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     

Catalytic partial oxidation of methane to synthesis gas in a ceramic membrane reactor

Methane has been selectively converted to synthesis gas using a two-zone fixed bed of a Ni/Al₂O₃ catalyst inside a modified ceramic membrane. The first zone of the reactor was surrounded by an impervious wall, and therefore behaved as a conventional fixed bed reactor. In the second zone, some of the reaction products could preferentially diffuse out of the reactor, which yielded higher than equilibrium methane conversions. The influence of the different operating conditions has been studied, and the performance of the membrane reactor has been compared to that of a fixed bed reactor. The membrane reactor has also been used at pressures above atmospheric (2 bar), with good conversions and selectivities.     

Removal of fulvic acid from aqueous media by adsorption onto modified vermiculite

Clay minerals are low cost materials that can be structurally modified and exploited for removal of natural organic matter from freshwaters. The present study shows that vermiculites modified by ion exchange with hexadecyltrimethylammonium or intercalation with poly(hydroxy iron) cations are potential adsorbents for removal of fulvic acid, whereas the adsorption on the raw clay mineral is negligible. The efficiency of the modified vermiculite was evaluated by measuring adsorption isotherms by the batch technique using initial fulvic acid concentrations between 2.5 and 50.0 mg L^− 1, with one hour of contact time. At least 94% of the fulvic acid initially present in a 20 mg L^− 1 solution was sorbed onto either the intercalated poly(hydroxy iron) cations or the organically modified vermiculite. Up to an initial concentration of 5.0 mg L^− 1 the adsorption is irreversible, and no quantifiable fulvic acid was measured in the desorption experiments. For initial fulvic acid concentrations between 10.0 and 50.0 mg L^− 1, desorption was between 2.3% and 4.9% for Fe(III) intercalated vermiculite, and between 1.4% and 9.2% for the organoclay. The adsorption percentages on intercalated poly(hydroxy iron) cations increased upon lowering pH and increasing the ionic strength, indicating the occurrence of strong binding mechanisms such as ligand exchange. Adsorption percentage of fulvic acid onto the organoclay also increased with lowering of pH, but in this case the adsorption percentages showed a small decrease at high ionic strength, suggesting that electrostatic attraction plays an important role in the adsorption process.     

Structure and Properties of Long-Wavelength-Transmitting Halide Glasses

The lower halides of zinc, namely, ZnCl₂, ZnBr₂, and ZnI₂, may act as network formers in glasses that also contain modifying alkali halides such as KCI, KBr, KI, NaI, or CsI. Compositions which contain only Br⁻ or I⁻ anions are of particular interest because of their extended infrared transmission, which includes the ∼10-μm region, in addition to full visible transparency. A series of modified zinc halide glasses were prepared and characterized by differential scanning calorimetry, middle and far Fourier transform infrared spectroscopy, and polarized Raman spectroscopy. T _g values were characteristically low, around 40°C. Bulk glass infrared transmission up to 15 to 20 μm was recorded. The most probable glass structures are discussed and compared to oxide glass models. An attenuation of  0.001 dB/km has been projected as a possible intrinsic minimum for optical fibers operating near ∼6 μm.     

Miscibility and morphology of poly(vinylidene fluoride)/poly[(vinylidene fluoride)‐ran‐trifluorethylene] blends

This study presents an investigation of the effect of the different crystalline phases of each blend component on miscibility when blending poly(vinylidene fluoride) (PVDF) and its copolymer poly[(vinylidene fluoride)‐ran‐trifluorethylene] [P(VDF–TrFE)] containing 72 mol % of VDF. It was found that, when both components crystallized in their ferroelectric phase, the PVDF showed a strong effect on the crystallinity and phase‐transition temperature of the copolymer, indicating partial miscibility in the crystalline state. On the other hand, immiscibility was observed when both components, after melting, were crystallized in their paraelectric phase. In this case, however, a decrease in crystallization temperatures suggested a strong interaction between monomers in the liquid state. Blend morphologies indicated that, in spite of the lack of miscibility in the crystalline state, there is at least miscibility between PVDF and P(VDF–TrFE) in the liquid state, and that a very intimate mixture of the two phases on the lamellar level can be maintained upon crystallization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1362–1369, 2002     

Off-line optimization and control for real time integration of a three-phase hydrogenation catalytic reactor

In order to develop and test the integration procedure, in this paper a real time process integration involving the optimization and control of the process is presented, in this case, with the two-layer approach. The used optimization algorithms were Levenberg–Marquardt and SQP that solve a non-linear least square problem subject to bounds on the variables. The two-layer approach is a hierarchical control structure where an optimization layer calculates the set points and manipulated variables to the advanced controller, which is based on the dynamic matrix control with constraints (QDMC). The non-isothermal dynamic model of the three-phase slurry catalytic reactor with appropriate solution procedure was utilized in this work (Vasco de Toledo, E. C., Santana, P. L., Maciel, M. R. W., & Maciel Filho, R. (2001). Dynamic modeling of a three-phase catalytic slurry reactor. Chemical Engineering Science, 56, 6055–6061). The model consists on mass and heat balance equations for the catalyst particles as well as for the bulk phases of gas and liquid. The model was used to describe the dynamic behavior of hydrogenation reaction of o-cresol to obtain 2-methil-cyclohexanol, in the presence of a catalyst Ni/SiO₂.     

Update on the pharmacology of Spirulina (Arthrospira), an unconventional food

Spirulina (Arthrospira), a filamentous, unicellular alga, is a cyanobacterium grown in certain countries as food for human and animal consumption. It is also used to derive additives in pharmaceuticals and foods. This alga is a rich source of proteins, vitamins, amino acids, minerals, and other nutrients. Its main use, therefore, is as a food supplement. Over the last few years, however, it has been found to have many additional pharmacological properties. Thus, it has been experimentally proven, in vivo and in vitro that it is effective to treat certain allergies, anemia, cancer, hepatotoxicity, viral and cardiovascular diseases, hyperglycemia, hyperlipidemia, immunodeficiency, and inflammatory processes, among others. Several of these activities are attributed to Spirulina itself or to some of its components including fatty acids omega-3 or omega-6, beta-carotene, alpha-tocopherol, phycocyanin, phenol compounds, and a recently isolated complex, Ca-Spirulan (Ca-SP). This paper aims to update and critically review the results published over the last few years with regards to these properties. The conclusion is that even if this cyanobacterium has been one of the most extensively studied from the chemical, pharmacological and toxicological points of view, it is still necessary to expand the research in order to have more consistent data for its possible use in human beings.     

The role of the Tm3+ concentration on CaMoO4 properties processed by microwave hydrothermal under stirring condition

The compounds based on calcium molybdate (CaMoO₄) are the subject of extensive research due to their excellent optical properties and a broad range of potential technological applications. In this work, we report a systematic study of CaMoO₄:Tm³⁺ phosphors synthesized by coprecipitation and processed in a microwave-hydrothermal system at low temperature (100°C) and stirring. The effect of the Tm³⁺ doping content (0%–12%) is studied in full detail to understand their role in the CaMoO₄:Tm³⁺ morphological, structural, and luminescent properties. The X-ray diffraction, Raman, and Fourier Transform Infrared spectroscopic techniques revealed that all the prepared powders have a tetragonal crystal structure with a distinct density of cation vacancies and structural disorders. The band gap remains almost constant for doping levels lower than 8%, but it narrows strongly for powders doped with 12% Tm³⁺ ions. The designed phosphors have shown two emission bands in which intensity depends on the Tm³⁺ ions doping level. For doping levels lower than 2%, the photoluminescence profile displays a broad emission band peaking at 543 nm (green). For concentrations higher than 4%, the band centered at 543 nm decreases in intensity and the near-infrared emission band at around 800 nm, assigned to ³F₃, ³H₄ → ³H₆ transitions from Tm³⁺ ion, become more intense. The outcomes of this work reveal that appropriated Tm³⁺ ions doping levels can be applied to suppress the PL emission in the visible range and improve that in the near-infrared region in CaMoO₄-based materials.     

Fabrication of hybrid proton-exchange membranes using a brandnew high temperature ionic liquid as charge transporting and clay modifier

The search for more compatibility between ionic liquids (ILs) and polymer matrices in proton-exchange membrane fuel cells (PEMFCs) is one of the ways in which IL leaking from proton-exchange membranes could be minimized. In this work, it is presented the synthesis of an aromatic high temperature ionic liquid (HTIL), which, incorporated into an aromatic matrix such as sulfonated polyether ether ketone (sPEEK), is expected to diminish the IL leaking that normally affects PEMFC. Phenylethylammonium trifluoromethane sulfonate (PhetaTfO) was successfully synthesized and characterized. Its melting point of 88°C makes it to classify as a HTIL and it was employed as modifier of natural Montmorillonite, forming the phenylethylammonium intercalated montmorillonite (MmtPheta) and thus, ternary membranes containing PhetaTfO, MmtPheta, and sPEEK were prepared and characterized. Immersion tests demonstrated a higher compatibility of PhetaTfO with matrix when compared to the reference DemaTfO, which was reflected in up to 30% lower IL loss by the synthesized IL than the DemaTfO; X-rays diffraction (XRD) patterns demonstrated that the modified clay was properly dispersed inside the membranes, while dynamic mechanical analyses (DMA) results indicated a strong plasticizer effect along the increase of PhetaTfO content inside the membrane, while at the same time, the conductivity increased in an exponential manner, which permitted to identify an empiric exponential equation to evaluate the effect of concentration on ionic conductivity. The maximum conductivity obtained at IL concentrations of around 38 wt% was 0.2 mS/cm. It could expect high ionic conductivities of 10 mS/cm when the concentration of this IL is 60%; nevertheless, in order to achieve that, crosslinking treatments should be done to give the membranes enough mechanical resistance.     

Rheological,thermal and morphological properties of polyethylene terephthalate/polyamide 6/rice husk ash composites

This work deals with the rheological, morphological, and thermal properties of composites having poly(ethylene terephthalate) (PET), polyamide-6 (PA6), and their blends as matrices, and rice husk ash (RHA) as a filler. The study determines the effect of composition on the change in viscosity and rate of degradation during processing in a torque rheometer. Our data indicates that thermal stability and degradation during processing depend on matrix composition and filler concentration. SEM micrographs show both partial adhesion of the filler to the matrices and filler pullout. Optical microscopy shows particle agglomeration and that agglomerate size increased with filler content. FTIR investigates the shifting of absorption bands of PET/PA6 composite after the addition of RHA and attributes the selective dispersion of RHA to the formation of hydrogen bonds. Our data supports the idea that filler employed here is an option to develop polymer composites with improved properties.