A novel electrocatalyst support with proton conductive properties for polymer electrolyte membrane fuel cell applications

The objective of this study is to graft the Surface of carbon black, by chemically introducing polymeric chains (Nafion (R) like) with proton-conducting properties. This procedure aims for a better interaction of the proton-conducting phase with the metallic catalyst particles, as well as hinders posterior support particle agglomeration. Also loss of active surface call be prevented. The proton conduction between the active electrocatalyst site and the Nafion (R) ionomer membrane should be enhanced, thus diminishing the ohmic drop ill the polymer electrolyte membrane fuel cell (PEMFC). PtRu nanoparticles were supported on different carbon materials by the impregnation method and direct reduction with ethylene glycol and characterized using amongst others FTIR, XRD and TEM. The screen printing technique was used to produce membrane electrode assemblies (MEA) for single cell tests in H(2)/air(PEMFC) and methanol operation (DMFC). In the PEMFC experiments, PtRu supported on grafted carbon shows 550 mW cm(-2) gmetal(-1) power density, which represents at least 78% improvement in performance, compared to the power density of commercial PtRu/C ETEK. The DMFC results of the grafted electrocatalyst achieve around 100% improvement. The polarization Curves results clearly show that the main Cause of the observed effect is the reduction in ohmic drop, caused by the grafted polymer. (C) 2009 Elsevier B.V. All rights reserved.

Toxicity and recalcitrant compound removal from bleaching pulp plant effluents by an integrated system: anaerobic packed-bed bioreactor and ozone

Effluents originated in cellulose pulp manufacturing processes are usually toxic and recalcitrant, specially the bleaching effluents, which exhibit high contents of aromatic compounds (e.g. residual lignin derivates). Although biological processes are normally used, their efficiency for the removal of toxic lignin derivates is low. The toxicity and recalcitrance of a bleached Kraft pulp mill were assessed through bioassays and ultraviolet absorption measurements, i.e. acid soluble lignin (ASL), UV(280), and specific ultraviolet absorption (SUVA), before and after treatment by an integrated system comprised of an anaerobic packed-bed bioreactor and oxidation step with ozone. Furthermore, adsorbable organic halides (AOX) were measured. The results demonstrated not only that the toxic recalcitrant compounds can be removed successfully using integrated system, but also the ultraviolet absorption measurements can be an interesting control-parameter in a wastewater treatment.

Influence of EVA and acrylate polymers on some mechanical properties of cementitious repair mortars

In repair works of reinforced concrete, patch repairs tend to crack in the interfacial zone between the mortar and the old concrete. This occurs basically due to the high degree of restriction that acts on a patch repair. For this reason, the technology of patch repair needs to be the subject of a discussion involving professionals who work with projects, construction maintenance and mix proportioning of repair mortars. In the present work, a study is presented on the benefits that the ethylene vinyl acetate copolymer (EVA) and acrylate polymers can provide in the mix proportioning of a repair mortar with respect to compressive, tensile and direct-shear bond strength. The results indicated that the increase in bond strength and the reduction in the influence of the deficiency in Curing conditioning are the main contributions offered by the polymers studied here. (C) 2009 Elsevier, Ltd. All rights reserved.

Discoloration and fungal growth on three fiber cement formulations exposed in urban, rural and coastal zones

Three formulations of fiber cement were evaluated for fungal colonization and color change after five years of exposure in aging stations located in urban (Sao Paulo), rural (Pirassununga) and coastal (Rio Grande) zones in Brazil. The lowest color change and fungal colonization were registered in Rio Grande, which has a temperate climate, as opposed to Sao Paulo and Pirassununga, which are tropical. The highest fungal colonization was recorded in Sao Paulo, one of the most air polluted cities in Brazil. Pirassununga samples had an intermediate fungal colonization, in spite of showing the highest color change with visible dark spots on the surfaces. These spots were identified as cyanobacteria, which significantly contributed to the darkening of the specimens. The fiber cement formulation, varying in proportion of organic fibers such as poly (vinyl alcohol) and cellulose, was less significant for fungal bioreceptivity than the characteristics of the exposure site. The most frequent fungal genus found in the tropical climate, in both urban and rural zones, and the main one responsible for the higher records in Sao Paulo, was Scytalidiurn sp. which was registered for the first time on this building material in Brazil. (C) 2010 Elsevier Ltd. All rights reserved.

Polymer toughening using residue of recycled windshields: PVB film as impact modifier

In this work, poly(vinyl butyral) (PVB) film originated from the mechanical separation of windshields was tested as all impact modifier of Polyamide-6 (PA-6). The changes undergone by PVB film during the recycling process and the blend manufacturing were evaluated by thermal analyses, infrared spectroscopy and loss oil ignition. Blends of PA-6/original PVB film and PA-6/recovered PVB film were obtained in concentrations ranging from 90/10 to 60/40. The mechanical properties of the blends were investigated and explained in light of the blends morphologies, which in turns were correlated to the changes undergone by the PVB film during the recycling process. The original film presented a plasticizer content of 33 wt.%, which decreased to as low as 20 wt.%, after the recycling and blend preparation processes. The PA-6/PVB film blends presented lower values of tensile strength and Young`s modulus than Polyamide-6, but all blends presented a dramatic increase in their toughness, with a special feature for the 40 wt.%(, blend, which resulted in a super toughened material (impact strength exceeding 500 J/m). Similar results were obtained with recovered PVB film and super tough blends were also obtained. The use of recovered PVB resulted in a smaller improvement of the impact strength due to the loss of plasticizer undergone during the recycling process. The morphological observations showed that if the interparticle distance is smaller than around 0.2 mu m (critical value), the notched Izod impact strength values increase considerably and the fracture surface of blends exhibit characteristics of tough failure. (C) 2007 Elsevier Ltd. All rights reserved.

Influence of the rubbery phase on the crystallinity and thermomechanical properties of poly(3-hydroxybutyrate)/elastomer blends

Poly(3-hydroxybutyrate) (PHB) is a very promising biopolymer. In order to improve its processability and decrease its brittleness, PHB/elastomer blends can be prepared. In the work reported, the effect of the addition of a rubbery phase, i.e. ethylene - propylene-diene terpolymer (EPDM) or poly(vinyl butyral) (PVB), on the properties of PHB was studied. The effects of rubber type and of changing the PHB/elastomer blend processing method on the crystallinity and physical properties of the blends were also investigated. For blends based on PHB, the main role of EPDM is its nucleating effect evidenced by a decrease of crystallization temperature and an increase of crystallinity with increasing EPDM content regardless of the processing route. While EPDM has a weak effect on PHB glass transition temperature, PVB induces a marked decrease of this temperature thank to its plasticizer that swells the PHB amorphous phase. A promising solution to improve the mechanical properties of PHB seems to be the melt-processing of PHB with both plasticizer and EPDM. In fact, the plasticizer is more efficient than the elastomer in decreasing the PHB glass transition temperature and, because of the nucleating effect of EPDM, the decrease of the PHB modulus due to the plasticizer can be counterbalanced. (C) 2010 Society of Chemical Industry

In-Line Monitoring of Particle Size during Emulsion Polymerization under Different Operational Conditions using NIR Spectroscopy

In the present work, the sensitivity of NIR spectroscopy toward the evolution of particle size was studied during emulsion homopolymerization of styrene (Sty) and emulsion copolymerization of vinyl acetate-butyl acrylate conducted in a semibatch stirred tank and a tubular pulsed sieve plate reactor, respectively. All NIR spectra were collected online with a transflectance probe immersed into the reaction medium. The spectral range used for the NIR monitoring was from 9 500 to 13 000 cm(-1), where the absorbance of the chemical components present is minimal and the changes in the NIR spectrum can be ascribed to the effects of light scattering by the polymer particles. Off-line measurements of the average diameter of the polymer particles by DLS were used as reference values for the development of the multi-variate NIR calibration models based on partial least squares. Results indicated that, in the spectral range studied, it is possible to monitor the evolution of the average size of the polymer particles during emulsion polymerization reactions. The inclusion of an additional spectral range, from 5 701 to 6 447 cm(-1), containing information on absorbances (""chemical information"") in the calibration models was also evaluated.

Development of a Continuous Emulsion Copolymerization Process in a Tubular Reactor

This contribution describes the development of a continuous emulsion copolymerization processs for vinyl acetate and n-butyl acrylate in a tubular reactor. Special features of this reactor include the use of oscillatory (pulsed) flow and internals (sieve plates) to prevent polymer fouling and promote good radial mixing, along with a controlled amount of axial mixing. The copolymer system studied (vinyl acetate and butyl acrylate) is strongly prone to composition drift due to very different reactivity ratios. An axially dispersed plug flow model, based on classical free radical copolymerization kinetics, was developed for this process and used successfully to optimize the lateral feeding profile to reduce compositional drift. An energy balance was included in the model equations to predict the effect of temperature variations on the process. The model predictions were validated with experimental data for monomer conversion, copolymer composition, average particle size, and temperature measured along the reactor length.

Effect of cerium (IV) ions on the anticorrosion properties of siloxane-poly(methyl methacrylate) based film applied on tin coated steel

This work investigates the influence of the addition of cerium (IV) ions on the anticorrosion properties of organic-inorganic hybrid coatings applied to passivated tin coated steel. In order to evaluate the specific effect of cerium (IV) addition on nanostructural features of the organic and inorganic phases of the hybrid coating, the hydrolytic polycondensation of silicon alkoxide and the radical polymerization of the methyl methacrylate (MMA) function were induced separately. The corrosion resistance of the coatings was evaluated by means of linear polarization, Tafel type curves and electrochemical impedance measurements. The impedance results obtained for the hybrid coatings were discussed based on an electrical equivalent circuit used to fit the experimental data. The electrochemical results clearly showed the improvement of the protective properties of the organic-inorganic hybrid coating mainly when the cerium (IV) was added to the organic phase solution precursor, which seemed to be due to the formation of a more uniform and densely reticulated siloxane-PMMA film. (C) 2010 Elsevier Ltd. All rights reserved.

Chemical interaction between EVA and Portland cement hydration at early-age

Ethylene/vinyl acetate (EVA) copolymer. as latex or redispersable powder, is added to mortars and concrete to improve the fracture toughness, impermeability and bond strength to various substrates. The physical and chemical interactions were already proved after one day of hydration but during the first hour just the physical interaction was identified and some evidences of a chemical interaction. The aim of this paper was to evaluate the chemical interaction between EVA and Portland cement during the first hours of hydration in the thermogravimetric analysis. The results confirmed that the EVA hydrolyses in pH alkaline and consumes calcium ions from the solution, forming an organic salt (calcium acetate). reducing the calcium hydroxide content. And, its interaction occurred in the first 15 min of hydration. (C) 2009 Elsevier Ltd. All rights reserved.

Novel deoxy-selenylconduritols: chemoenzymatic synthesis and biological evaluation

The first synthesis of two selenyldeoxycyclitols (4-bromo-2-phenylselenyl conduritol F and 6-phenylselenylconduritol F) is reported via a chemoenzymatic enantioselective route. The key step of the synthesis is the selenolysis of a vinyl epoxide. The new compounds were evaluated for their capacity to inhibit the growth of different microorganisms using a modification of the agar diffusion technique with thin layer chromatography plates as support. (C) 2009 Elsevier Ltd. All rights reserved.

Consecutive biocatalysis-palladium catalysis II: Synthesis of conduritol-alkyne conjugates

The palladium-catalyzed cross-coupling reaction of potassium alkynyltrifluoroborates with a chemoenzymatically derived deoxyconduritol is described. Six new compounds were synthesized in moderate to good yields. The alkynyl cross-coupling reaction can be effected using 10 mol% of Pd(PPh(3))(4) as Catalyst in toluene-H(2)O in the presence Of Cs(2)CO(3) as the inorganic base. (C) 2009 Elsevier B.V. All rights reserved.

Copper salt-catalyzed homo-coupling reaction of potassium alkynyltrifluoroborates: a simple and efficient synthesis of symmetrical 1,3-diynes

The copper-catalyzed dimerization of alkynyltrifluoroborates proceeds readily with good yields. The homo-coupling reaction can be effected in DMSO, in the open air, using Cu(OAc)(2) as catalyst in the absence of any other additives. A variety of functional groups are tolerated. (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis of unnatural cyclitols via a combined enzymatic-palladium catalysis approach

The Suzuki-Miyaura cross-coupling reaction of a hydroxylated vinyl bromide obtained by a chemoenzymatic approach with a diverse range of potassium organotrifluoroborates has been accomplished catalyzed by Pd(PPh(3))(4) in satisfactory yields. A variety of functional groups are tolerated in the nucleophilic partner. (C) 2008 Elsevier B.V. All rights reserved.

Synthesis of symmetrical 1,3-diynes via homocoupling reaction of n-butyl alkynyltellurides

An ultrasound-assisted synthesis of symmetrical 1,3-diyne compounds with electron-withdrawing or donating substituents is described and illustrated by the palladium-catalyzed homocoupling reaction of n-butyl alkynyltellurides. This procedure offers easy access to 1,3-diynes in very short reaction times, and the products are achieved in good to excellent yields. (C) 2009 Elsevier Ltd. All rights reserved.