Supertoughness in Polysulfone/Poly(ethylene‐octene) Blends

Summary: Poly(sulfone of Bisphenol A) (PSU) based blends were obtained by melt blending PSU with up to 15 wt.‐% poly(ethylene‐octene) either modified with maleic anhydride (mPEO) or not (PEO). The dispersed particle size was small and similar in blends with PEO or mPEO. These facts indicated respectively that the interfacial tension was low and the lack of compatibilizing effect of mPEO. Some preferential presence of PEO in the outer surface of the specimens was observed, and was attributed to the large viscosity difference between the two components of the blends. This had no effect on the modulus of elasticity, but speeded up both the yield stress and ductility decreases at rubber contents above 3.25 wt.‐%. However, despite the immiscibility of the components, and thanks to the small particle size of the blends, super‐toughness was attained in the unmodified PSU/PEO blends. This was at PEO contents (3.25 wt.‐%) at which the modulus, yield stress and ductility of the blends were almost as good as those of pure PSU. It appeared that a change of the chemical nature of the rubber did not influence by itself super‐toughness, unless it was accompanied by either a morphological or adhesion change.

Impact strength of PSU‐based blends vs. PEO (○) or mPEO (?) content.     

Separation of Acylglycerides Obtained by Enzymatic Esterification Using Solvent Extraction

New avenues to add value to glycerol are currently being explored. One of them is the synthesis of structured lipids through glycerol esterification. In this work we have analyzed the recovery and purification of dicaprin obtained by esterification of glycerol with capric acid (C) in heptane, mediated by Lipozyme RM IM. This is an intermediate step to obtain lipids MLM. In the first stage, the diglyceride synthesis MGM (being G a central HC–OH) was carried out. When M = C, the diglyceride is CGC. Recovery of the diglyceride CGC is required to carry out the esterification of the sn-2 position with palmitic acid (P), thus obtaining the triglyceride CPC. Different solvents were evaluated using Ecofac 1.0 (a molecular design software solvent) through a theoretical approach to explore the best solvents for the acylglycerides separation. Then, the performance of the selected solvents to separate dicaprin from mono and tricaprin was experimentally studied in a liquid–liquid extraction process. Previously, the remaining fatty acid had been neutralized. With liquid–liquid extraction in three simple steps, using ethanol/water, 94 % of the dicaprin obtained by enzymatic esterification was recovered with a purity of 89 % (wt%). It was also possible to obtain dicaprin with a purity of 97 % but with a yield of 56 %.     

Functionalization of carbon support and its influence on the electrocatalytic behaviour of Pt/C in H2 and CO electrooxidation

Chemical modification of Carbon Vulcan XC-72R for fuel cell applications has been undertaken. Treated carbons were used as carriers for the deposition of Pt nanoparticles and used as electrocatalysts. The influence of the carbon treatment, as well as that of the Pt nanoparticles generation and their deposition route has been studied. The behaviour of the electrocatalysts in the CO and hydrogen oxidation reaction (HOR) has been studied. It was observed that carbon pre-treatment lead to difference behaviour in the CO oxidation reaction compared with the performance over non treated supports. In this way, CO oxidation was controlled by the nature of the support rather than by the nature of the Pt particles alone.     

Improved toughness in HIPS obtained from different styrene/butadiene‐graded block copolymers through modification of the polydispersity index of the PS block

The polymerization of styrene in the presence of graded block copolymers with a polystyrene/polybutadiene composition of 40/60, 30/70, and 20/80 and with a polydispersity index (M_w /M_n ) in the polystyrene block varying from 1.1 to 1.6 was studied. As the polydispersity index of the polystyrene block increases, an improvement of up to 50% in the Izod impact toughness of the produced high‐impact polystyrene was achieved. The rubber particle morphology type, the size, and the volume fraction of the rubber phase particles could be modified through changes in the composition of the graded block copolymer. The changes that occurred in the rubber phase were mainly generated by the variation in the interfacial tension between the phases, and this variation was principally attributed to an increase in the polydispersity index of the polystyrene block in the precursor copolymer. POLYM. ENG. SCI., 46:1333–1341, 2006. © 2006 Society of Plastics Engineers     

On the nature of catalyst promotion by manganese in CO hydrogenation to oxygenates over RhMn/NaY

CO hydrogenation over Mn promoted Rh/NaY catalysts was studied at 10 bar and 250°C. Significant selectivity to oxygenates, mainly ethanol and ethyl acetate, was obtained after neutralizing the protons that are formed during reduction of Rh ions. Layered bed experiments show that protons act as sites catalyzing secondary reactions. Protons also convert Mn(OH)₂ to Mn²⁺ ions; the catalysts with highest selectivity to oxygenates contain MnO particles and Rh clusters. The results suggest chemical interaction of adsorbates on Rh_n clusters with those on MnO.     

Efficient three‐dimensional parallel simulations of PHEMTs

An efficient 3D semiconductor device simulator is presented for a memory distributed multiprocessor environment using the drift–diffusion (D–D) approach for carrier transport. The current continuity equation and the Poisson equation, required to be solved iteratively in the D–D approach, are discretized using a finite element method (FEM) on an unstructured tetrahedral mesh. Parallel algorithms are employed to speed up the solution. The simulator has been applied to study a pseudomorphic high electron mobility transistor (PHEMT). We have carried out a careful calibration against experimental I–V characteristics of the 120 nm PHEMT achieving an excellent agreement. A simplification of the device buffer, which effectively reduces the mesh size, is investigated in order to speed up the simulations. The 3D device FEM simulator has achieved almost a linear parallel scalability for up to eight processors. Copyright © 2005 John Wiley & Sons, Ltd.     

Physical properties of poly(cyclohexyl methacrylate)-b-poly(iso-butyl acrylate)-b-poly(cyclohexyl methacrylate) triblock copolymers synthesized by controlled radical polymerization

The microphase segregation of different poly(cyclohexyl methacrylate)-b-poly(iso-butyl acrylate)-b-poly(cyclohexyl methacrylate), PCH-b-PiBA-b-PCH, triblock copolymers obtained by atom transfer radical polymerization has been evaluated by dynamic mechanical thermal analysis through location of the two relaxations ascribed to cooperative motions of each block. Additionally, other secondary relaxations have been found, whose characteristics are also dependent on molecular weight of outer and rigid segments. The length of these hard blocks influences significantly the stiffness and microhardness found in these triblock copolymers. These two mechanical parameters increase as molecular weight of poly(cyclohexyl methacrylate) does. The morphological aspects have been examined by small angle X-ray scattering and atomic force microscopy.     

Mechanochemical synthesis of YNbO4:Eu nanocrystalline powder and its structural,microstructural and photoluminescence properties

In this research we prepared nanocrystalline YNbO₄:Eu³⁺ phosphor, i.e. nanophosphor, powder using an efficient mechanochemical method followed by annealing. X-ray diffraction analysis revealed that YNbO₄:Eu³⁺ crystallizes in monoclinic structure C2/c where, from the point of view of A and B in ABO₄ compounds, cation coordination can be noted as [6+2, 4+2]. Crystallite size of about 40 nm, was estimated using Debye Scherrer's equation. Raman spectroscopy with 785 and 532 nm excitation wavelengths is performed to record a majority of materials phonon modes and to provide more in depth understanding of the YNbO₄ structure. Scanning electron microscopy observations indicate that the mechanical treatment during synthesis is causing non-uniformity of the powder microstructure. High resolution photoluminescent measurements upon UV excitation showed intense emission coming from f–f transitions of the europium ion with the lifetime of 0.68 ms, suggesting that the obtained YNbO₄:Eu³⁺ is a good potential phosphor. A comparison of emissive properties with microcrystalline YNbO₄:Eu³⁺ was made and it showed higher values of emission intensity and lifetime of the nanocrystalline sample.     

Cr(VI) removal from synthetic and real wastewaters: The use of the invasive biomass Sargassum muticum in batch and column experiments

The macroalgae Sargassum muticum was selected for the treatment of solutions containing Cr(VI). Very acidic pH values were established as optimal for Cr(VI) reduction. Algae chemical modification reduced equilibrium time to 4 h. First order kinetic model was used to describe the reduction kinetic of Cr(VI). A column experiment allowed to distinguish the processes occurring during Cr(VI) elimination: its reduction to Cr(III) and the subsequent adsorption of this species formed. Under the selected conditions the biomass was capable of reducing all the incoming Cr(VI) during 77 h. Industrial wastewaters from chrome plating industry were also tested for chromium removal.     

The evaluation of scientific production: Towards a neutral impact factor

Measurement of research activity still remains a controversial question. The use of the impact factor from the Institute for Scientific Information (ISI) is quite widespread nowadays to carry out evaluations of all kinds; however, the calculation formula employed by ISI in order to construct its impact factors biases the results in favour of knowledge fields which are better represented in the sample, cite more in average and whose citations are concentrated in the early years of the articles. In the present work, we put forward a theoretical proposal regarding how aggregated normalization should be carried out with these biases, which allows comparing scientific production between fields, institutions and/or authors in a neutral manner. The technical complexity of such work, together with data limitations, lead us to propose some adjustments on the impact factor proposed by ISI which — although they do not completely solve the problem — reduce it and allow glimpsing the path towards more neutral evaluations. The proposal is empirically applied to three analysis levels: single journals, knowledge fields and the set of journals from the Journal Citation Report.