Rheological and morphological properties of high‐density polyethylene and poly(ethylene–octene) blends

The rheological and morphological properties of blends based on high‐density polyethylene (HDPE) and a commercial ethylene–octene copolymer (EOC) produced by metallocene technology were investigated. The rheological properties were evaluated in steady and dynamic shear experiments at 190°C in shear rates ranging from 90 s^?1 to 1500 s^?1 and frequency range between 10^?1 rad/s and 10² rad/s, respectively. These blends presented a high level of homogeneity in the molten state and rheological behavior was generally intermediate to those of the pure components. Scanning electron microscopy (SEM) showed that the blends exhibit dispersed morphologies with EOC domains distributed homogeneously and with particle size inferior to 2 μm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2240–2246, 2002     

The Influence of the Acid Sites on the Methylamines Synthesis with Cu-HZSM-5 Zeolite

There is a high industrial demand for MMA and DMA, however, the production of TMA is favored with the commercial catalysts. This work tested the methanol amination reaction with HZSM-5 and Cu/HZSM-5 zeolites (%Cu = 1.2, 3.7 and 6.0). Regarding the MMA selectivity, light differences were observed among Cu/HZSM-5 catalysts and pure zeolite, although the catalysts containing 3.7% copper was slightly more selective to MMA than the other metallic catalysts studied. From these results it is suggested that the metal loading present in the catalysts leads to a modification in the nature of the acidic sites, in particular, the selectivity depends on ratio Brönsted/Lewis acid sites. This modifications would facilitate the amines desorption during the reaction.     

Induced Defensive Response of Myrtle Oak to Foliar Insect Herbivory in Ambient and Elevated Co2

The rising level of atmospheric CO2 has stimulated several recent studies attempting to predict the effects of increased CO2 on ecological communities. However, most of these studies have been conducted in the benign conditions of the laboratory and in the absence of herbivores. In the current study, we utilized large octagonal chambers, which enclosed portions of an intact scrub-oak community to investigate the interactive effects of CO2 and insect herbivory on myrtle oak, Quercus myrtifolia. Specifically, we assessed the effects of ambient and elevated CO2 (2x current concentrations) on percent foliar nitrogen, C:N ratio, total relative foliar tannin content, and the presence of leaf damage caused by leaf mining and leaf chewing insects that feed on myrtle oak. Total foliar N declined and C:N ratios increased significantly in oaks in elevated CO2 chambers. The percentages of leaves damaged by either leafminers or leaf chewers tended to be lower in elevated compared to ambient chambers, but they co-occurred on leaves less than expected, regardless of CO2 treatment. Leaves that had been either mined or chewed exhibited a similar wounding or defensive response; they had an average of 25 and 21% higher protein binding ability, which is correlated with tannin concentration, compared to nondamaged control leaves, respectively. While the protein-binding ability (expressed as total percent tannin) of leaves from elevated CO2 was slightly higher than from leaves grown in ambient chambers, this difference was not significant.     

Lipid composition of the membrane released after an in vitro acrosome reaction of epididymal boar sperm

Prior to fertilization, mammalian sperm must undergo the acrosome reaction, which involves modifications of the plasma and outer acrosomal membranes followed by vesiculation and release of the membranes. The membrane fraction that was released from caudal boar sperm undergoing an in vitro acrosome-like reaction was isolated and characterized with respect to density, marker enzymes and lipid composition. This membrane had a lower phospholipid/protein ratio (mg/mg) than the sperm plasma membrane, whereas both membranes had similar molar sterol/phospholipid ratios. The major phospholipid was sphingomyelin, followed by phosphatidylethanolamine and phosphatidylcholine, whereas in the plasma membrane the order was reversed; the two major phosphoglycerides contained alkylacyl and alkenylacyl species in addition to the diacyl species. The released membrane also contained lower amounts of cholesterol sulfate and unsaturated fatty acids than the plasma membranes. These results, in combination with our studies on the changes of the sperm membranes during maturation and acrosome reaction, will allow a better understanding of the mechanism of the sperm acrosome reaction.     

Two new aluminophosphates, IST-1 and IST-2: First examples of a dual templating role of water and methylamine in generating microporous structures

This study is aimed at exploring the ability of very small sized N-bearing molecules to generate and stabilize microporous aluminophosphates. Two new AlPO₄-n materials, called IST-1 and IST-2, have been obtained in aqueous media using, as main template, methylamine (MA), directly added, or generated in situ from methylformamide (MF) degradation. While IST-1 topology proved to be novel, IST-2 appears structurally related to AlPO₄-53(A). The obtained materials were characterized by powder XRD, TG/DSC, SEM and solid-state NMR. Tetraalkylammonium (TEA) cations were used as potential co-templates but only MA and water were found incorporated in the pore volumes of both structures, which argues for their true templating role. In IST-1, ¹³C solid-state NMR studies showed that half of MA species, presumably protonated, is H-bonded to framework oxygens while the other half surprisingly bonds directly to framework Al atoms. ¹³C NMR showed that only protonated MA occurs in IST-2 channels. TEA⁺ cations definitely do not play any specific template role. They indirectly favor the crystallization of IST-1 or IST-2 devoid from other crystalline or amorphous side phases, by interacting with part of the Al and P in solution and forming soluble [AlPO₄(OH)]–[TEA,HMA] complexes, substantially modifying the compositions of gels precursors to each phase during nucleation and/or growth steps. While both IST-1 and IST-2 crystallize from gels of similar initial compositions, it was demonstrated that the new MA/T ratio (T = Al or P) obtained after in situ complexation was the key parameter that specifically governs the crystallization of each phase.     

Long-term cyclability of nanostructured LiFePO4

Amorphous LiFePO₄ was obtained by lithiation of FePO₄ synthesized by spontaneous precipitation from equimolar aqueous solutions of Fe(NH₄)₂(SO₄)₂·6H₂O and NH₄H₂PO₄, using hydrogen peroxide as oxidizing agent. Nano-crystalline LiFePO₄ was obtained by heating amorphous nano-sized LiFePO₄ for different periods of time. The materials were characterized by TG, DTA, X-ray powder diffraction, scanning electron microscopy (SEM) and BET. All materials showed very good electrochemical performance in terms of energy and power density. Upon cycling, a capacity fading affected the materials, thus reducing the electrochemical performance. Nevertheless, the fading decreased upon cycling and after the 200th cycle the cell was able to cycle for more than 500 cycles without further fading.     

Twin-image suppression in digital in-line holography based on wave-front filtering

Pattern Analysis and Applications - Digital holography is an imaging process able to recreate three-dimensional representations of objects from recording pattern interference among distinct waves....     

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.     

Synthesis and characterization of photopolymerizable hydrogels based on poly (ethylene glycol) for biomedical applications

Hydrogels are polymeric materials widely used in medicine due to their similarity with the biological components of the body. Hydrogels are biocompatible materials that have the potential to promote cell proliferation and tissue support because of their hydrophilic nature, porous structure, and elastic mechanical properties. In this work, we demonstrate the microwave-assisted synthesis of three molecular weight varieties of poly(ethylene glycol) dimethacrylate (PEGDMA) with different mechanical and thermal properties and the rapid photo of them using 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184) as UV photoinitiator. The effects of the poly(ethylene glycol) molecular weight and degree of acrylation on swelling, mechanical, and rheological properties of hydrogels were investigated. The biodegradability of the PEGDMA hydrogels, as well as the ability to grow and proliferate cells, was examined for its viability as a scaffold in tissue engineering. Altogether, the biomaterial hydrogel properties open the way for applications in the field of regenerative medicine for functional scaffolds and tissues.     

Synthesis of amphiphilic (meth)acrylates with oligo(ethylene glycol) and (or) oligo(propylene glycol) blocks by the esterification of (meth)acrylic acid

Thermoresponsive PEG-based (PEG stands polyethylene glycol) polymers are unique for use in medicine because of their low toxicity, good biocompatibility and biodegradability, but usually more hydrophobic and more toxic comonomers are used to adjust lower critical solution temperature (LCST). A convenient way to overcome this problem and to finely tune LCST is to use alkoxy oligo(ethylene glycol)- or alkoxy oligo(propylene glycol) (meth)acrylates as starting comonomers. Here we report on the conditions for the simple and affordable synthesis of methoxy oligo(propylene glycol) (meth)acrylate- and methoxy oligo(propylene glycol)-block-oligo(ethylene glycol) (meth)acrylate-based macromonomers with high yields (80%–98.7%) by the acid-catalyzed esterification of (meth)acrylic acid with alkoxy oligo(alkylene glycols) containing oligo(ethylene glycol) (OEG) and/or oligo(propylene glycol) (OPG) blocks. p-Toluene sulphonic acid (pTSA), alkyl(C₁₂–C₁₄)benzene sulfonic acid (ABSA) and H₂SO₄ were used as catalysts. It has been shown that pTSA and ABSA are practically the same in catalytic activity and are superior to sulfuric acid. The reaction orders with respect to catalyst was found to be close to 1 in all cases. It has been shown that the reaction is actually insensitive to the lengths of OEG and OPG blocks, as well as to the structure of the terminal alkyl group, while the esterification of acrylic acid (AA) proceeds much faster compared to methacrylic acid (MAA) one under the same conditions. The influence of temperature on the equilibrium conversions of alcohols was determined, which were found to be 89%–93% for the esterification of AA and 61%–86% for MAA in the temperature range of 60–120°C. A further increase in conversion was achieved by introducing an azeotropic agent (toluene), its optimal concentration was found to be 10%–15%.