Compositional and textural properties of milkfat-soybean oil enzymatic interesterification

Milkfat-soybean oil blends were enzymatically interesterified (EIE) by Aspergillus niger lipase immobilized on SiO(2)-PVA hybrid composite in a solvent free system. An experimental mixture design was used to study the effects of binary blends of milkfat-soybean oil (MF:SBO) at different proportions (0:100; 25:75; 33:67; 50:50; 67:33; 75:25; 100:0) on the compositional and textural properties of the EIE products, considering, as response variables, the interesterification yield (IY), consistency and hardness. Lipase-catalysed interesterification reactions increased the relative proportion of TAGs` C(46)-C(52) and decreased the TAGs` C(40)-C(42) and C(54) concentrations. The highest IY was attained (10.8%) for EIE blend of MF:SBO 67:33 resulting in a more spreadable material at refrigerator temperature in comparison with butter, milkfat or non-interesterified (NIE) blend. In this case, consistency and hardness values were at least 32% lower than values measured for butter. Thus, using A. niger lipase immobilized on SiO(2)-PVA improves the textural properties of milkfat and has potential for development of a product incorporating unsaturated and essential fatty acids from soybean oil. (C) 2010 Elsevier Ltd. All rights reserved.

Heat treatment influence on the superconducting properties of nanometric-scale Nb(3)Sn wires with Cu-Sn artificial pinning centers

Since the discovery of Nb(3)Sn superconductors many efforts have been expended to improve the transport properties in these materials. In this work, the heat treatment profiles for Nb(3)Sn superconductor wires with Cu(Sn) artificial pinning centers (APCs) with nanometric-scale sizes were analyzed in an attempt to improve the critical current densities and upper critical magnetic field. The methodology to optimize the heat treatment profiles in respect to the diffusion, reaction and formation of the superconducting phases is described. Microstructural characterization, transport and magnetic measurements were performed in an attempt to relate the microstructure to the pinning mechanisms acting in the samples. It was concluded that the maximum current densities occur due to normal phases (APCs) that act as the main pinning centers in the global behavior of the Nb(3)Sn superconducting wire. The APC technique was shown to be very powerful because it permitted mixing of the pinning mechanism. This achievement was not possible in other studies in Nb(3)Sn wires reported up to now.

Use of activated charcoal and ion-exchange resin to cleaN up and concentrate enzymes in extracts from biodegraded wood.

Use of activated charcoal and ion-exchange resin to cleaN up and concentrate enzymes in extracts from biodegraded wood. Ceriporiopsis subvermispora was used for the biodegradation of Eucalyptus grandis chips in the presence or absence of co-substrates (glucose and corn steep liquor) during 7, 14 and 28 days. Afterwards, the biodegraded chips were extracted with 50 mM sodium acetate buffer (pH 5.5) supplemented with 0.01% Tween 60. High activities of manganese peroxidases (MnPs) were observed in all the extracts, both in the absence (430, 765 and 896 UI kg(-1) respectively) and in the presence of co-substrates (1,013; 2,066 and 2,323 UI kg(-1) respectively). The extracts presented a high ratio between absorbances at 280 and 405 nm, indicating a strong abundance of aromatic compounds derived from lignin over heme-peroxidases. Adsorption into activated charcoal showed to be an adequate strategy to reduce the absorbance at 280 urn in all the extracts. Moreover, it allowed to maximize the capacity of an anion exchange resin bed (DEAE-Sepharose) used to concentrate the MnPs present in the extracts. It was concluded that the use of activated charcoal followed by adsorption into DEAE Sepharose is a strategy that can be used to concentrate MnPs in extracts obtained during the biodegradation of E. grandis by C. subvermispora.

Evaluation of the catalytic properties of Burkholderia cepacia lipase immobilized on non-commercial matrices to be used in biodiesel synthesis from different feedstocks

The objective of this work was to produce an immobilized form of lipase from Burkholderia cepacia (lipase PS) with advantageous catalytic properties and stability to be used in the ethanolysis of different feedstocks, mainly babassu oil and tallow beef. For this purpose lipase PS was immobilized on two different non-commercial matrices, such as inorganic matrix (niobium oxide, Nb(2)O(5)) and a hybrid matrix (polysiloxane-polyvinyl alcohol, SiO(2)-PVA) by covalent binding. The properties of free and immobilized enzymes were searched and compared. The best performance regarding all the analyzed parameters (biochemical properties, kinetic constants and thermal stability) were obtained when the lipase was immobilized on SiO(2)-PVA. The superiority of this immobilized system was also confirmed in the transe-sterification of both feedstocks, attained higher yields and productivities. (C) 2010 Elsevier Ltd. All rights reserved.

Linoleic acid peroxidation and lignin degradation by enzymes produced by Ceriporiopsis subvermispora grown on wood or in submerged liquid cultures

Ceriporiopsis subvermispora is a white-rot fungus used in biopulping processes and seems to use the fatty acid peroxidation reactions initiated by manganese-peroxidase (MnP) to start lignin degradation. The present work shows that C. subvermispora was able to peroxidize unsaturated fatty acids during wood biotreatment under biopulping conditions. In vitro assays showed that the extent of linoleic acid peroxidation was positively correlated with the level of MnP recovered from the biotreated wood chips. Milled wood was treated in vitro by partially purified MnP and linoleic acid. UV spectroscopy and size exclusion chromatography (SEC) showed that soluble compounds similar to lignin were released from the milled wood. SEC data showed a broad elution profile compatible with low molar mass lignin fractions. MnP-treated milled wood was analyzed by thioacidolysis. The yield of thioacidolysis monomers recovered from guaiacyl and syringyl units decreased by 33% and 20% in MnP-treated milled wood, respectively. This has suggested that lignin depolymerization reactions have occurred during the MnP/linoleic acid treatment. (C) 2009 Elsevier Inc. All rights reserved.

Biomimetic oxidative treatment of spruce wood studied by pyrolysis-molecular beam mass spectrometry coupled with multivariate analysis and (13)C-labeled tetramethylammonium hydroxide thermochemolysis: implications for fungal degradation of wood

In this work, pyrolysis-molecular beam mass spectrometry analysis coupled with principal components analysis and (13)C-labeled tetramethylammonium hydroxide thermochemolysis were used to study lignin oxidation, depolymerization, and demethylation of spruce wood treated by biomimetic oxidative systems. Neat Fenton and chelator-mediated Fenton reaction (CMFR) systems as well as cellulosic enzyme treatments were used to mimic the nonenzymatic process involved in wood brown-rot biodegradation. The results suggest that compared with enzymatic processes, Fenton-based treatment more readily opens the structure of the lignocellulosic matrix, freeing cellulose fibrils from the matrix. The results demonstrate that, under the current treatment conditions, Fenton and CMFR treatment cause limited demethoxylation of lignin in the insoluble wood residue. However, analysis of a water-extractable fraction revealed considerable soluble lignin residue structures that had undergone side chain oxidation as well as demethoxylation upon CMFR treatment. This research has implications for our understanding of nonenzymatic degradation of wood and the diffusion of CMFR agents in the wood cell wall during fungal degradation processes.

Multipoint covalent immobilization of lipase on chitosan hybrid hydrogels: influence of the polyelectrolyte complex type and chemical modification on the catalytic properties of the biocatalysts

This work aimed at the production of stabilized derivatives of Thermomyces lanuginosus lipase (TLL) by multipoint covalent immobilization of the enzyme on chitosan-based matrices. The resulting biocatalysts were tested for synthesis of biodiesel by ethanolysis of palm oil. Different hydrogels were prepared: chitosan alone and in polyelectrolyte complexes (PEC) with kappa-carrageenan, gelatin, alginate, and polyvinyl alcohol (PVA). The obtained supports were chemically modified with 2,4,6-trinitrobenzene sulfonic acid (TNBS) to increase support hydrophobicity, followed by activation with different agents such as glycidol (GLY), epichlorohydrin (EPI), and glutaraldehyde (GLU). The chitosan-alginate hydrogel, chemically modified with TNBS, provided derivatives with higher apparent hydrolytic activity (HA(app)) and thermal stability, being up to 45-fold more stable than soluble lipase. The maximum load of immobilized enzyme was 17.5 mg g(-1) of gel for GLU, 7.76 mg g(-1) of gel for GLY, and 7.65 mg g(-1) of gel for EPI derivatives, the latter presenting the maximum apparent hydrolytic activity (364.8 IU g(-1) of gel). The three derivatives catalyzed conversion of palm oil to biodiesel, but chitosan-alginate-TNBS activated via GLY and EPI led to higher recovered activities of the enzyme. Thus, this is a more attractive option for both hydrolysis and transesterification of vegetable oils using immobilized TLL, although industrial application of this biocatalyst still demands further improvements in its half-life to make the enzymatic process economically attractive.

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.

Effect of pH and oxalic acid on the reduction of Fe(3+) by a biomimetic chelator and on Fe(3+) desorption/adsorption onto wood: Implications for brown-rot decay

Fenton reaction is thought to play an important role in wood degradation by brown-rot fungi. In this context, the effect of oxalic acid and pH on iron reduction by a biomimetic fungal chelator and on the adsorption/desorption of iron to/from wood was investigated. The results presented in this work indicate that at pH 2.0 and 4.5 and in the presence of oxalic acid, the phenolate chelator 2,3-dihydroxybenzoic acid (2,3-DHBA) is capable of reducing ferric iron only when the iron is complexed with oxalate to form Fe mono-oxalate (Fe(C(2)O(4))(+)). Within the pH range tested in this work, this complex formation occurs when the oxalate:Fe(3+) molar ratio is less than 20 (pH 2.0) or less than 10 (pH 4.5). When aqueous ferric iron was passed through a column packed with milled red spruce (Picea rubens) wood equilibrated at pH 2.0 and 4.5. it was observed that ferric iron binds to wood at pH 4.5 but not at pH 2.0, and the bound iron could then be released by application of oxalic acid at pH 4.5. The release of bound iron was dependent on the amount of oxalic acid applied in the column. When the amount of oxalate was at least 20-fold greater than the amount of iron bound to the wood, all bound iron was released. When Fe-oxalate complexes were applied to the milled wood column equilibrated in the pH range of 2-4.5, iron from Fe-oxalate complexes was bound to the wood only when the pH was 3.6 or higher and the oxalate:Fe(3+) molar ratio was less than 10. When 2,3-DHBA was evaluated for its ability to release iron bound to the milled wood, it was found that 2,3-DHBA possessed a greater affinity for ferric iron than the wood as 2,3-DHBA was capable of releasing the ferric iron bound to the wood in the pH range 3.6-5.5. These results further the understanding of the mechanisms employed by brown-rot fungi in wood biodegradation processes. (C) 2009 Elsevier Ltd. All rights reserved.

Evaluation of Electrical Properties of Lap Joints for BSCCO and YBCO Tapes

The joint process between tapes of coated conductors is a critical issue for the most of the applications of high temperature superconductors (HTS). Using different fabrication techniques joints of YBCO coated superconductors were prepared and characterized through electrical measurements. For soldering material low melting point eutectic alloys, such as In-Sn (m.p. 116 degrees C) and Sn-Pb (m. p. 189 degrees C) were selected to prepare lap joints with effective length between 1 to 20 cm. The splice resistance and the critical current of the joints were evaluated by I-V curve measurements with the maximum current strength above the critical current, in order to evaluate the degree of degradation for each joint method. Pressed lap joints prepared with tapes without external reinforcement presented low resistance lap joint nevertheless some critical current degradation occurs when strong pressing is applied. When mechanical pressure is applied during the soldering process we can reduce the thickness of the solder alloy and a residual resistance arises from contributions of high resistivity matrix and external reinforcement. The lap joints for reinforced tape were prepared using two methods: the first, using ""as-supplied"" tape and the other after reinforcement-removal; in the latter case, the tapes were resoldered using Sn-Pb alloy. The results using several joint geometries, distinct surface preparation processes and different soldering materials are presented and analysed. The solder alloy with lower melting point and the longer joint length presented the smallest joint resistance.

Influence of Granulometry and Organic Treatment of a Brazilian Montmorillonite on the Properties of Poly(styrene-co-n-butyl acrylate)/Layered Silicate Nanocomposites Prepared by Miniemulsion Polymerization

The influence of granulometry and organic treatment of a Brazilian montmorillonite (MMT) clay on the synthesis and properties of poly(styrene-co-n-butyl acrylate)/layered silicate nanocomposites was studied. Hybrid latexes of poly(styrene-co-butyl acrylate)/MMT were synthesized via miniemulsion polymerization using either sodium or organically modified MMT. Five clay granulometries ranging from clay particles smaller than 75 mu m to colloidal size were selected. The size of the clay particles was evaluated by Specific surface area measurements (BET). Cetyl trimethyl ammonium chloride was used as an organic modifier to enhance the clay compatibility with the monomer phase before polymerization and to improve the clav distribution and dispersion within the polymeric matrix after polymerization. The sodium and organically modified natural clays as well as the composites were characterized by X-ray diffraction analysis. The latexes were characterized by dynamic light scattering. The mechanical, thermal, and rheological properties of the composites obtained were characterized by dynamical-mechanical analysis, thermogravimetry, and small amplitude oscillatory, shear tests, respectively. The results showed that smaller the size of the organically modified MMT, the higher the degree of exfoliation of nanoplatelets. Hybrid latexes in presence of Na-MMT resulted in materials with intercalated structures. (C) 2009 Wiley, Periodicals, Inc. J Appl Polym Sci 112: 1949-1958, 2009

Laboratory and mill scale evaluation of biopulping of Eucalyptus grandis Hill ex Maiden with Phanerochaete chrysosporium RP-78 under non-aseptic conditions

Biopulping of Eucalyptus grandis wood chips with Phanerochaete chrysosporium RP-78 was evaluated under non-aseptic conditions in laboratory and mill wood-yard. The ability of P. chrysosporium to compete with indigenous fungi present in fresh wood chips was notorious under controlled laboratory experiments. A subsequent step involved an industrial test performed with 10-ton of fresh wood chips inoculated and maintained at 37 +/- 38 degrees C for 39 days in a biopulping pilot plant. Biotreated wood chips were pulped in a chemithermomechanical pulping mill. Net energy consumption during refining was 745 kWh ton(-1) and 610 kWh ton(-1) of processed pulp for control and biotreated wood chips, respectively. Accordingly, 18.5% net energy saving could be achieved. Biopulps contained lower shive content and had improved strength properties compared to control pulps. Tensile index improved from 25 +/- 1 N m g(-1) to 33.6 +/- 0.5 N m g(-1) and delamination strength from 217 +/- 19 kPa to 295 +/- 30 kPa.

Thermal, structural and optical properties of Al(2)CoO(4)-Crocoite composite nanoparticles used as pigments

Al(2)CoO(4)-PbCrO(4) and Al(2)CoO(4)-Pb(2)CrO(5) crystalline powders in different proportions were obtained by the polymeric precursor method. Differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques were used to accurately characterize the distinct thermal events occurring during synthesis. The TG and DSC results revealed a series of overlapping decomposition reactions due to different exothermal events, which were identified as H(2)O and NO(x) elimination and polymer pyrolysis. The X-ray diffraction patterns of the xAl(2)CoO(4)-(1 - x)PbCrO(4) and xAl(2)CoO(4)-(1 - x)Pb(2)CrO(5) mixed compounds, with x = 1, 0.75, 0.5, 0.25 and 0, were obtained in the crystalline form with their respective phases, and proved consistent with the nominal compositions. The synthesis of these two systems yielded nine different colors and shades.

Behaviour of biofuel addition on metallurgical properties of sinter

Blast furnace gas yield is essentially controlled by a gas-solid reaction phenomenon, which strongly influences hot metal manufacturing costs. As a result of rising prices for reducing agents on the international market, Companhia Siderurgica Nacional decided to inject natural gas into its blast furnaces. With more gas inside the furnace, the burden permeability became even more critical. To improve blast furnace gas yield, a new technological approach was adopted; raising the metallic burden reaction surface. To that end, a special sinter was developed with permeability being controlled by adding micropore nucleus forming agents, cellulignin coal, without, however, degrading its mechanical properties. This paper shows the main process parameters and the results from physicochemical characterisation of a sinter with controlled permeability, on a pilot scale, compared to those of conventional sinter. Gas flow laboratory simulations have conclusively corroborated the positive effects of micropore nucleus forming agents on enhancing sinter permeability.

Influence of laser surface texturing on surface microstructure and mechanical properties of adhesive joined steel sheets

This work discusses the resultant microstructure of laser surface treated galvanised steel and the mechanical properties of adhesively bonded surfaces therein. The surface microstructure obtained at laser intensities between 170 and 1700 MW cm 22 exhibit zinc melting and cavity formation. The wavy surface morphology of the treated surface exhibits an average roughness Ra between 1.0 and 1.5 mu m, and a mean roughness depth R(z) of 8.6 mu m. Atomic force microscopic analyses revealed that the R(z) inside the laser shot cavities increased from 68 to 243 nm when the incident laser intensity was increased from 170 to 1700 MW cm(-2). X-ray fluorescence analyses were used to measure Zn coating thicknesses as a function of process parameters. Both X-ray fluorescence and X-ray diffraction analyses demonstrated that the protective coating remains at the material surface, and the steel structure beneath was not affected by the laser treatment. Tensile tests under peel strength conditions demonstrated that the laser treated adhesively joined samples had resistance strength up to 88 MPa, compared to a maximum of only 23 MPa for the untreated surfaces. The maximum deformation for rupture was also greatly increased from 0.07%, for the original surface, to 0.90% for the laser treated surfaces.