Linear viscoelasticity of styrenic block copolymers-clay nanocomposites

In this work, the rheological behavior of block copolymers with different morphologies (lamellar, cylindrical, spherical, and disordered) and their clay-containing nanocomposites was studied using small amplitude oscillatory shear. The copolymers studied were one asymmetric starblock styrene-butadiene-styrene copolymer and four styrene-ethylene/butylenes-styrene copolymers with different molecular architectures, one of them being modified with maleic anhydride. The nanocomposites of those copolymers were prepared by adding organophilic clay using three different preparation techniques: melt mixing, solution casting, and a hybrid melt mixing-solution technique. The nanocomposites were characterized by X-ray diffraction and transmission electron microscopy, and their viscoelastic properties were evaluated and compared to the ones of the pure copolymers. The influence of copolymer morphology and presence of clay on the storage modulus (G`) curves was studied by the evaluation of the changes in the low frequency slope of log G` x log omega (omega: frequency) curves upon variation of temperature and clay addition. This slope may be related to the degree of liquid- or solid-like behavior of a material. It was observed that at temperatures corresponding to the ordered state, the rheological behavior of the nanocomposites depended mainly on the viscoelasticity of each type of ordered phase and the variation of the slope due to the addition of clay was small. For temperatures corresponding to the disordered state, however, the rheological behavior of the copolymer nanocomposites was dictated mostly by the degree of clay dispersion: When the clay was well dispersed, a strong solid-like behavior corresponding to large G` slope variations was observed.

Phase equilibria of lysozyme precipitation with the volatile salt ammonium carbamate

Lysozyme precipitation induced by the addition of the volatile salt ammonium carbamate was studied through cloud-point measurements and precipitation assays. Phase equilibrium experiments were carried out at 5.0, 15.0 and 25.0 degrees C and the compositions of the coexisting phases were determined. A complete separation of the coexisting liquid and solid phases could not be achieved. Nevertheless it was possible to determine the composition of the solid precipitate through the extensions of experimental tie lines. The same precipitate was found at all temperatures. Lysozyme enzymatic activities of the supernatant and precipitate phases were also determined. The activity balance suggests that ammonium carbamate preserves lysozyme activity after the salting-out precipitation. (C) 2010 Elsevier B.V. All rights reserved.

Precipitation of Porcine Insulin With Carbon Dioxide

Recent works have pointed to the use of volatile electrolytes such as carbon dioxide (CO(2)) dissolved in aqueous solutions as a promising alternative to the precipitating agents conventionally used for protein recovery in the food and pharmaceutical industries. In this work we investigated experimental and theoretical aspects of the precipitation of porcine insulin, a biomolecule of pharmaceutical interest, using CO(2) as an acid- precipitating agent. The Solubility of porcine insulin in NaHCO(3) solutions in pressurized CO(2) was determined as a function of temperature and pressure, with a minimum being observed close to the protein isoclectric point. A thermodynamic model was developed and successfully utilized to correlate the experimental data. Insulin was considered a polyelectrolyte in the model and its self-association reactions were also taken into account. The biological activity of insulin was maintained after precipitation With CO(2), although some activity can be lost if foam is formed in the depressurization step. Biotechnol. Bioeng. 2009;103: 909-919. (C) 2009 Wiley Periodicals, Inc.

Cryogenic operation of FinFETs aiming at analog applications

FinFETs are recognized as promising candidates for the CMOS nanometer era. In this paper the most recent results for cryogenic operation of FinFETs will be demonstrated with special emphasis on analog applications. Threshold voltage, subthreshold slope and carrier mobility will be studied. Also some important figures of merit for analog circuit operation as for readout electronics, such as transconductance, output conductance and intrinsic voltage gain will be covered. It is demonstrated that the threshold voltage of undoped narrow FinFETs is less temperature-dependent than for a planar single-gate device with similar doping concentration. The temperature reduction improves the transconductance over drain current ratio in any operational region. On the other hand, the output conductance is degraded when the temperature is reduced. The combination of these effects shows that the intrinsic gain of a L = 90 nm FinFET is degraded by 2 dB when the temperature reduces from 300 K to 100 K. (C) 2009 Elsevier Ltd. All rights reserved.

Cryogenic Operation of Junctionless Nanowire Transistors

This letter presents the properties of nMOS junctionless nanowire transistors (JNTs) under cryogenic operation. Experimental results of drain current, subthreshold slope, maximum transconductance at low electric field, and threshold voltage, as well as its variation with temperature, are presented. Unlike in classical devices, the drain current of JNTs decreases when temperature is lowered, although the maximum transconductance increases when the temperature is lowered down to 125 K. An analytical model for the threshold voltage is proposed to explain the influence of nanowire width and doping concentration on its variation with temperature. It is shown that the wider the nanowire or the lower the doping concentration, the higher the threshold voltage variation with temperature.

Determining the effect of grain size and maximum induction upon coercive field of electrical steels

Although theoretical models have already been proposed, experimental data is still lacking to quantify the influence of grain size upon coercivity of electrical steels. Some authors consider a linear inverse proportionality, while others suggest a square root inverse proportionality. Results also differ with regard to the slope of the reciprocal of grain size-coercive field relation for a given material. This paper discusses two aspects of the problem: the maximum induction used for determining coercive force and the possible effect of lurking variables such as the grain size distribution breadth and crystallographic texture. Electrical steel sheets containing 0.7% Si, 0.3% Al and 24 ppm C were cold-rolled and annealed in order to produce different grain sizes (ranging from 20 to 150 mu m). Coercive field was measured along the rolling direction and found to depend linearly on reciprocal of grain size with a slope of approximately 0.9 (A/m)mm at 1.0 T induction. A general relation for coercive field as a function of grain size and maximum induction was established, yielding an average absolute error below 4%. Through measurement of B(50) and image analysis of micrographs, the effects of crystallographic texture and grain size distribution breadth were qualitatively discussed. (C) 2011 Elsevier B.V. All rights reserved.

Transport Barkhausen-like noise in uniaxially pressed Bi(1.65)Pb(0.35)Sr(2)Ca(2)Cu(3)O(10+delta) ceramic samples

We report on the detection of the transport Barkhausen-like noise (TBN) in polycrystalline samples of Bi(1.65)Pb(0.35)Sr(2)Ca(2) Cu(3)O(10+delta) (Bi-2223) which were subjected to different uniaxial compacting pressures. The transport Barkhausen-like noise was measured when the sample was subjected to an ac triangular-shape magnetic field (f similar to 1 Hz) with maximum amplitude B(max) approximate to 5.5 mT, in order to avoid the flux penetration within the superconducting grains. Analysis of the TBN signal, measured for several values of excitation current density, indicated that the applied magnetic field in which the noise signal first appears, B(a)(t(i)), is closely related to the magnetic-flux pinning capability of the material. The combined results are consistent with the existence of three different superconducting levels within the samples: (i) the superconducting grains; (ii) the superconducting clusters; and (iii) the weak-links. We finally argue that TBN measurements constitute a powerful tool for probing features of the intergranular transport properties in polycrystalline samples of high-T(c) superconductors. (C) 2010 Elsevier B.V. All rights reserved.

Thin titanium oxide films deposited by e-beam evaporation with additional rapid thermal oxidation and annealing for ISFET applications

Titanium oxide (TiO(2)) has been extensively applied in the medical area due to its proved biocompatibility with human cells [1]. This work presents the characterization of titanium oxide thin films as a potential dielectric to be applied in ion sensitive field-effect transistors. The films were obtained by rapid thermal oxidation and annealing (at 300, 600, 960 and 1200 degrees C) of thin titanium films of different thicknesses (5 nm, 10 nm and 20 nm) deposited by e-beam evaporation on silicon wafers. These films were analyzed as-deposited and after annealing in forming gas for 25 min by Ellipsometry, Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy (RAMAN), Atomic Force Microscopy (AFM), Rutherford Backscattering Spectroscopy (RBS) and Ti-K edge X-ray Absorption Near Edge Structure (XANES). Thin film thickness, roughness, surface grain sizes, refractive indexes and oxygen concentration depend on the oxidation and annealing temperature. Structural characterization showed mainly presence of the crystalline rutile phase, however, other oxides such Ti(2)O(3), an interfacial SiO(2) layer between the dielectric and the substrate and the anatase crystalline phase of TiO(2) films were also identified. Electrical characteristics were obtained by means of I-V and C-V measured curves of Al/Si/TiO(x)/Al capacitors. These curves showed that the films had high dielectric constants between 12 and 33, interface charge density of about 10(10)/cm(2) and leakage current density between 1 and 10(-4) A/cm(2). Field-effect transistors were fabricated in order to analyze I(D) x V(DS) and log I(D) x Bias curves. Early voltage value of -1629 V, R(OUT) value of 215 M Omega and slope of 100 mV/dec were determined for the 20 nm TiO(x) film thermally treated at 960 degrees C. (C) 2009 Elsevier B.V. All rights reserved.

Technological characterization of phosphate ore types from the Salitre Alkaline Complex, MG - Fosfertil Area

The present study was carried out on six different ore types from the Salitre Alkaline Complex aiming to determine their mineralogical composition and the major features that are relevant in the mineral processing. The P(2)O(5) grades vary from 9 to 25%. The slime content (-0, 020 mm) varies between 20 and 34% (w/w) and carries 17-22% of the P(2)O(5) content. The samples essentially consist of apatite, iron oxi-hydroxides, ilmenite, clay minerals, carbonate, quartz, pyroxene, perovskite, secondary phosphates and other minor accessory minerals. Below 0.21 mm, apatite essentially occurs in free particles showing a clean surface or a weak coating of it-on oxi-hydroxides; the highly covered apatite (not recoverable by flotation) varies from 6 to 9%. In the deslimed fraction (above 0.020 mm) more than 97% of the total phosphor content occurs as apatite; the estimated P 2 0 5 potential recovery in flotation concentration is over 90% (71-76% overall recovery).

Time stability of soil water storage measured by neutron probe and the effects of calibration procedures in a small watershed

The knowledge of soil water storage (SWS) of soil profiles is crucial for the adoption of vegetation restoration practices. With the aim of identifying representative sites to obtain the mean SWS of a watershed, a time stability analysis of neutron probe evaluations of SWS was performed by the means of relative differences and Spearman rank correlation coefficients. At the same time, the effects of different neutron probe calibration procedures were explored on time stability analysis. mean SWS estimation. and preservation of the spatial variability of SWS. The selected watershed, with deep gullies and undulating slopes which cover an area of 20 ha, is characterized by an Ust-Sandiic Entisol and an Aeolian sandy soil. The dominant vegetation species are bunge needlegrass (Stipa bungeana Trim) and korshinsk peashrub (Carugano Korshinskii kom.). From June 11, 2007 to July 23,2008, SWS of the top1 m soil layer was evaluated for 20 dates, based on neutron probe data of 12 sampling sites. Three calibration procedures were employed: type 1, most complete, with each site having its own linear calibration equation (TrE); type II. with TrE equations extended over the whole field: and type III, with one single linear calibration curve for the whole field (UnE) and also correcting its intercept based on site specific relative difference analysis (RdE) and on linear fitting of data (RcE), both maintaining the same slope. A strong time stability of SWS estimated by TrE equations was identified. Soil particle size and soil organic matter content were recognized as the influencing factors for spatial variability of SWS. Land use influenced neither the spatial variability nor the time stability of SWS. Time stability analysis identified one site to represent the mean SWS of the whole watershed with mean absolute percentage errors of less than 10%, therefore. this site can be used as a predictor for the mean SWS of the watershed. Some equations of type II were found to be unsatisfactory to yield reliable mean SWS values or in preserving the associated soil spatial variability. Hence, it is recommended to be cautious in extending calibration equations to other sites since they might not consider the field variability. For the equations with corrected intercept (type III), which consider the spatial variability of calibration in a different way in relation to TrE, it was found that they can yield satisfactory means and standard deviation of SWS, except for the RdE equations, which largely leveled off the SWS values in the watershed. Correlation analysis showed that the neutron probe calibration was linked to soil bulk density and to organic matter content. Therefore, spatial variability of soil properties should be taken into account during the process of neutron probe calibration. This study provides useful information on the mean SWS observation with a time stable site and on distinct neutron probe calibration procedures, and it should be extended to soil water management studies with neutron probes, e.g., the process of vegetation restoration in wider area and soil types of the Loess Plateau in China. (C) 2009 Elsevier B.V. All rights reserved.

Changes in wood-water relationship due to heat treatment assessed on micro-samples of three Eucalyptus species

Wood-water relationship of untreated and heat-treated wood was studied. Specimens of Eucalyptus grandis, E saligna, and E citriodora were submitted to five conditions of heat treatment: 180 degrees C and 220 degrees C with air; 220 degrees C, 250 degrees C, and 280 degrees C with N(2). The wood-water relationships were accurately studied in a special device, in which the moisture content (MC) of the sample was measured with a highly sensitive electronic microbalance placed in a climatic chamber. The dimensions of the sample were collected continuously without contact by means of two high-speed laser scan micrometers. Sorption curves and shrinkage-MC relationships were observed. To study the effects of heat treatment, the following parameters were also determined: fiber saturation point (FPS), wood anisotropy (T/R ratio), shrinkage slope, reduction in hygroscopicity, and anti-shrink efficiency (ASE). The physical properties were significantly affected only at 220 degrees C and above. At heat temperature levels higher than 220 degrees C, the reduction in hygroscopicity and ASE are higher than 40% and continue to be reduced with increasing temperature level. This work also demonstrates that heat treatment does not change the slope of the curves shrinkage vs. MC, proving that heat treatment affects the domain of alterations in wood properties, but not the behavior within this domain.

Spatial pattern of black spot incidence within citrus trees related to disease severity and pathogen dispersal

Guignardia citricarpa, the causal agent of citrus black spot, forms airborne ascospores on decomposing citrus leaves and water-spread conidia on fruits, leaves and twigs. The spatial pattern of diseased fruit in citrus tree canopies was used to assess the importance of ascospores and conidia in citrus black spot epidemics in Sao Paulo State, Brazil. The aggregation of diseased fruit in the citrus tree canopy was quantified by the binomial dispersion index (D) and the binary form of Taylor`s Power Law for 303 trees in six groves. D was significantly greater than 1 in 251 trees. The intercept of the regression line of Taylor`s Power Law was significantly greater than 0 and the slope was not different from 1, implying that diseased fruit was aggregated in the canopy independent of disease incidence. Disease incidence (p) and severity (S) were assessed in 2875 citrus trees. The incidence-severity relationship was described (R-2 = 88.7%) by the model ln(S) = ln(a) + bCLL(p) where CLL = complementary log-log transformation. The high severity at low incidence observed in many cases is also indicative of low distance spread of G. citricarpa spores. For the same level of disease incidence, some trees had most of the diseased fruit with many lesions and high disease severity, whereas other trees had most of the fruit with few lesions and low disease severity. Aggregation of diseased fruit in the trees suggests that splash-dispersed conidia have an important role in increasing the disease in citrus trees in Brazil.

Effect of cooking on non-starch polysaccharides of hard-to-cook beans

Experiments carried out to study changes induced by hard-to-cook (HTC) phenomenon in the non-starch polysaccharides of beans stored at 30 degrees C and 75% RH for 8 months showed that the development of HTC did not affect the amounts of soluble and insoluble fibre in cooked seeds but changed their carbohydrates physical properties. Aged beans non-starch polysaccharides presented lower water-solubility and underwent lower degradation of galacturonans and arabinose-rich polysaccharides when submitted to cooking. The decrease in non-starch polysaccharides water-solubility produced a shift in the polymers fractionation profile which resulted in an increase of weak and middle-alkali soluble polymers bulk as well as in their arabinose and uronic acid contents. Uronic acid contents were higher in polymers released by 1 M NaOH and in the cellulose-rich residues while the arabinose contents were higher in the mild-alkali soluble polymers of aged seeds. Methylation analysis showed no evident alterations in the xyloglucans and arabinans branching degree with beans ageing. However, both, the molecular mass of water-soluble pectins and CDTA-soluble pectins, increased. Even though changes in the non-starch polysaccharide solubility were not related to the decrease in the arabinan and xyloglucan degree of branching they may be related to the formation of new chemical interactions other than hydrogen bond. There was a correlation between acidic and neutral polysaccharides insolubilisation in beans ageing and probably in beans hardening. After processing, aged seeds present higher amounts of insoluble fibre when compared to normal beans. (C) 2008 Elsevier Ltd. All rights reserved.

Stability of clavulanic acid under variable pH, ionic strength and temperature conditions. A new kinetic approach

Clavulanic acid (CA) is a beta-lactam antibiotic that alone exhibits only weak antibacterial activity, but is a potent inhibitor of beta-lactamases enzymes. For this reason it is used as a therapeutic in conjunction with penicillins and cephalosporins. However, it is a well-known fact that it is unstable not only during its production phase, but also during downstream processing. Therefore, the main objective of this study was the evaluation of CA long-term stability under different conditions of pH and temperature, in the presence of variable levels of different salts, so as to suggest the best conditions to perform its simultaneous production and recovery by two-phase polymer/salt liquid-liquid extractive fermentation. To this purpose, the CA stability was investigated at different values of pH (4.0-8.0) and temperature (20-45 degrees C), and the best conditions were met at a pH 6.0-7.2 and 20 degrees C. Its stability was also investigated at 30 degrees C in the presence of NaCl, Na(2)SO(4), CaCl(2) and MgSO(4) at concentrations of 0.1 and 0.5 M in Mcllvaine buffer (pH 6.5). All salts led to increased CA instability with respect to the buffer alone, and this effect decreased in following sequence: Na(2)SO(4) > MgSO(4) > CaCl(2) > NaCl. Kinetic and thermodynamic parameters of CA degradation were calculated adopting a new model that took into consideration the equilibrium between the active and a reversibly inactivated form of CA after long-time degradation. (C) 2009 Elsevier B.V. All rights reserved.

Synthesis and characterization of the [Ru(3)O(CH(3)COO)(6)(py)(2)(BPE)Ru(bpy)(2)Cl](PF(6))(2) dimer

The polymetallic [Ru(3)O(CH(3)COO)(6)(py)(2)(BPE)Ru( bpy)(2)Cl](PF(6))(2) complex (bpy = 2,2`-bipyridine, BPE = trans- 1,2-bis(4-pyridil) ethylene and py = pyridine) was assembled by the combination of an electroactive [Ru(3)O] moiety with a [ Ru( bpy) 2( BPE) Cl] photoactive centre, and its structure was determined using positive ion electrospray (ESI-MS) and tandem mass (ESI-MS/MS) spectrometry. The [Ru(3)O(CH(3)COO)(6)(py)(2)(BPE)Ru(bpy)(2)Cl] (2+) doubly charged ion of m/z 732 was mass-selected and subject to 15 eV collision-induced dissociation, leading to a specific dissociation pattern, diagnostic of the complex structure. The electronic spectra display broad bands at 409, 491 and 692 nm ascribed to the [Ru(bpy)(2)(BPE)] charge-transfer bands and to the [Ru(3)O] internal cluster transitions. The cyclic voltammetry shows five reversible waves at - 1.07 V, 0.13 V, 1.17 V, 2.91 V and - 1.29 V (vs SHE) assigned to the [Ru(3)O](-1/0/+ 1/+ 2/+3) and to the bpy (0/-1) redox processes; also a wave is observed at 0.96 V, assigned to the Ru (+2/+ 3) pair. Despite the conjugated BPE bridge, the electrochemical and spectroelectrochemical results indicate only a weak coupling through the pi-system, and preliminary photophysical essays showed the compound decomposes under visible light irradiation.