blend. This decrease could have been caused either by the POMA dedoping during the blend preparation process or by its dispersion into the insulating matrix. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 752–758, 2003     

Filters of implication reducts of basic algebras

Since basic algebras were introduced as a common generalization of MV-algebras and orthomodular lattices, their implication reducts form a common generalization of BCK-algebras and orthoimplication algebras introduced by J. C. Abbott. As shown in our previous paper, congruences in these implication reducts are in a one-to-one correspondence with their kernels. Hence, to characterize congruences it is enough to describe its kernels which is done in the paper.     

Modification of porous copolymers network based on acrylonitrile

Summary The preparation of a chelating ion-exchange network based on acrylonitrile was carried out by chemical modification with hydroxylamine. The beads of resin were synthesized by aqueous suspension copolymerization of acrylonitrile (AN), styrene (STY) and divinylbenzene (DVB). The influence of diluent used in the suspension polymerization on the structure of the resulting copolymers was evaluated. The diluents employed were heptane (HEP), toluene (TOL) and anisole (ANI). It was found that the AN incorporation into copolymer structure was dependent on the diluent used. Conversion of nitrile groups into the amidoxime was conducted by treatment with hydroxylamine under alkaline solution. The resins were characterized by apparent density, surface area, average pore diameter, elemental analysis (CHN), FTIR and optical microscopy. Based on the results obtained, it was possible to control the porosity by diluent employed in the synthesis and to modify chemically a resin containing nitrile groups by hydroxylamine reaction. Received: 6 October 2001/Revised version: 2 April 2002/ Accepted: 11 April 2002     

The effect of H2 treatment on the activity of activated carbon for the oxidation of organic contaminants in water and the H2O2 decomposition

In this work, hydrogen peroxide reactions, i.e. H₂O₂ decomposition and oxidation of organics in aqueous medium, were studied in the presence of activated carbon. It was observed that the carbon pre-treatment with H₂ at 300, 500, 700 and 800 °C resulted in an increase in activity for both reactions. The carbons were characterized by BET nitrogen adsorption, thermogravimetric analyses (TG), temperature programmed reduction (TPR), electron paramagnetic resonance (EPR), iodometric titration and determination of the acid/basic sites. TPR experiments showed that activated carbon reacts with H₂ at temperatures higher than 400 °C. The treatment produces a slight increase in the surface area. EPR analyses indicate the absence of unpaired electrons in the carbon. Iodometric titrations and TG analyses suggested that the treatment with H₂ generates reduction sites in the carbon structure, with concentration of approximately 0.33, 0.53, 0.59, 0.65 and 0.60 mmol/g for carbons treated at 25, 300, 500, 700 and 800 °C, respectively. It was also observed the appearance of basic sites which might be related to the reduction sites. It is proposed that these reducing sites in the carbon can activate H₂O₂ to generate HO^* radicals which can lead to two competitive reactions, i.e. the hydrogen peroxide decomposition or the oxidation of organics in water.     

Synthesis, characterization and crystal structure of a novel thiocyanate–ruthenium(II) complex

The cis-[Ru(dppb)(Me-bipy)(NCS)₂], dppb = 1,4-bis (diphenylphosphino)butane, Me-bipy = 4,4′-dimethyl-2,2′-bipyridine, and NCS = thiocyanate, was synthesized and characterized by spectroscopic and electrochemical techniques and its structure was determined by crystal X-ray analysis. The crystal structure reveals that the coordination geometry around the Ru(II) center is distorted octahedron where two molecules of thiocyanate are bonded to the ruthenium through nitrogen atom in cis orientation. The half-wave formal potential value E_1/2 = 0.8 V (versus Ag/AgCl) observed is considerable higher than that for the cis-[RuCl₂(dppb)(Me-bipy)] complex, E_1/2 = 0.6 V (versus Ag/AgCl), well illustrating the strong π-acceptor effect the NCS ligand toward the backbonding interaction with the Ru(II) metal center. The MLCT absorption bands of the thiocyanate complex present a higher molar absorptivity (about 12%) compared with the cis-[RuCl₂(dppb)(Me-bipy)] complex, in the same experimental conditions. These properties make the complex potentially promising for the photosensitization process.     

Influence of anionic form on thermooxidation of TMAHP–cellulose

With the help of DTA, DTG elementary analysis of carbonized residues and ESR spectroscopy the influence of anionic form on thermooxidation of trimethylammoniumhydroxyprophyl (TMAHP)–cellulose was studied. At 300°C the percentage of carbon in carbonized residue thermolyzed in oxidative atmosphere is higher than for the sample degraded in inert atmosphere. The percentage of hydrogen decreases simultaneously. The concentration of free radicals in thermolyzed residue also increases due to the presence of oxygen. We propose that oxygen is abstracting the hydrogen atoms from polysaccharide and unpaired electrons on carbon atoms are produced. At 400°C the percentage of carbon in residues prepared at inert atmosphere is higher than for residue formed at oxidative atmosphere. Also the concentration of free radicals in thermolyzed residues obtained in inert atmosphere is greater than for those from oxidative ones. That is why suppose that at this temperature oxygen is bonded to polysaccharide residue and free radicals are terminated. From the semiquantitative DTA we can make the following sequence of samples according to their increasing thermooxidative effect: unmodified cellulose < A–HSO < A–Br^? < A–I^? < A–NO < A–H₂PO < A–CH₃COO^? < A–HCO < A–F^? < A–Cl^?1 < A–OH^p?.     

The potentiometric behaviour of copolymers of methacrylic acid in water-ethanol solutions

Summary The synthesis is reported of copolymers of styrene with methacrylic acid and of methyl methacrylate with methacrylic acid by radical copolymerization, of copolymers of methyl methacrylate with methacrylic acid by partial alkaline hydrolysis of poly(methyl methacrylate), and of block copolymers of styrene with methacrylic acid. Modified titration curves of all these copolymers were recorded in water and water-ethanol solutions. In a solution containing 50 mass.% ethanol, only small differences could be observed between the potentiometric behaviour of the individual copolymers and polymethacrylic acid. Also, there were no essential differences in any of the solvents used between the potentiometric behaviour of block copolymers of styrene with methacrylic acid, on the one hand, and polymethacrylic acid, on the other. On the contrary, maxima and minima were always observed on the modified titration curves of statistical copolymers with a higher content of the hydrophobic comonomer in solutions with a high water content. Thus, using the modified titration curves, it is possible to decide whether a given copolymer is of the block or statistical type.     

Investigation of Flow Patterns in Continuous‐flow Stirred Vessels by Laser Doppler Velocimetry

The flow structure of a continuous‐flow reactor stirred by a Rushton turbine was investigated by laser Doppler velocimetry for two different mean residence time‐mixing time ratios. Velocity measurements were obtained for two inlet locations, corresponding to the incoming liquid stream being fed co‐currently or counter‐currently to the flow discharged by the turbine. In all investigated configurations and for all operating conditions, it was found that the flow disruption caused by the incoming liquid stream was observable mainly in the first vessel quarter, which followed the feed‐tube plane. From comparison of the velocities encountered in the various planes in the continuous‐flow reactor to the velocities of the batch reactor, it was also concluded that it may be possible to intensify the usage of the turbine‐stirred vessel by decreasing the characteristic times ratio, without considerable flow by‐pass and/or short‐circuiting problems.     

Diffusion of ellipsoidal granular particles in shear flow

The diffusion of nonspherical particles has not been well understood due to the complexity of their contact mechanics and self-organization of their orientations. We perform discrete element method simulations of monodisperse ellipsoids in a shear flow with Lees-Edwards boundary conditions to quantify the relation between the diffusion coefficient and the flow parameters. The results indicate that the particle aspect ratio strongly affects the diffusion coefficient by influencing the particle orientation and alignment. We develop a scaling law for the diffusion coefficient perpendicular to the flow direction, D_yy, which combines the influences of the shear rate , the solids fraction f, the effective particle diameter d_eff and the particle aspect ratio Z. We show that , where k_d is a dimensionless pre-factor, and a fit is obtained for the functional form of χ(f, Z). This scaling law will be useful in developing continuum transport models for applications.     

The role of Lewis bases on the improvement of the stereospecificity and activity of TiCl3/AlClEt2 catalyst system

Summary The effect of di-n-butyl ether (DBE) in the synthesis of a highly active propylene polymerization catalyst was studied. Electron-donors having ester and phosphate groups (ethyl benzoate-EB, diisobutyl phthalate-DIBP and tri-n-butyl phosphate-TBP) were added as second internal bases (IB₂) to the catalysts prepared by the reduction of TiCl₄ with AlClEt₂ (DEAC) in the presence of DBE as a first internal base (IB₁). The crystalline forms were examined for all catalyst samples by X-ray method. Special attention has been paid to the -TiCl₃ samples showing the best catalytic properties. These catalysts were evaluated in propylene polymerization in the absence and presence of external bases (EB, DIBP and DBE). The effects of internal and external bases on the catalyst activity and stereo-specificity are discussed.