340 resultados para REDOX BEHAVIOR


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During the transition from single crystalline to polycrystalline behavior, the available data show the strength increasing or decreasing as the number of grains in a cross section is reduced. Tensile experiments were conducted on polycrystalline Ni with grain sizes (d) between 16 and 140 mu m and varying specimen thickness (t), covering a range of lambda (-t/d) between similar to 0.5 and 20. With a decrease in lambda, the data revealed a consistent trend of strength being independent of lambda at large lambda, an increase in strength, and then a decrease in strength. Microstructural studies revealed that lower constraints enabled easier rotation of the surface grains and texture evolution, independent of the specimen thickness. In specimen interiors, there was a greater ease of rotation in thinner samples. Measurements of misorientation deviations within grains revealed important differences in the specimen interiors. A simple model is developed taking into account the additional geometrically necessary dislocations due to variations in the behavior of surface and interior grains, leading to additional strengthening. A suitable combination of this strengthening and surface weakening can give rise to wide range of possibilities with a decrease in lambda, including weakening, strengthening, and strengthening and weakening.

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Zn1-xMgxO ( <= x <= 0.1) ceramics were fabricated by conventional solid-state reaction of co-precipitated zinc oxide and magnesium hydroxide nanoparticles. Structural and morphological properties of the fabricated ceramics were studied using X-ray diffraction and scanning electron microscopic analysis. The dielectric measurements of the ceramics were carried out as a function of frequency and temperature respectively. Interestingly, Mg doped ZnO (MZO) samples exhibited colossal dielectric response (similar to 1 x 10(4) at 1 kHz) with Debye like relaxation. The detailed dielectric studies and thermal analyses showed that the unusual dielectric response of the samples were originated from the defected grain and grain boundary (GB) conductivity relaxations due to the absorbed atmospheric water vapor (moisture). Impedance spectroscopy was employed to determine the defected grain and GB resistances, capacitances and which supported Maxwell-Wagner type relaxation phenomena. (C) 2015 Elsevier Ltd. All rights reserved.

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Determination of shear strength of brick-mortar bed joint is critical to overcome the sliding-shear or joint-shear failure in masonry. In the recent past, researchers have attempted to enhance the shear strength and deformation capacity of brick-mortar bed joints by gluing fiber-reinforced polymer (FRP) composite across the bed joint. FRP composites offer several advantages like high strength-to-weight ratio, and ease of application in terms of labor, time, and reduced curing period. Furthermore, FRP composites are desirable for strengthening old masonry buildings having heritage value because of its minimal interference with the existing architecture. A majority of earlier studies on shear strengthening of masonry available in the literature adopted masonry having the ratio of modulus of elasticity of masonry unit (Emu) to modulus of elasticity of mortar (Em) greater than one. Information related to shear behavior of FRP glued masonry composed of masonry units having Young's modulus lower than mortar is limited. Hence the present study is focused on characterizing the interfacial behavior of brick-mortar bed joint of masonry assemblages composed of solid burnt clay bricks and cement-sand mortar (E-mu/E-m ratio less than one), strengthened with FRP composites. Masonry triplets and prisms with bed joint inclined to loading axis (0 degrees, 30 degrees, 45 degrees, 60 degrees and 90 degrees) are employed in this study. Glass and carbon FRP composites composed of bidirectional FRP fabric with equal density in both directions are used for strengthening masonry. Masonry triplets are glued with glass and carbon FRP composites in two configurations: (1) both faces of the triplet specimens are fully glued with GFRP composites; and (2) both faces of the triplet specimens are glued with GFRP and CFRP composites in strip form. The performance of masonry assemblages strengthened with FRP composites is assessed in terms of gain in shear strength, shear displacement, and postpeak behavior for various configurations and types of FRP composites considered. A semianalytical model is proposed for the prediction of shear strength of masonry bed joints glued with FRP composites. A composite failure envelope consisting of a Coulomb friction model and a compression cap is obtained for unreinforced masonry and GFRP-strengthened masonry based on the test results of masonry triplets and masonry prisms with bed joints having various inclinations to the loading (C) 2015 American Society of Civil Engineers.

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The hot deformation behavior of Nb-1 wt.%Zr alloy was studied using uniaxial compression tests carried out in vacuum to a true strain of 0.6 in the temperature range of 900 to 1700 degrees C and the strain rate range of 3 x 10(-3) to 10 s(-1). The optimum regime of hot workability of Nb-1Zr alloy was determined from the strain rate sensitivity (m) contour plots. A high m of about 02 was obtained in the temperature and strain rate range of 1200-1500 degrees C and 10(-3) to 10(-1) s(-1) and 1600-1700 degrees C and 10(-1) to 1 s(-1). Microstructure of the deformed samples showed features of dynamic recrystallization within the high strain rate sensitivity domain. Compared to the study on Nb-1Zr-0.1C alloy, Nb-1Zr showed a lower flow stress and an optimum hot working domain at lower temperatures. In the 1500 to 1700 degrees C range the apparent activation energy of deformation for Nb-1Zr was 259 kJ mol(-1), the stress exponent 5, and the activation volume about 200 to 700 b(3). (C) 2015 Elsevier Ltd. All rights reserved.

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The ability of Mycobacterium tuberculosis to resist intraphagosomal stresses, such as oxygen radicals and low pH, is critical for its persistence. Here, we show that a cytoplasmic redox sensor, WhiB3, and the major M. tuberculosis thiol, mycothiol (MSH), are required to resist acidic stress during infection. WhiB3 regulates the expression of genes involved in lipid anabolism, secretion, and redox metabolism, in response to acidic pH. Furthermore, inactivation of the MSH pathway subverted the expression of whiB3 along with other pH-specific genes in M. tuberculosis. Using a genetic biosensor of mycothiol redox potential (E-MSH), we demonstrated that a modest decrease in phagosomal pH is sufficient to generate redox heterogeneity in E-MSH of the M. tuberculosis population in a WhiB3-dependent manner. Data indicate that M. tuberculosis needs low pH as a signal to alter cytoplasmic E-MSH, which activates WhiB3-mediated gene expression and acid resistance. Importantly, WhiB3 regulates intraphagosomal pH by down-regulating the expression of innate immune genes and blocking phagosomal maturation. We show that this block in phagosomal maturation is in part due to WhiB3-dependent production of polyketide lipids. Consistent with these observations, Mtb Delta whiB3 displayed intramacrophage survival defect, which can be rescued by pharmacological inhibition of phagosomal acidification. Last, Mtb Delta whiB3 displayed marked attenuation in the lungs of guinea pigs. Altogether, our study revealed an intimate link between vacuolar acidification, redox physiology, and virulence in M. tuberculosis and discovered WhiB3 as crucial mediator of phagosomal maturation arrest and acid resistance in M. tuberculosis.

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The stereology, variant distribution and coarsening behavior of semicoherent alpha(hcp) precipitates in a beta(bcc) matrix of a Ti5553 alloy has been analyzed, and a dominant 3-variant cluster has been observed in which the variants are related to each other by an axis-angle pair <<11(2)over bar> 0 >/60 degrees. Shape and spatial distribution independent elastic self and interaction energies for all pairwise and triplet combinations of a have been calculated and it is found that the 3-cluster combination that is experimentally observed most frequently has the lowest energy for the semicoherent state. The coarsening behavior of the delta distribution follows LSW kinetics after an initial transient, and has been modeled by phase field methods. (C) 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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A real-space high order finite difference method is used to analyze the effect of spherical domain size on the Hartree-Fock (and density functional theory) virtual eigenstates. We show the domain size dependence of both positive and negative virtual eigenvalues of the Hartree-Fock equations for small molecules. We demonstrate that positive states behave like a particle in spherical well and show how they approach zero. For the negative eigenstates, we show that large domains are needed to get the correct eigenvalues. We compare our results to those of Gaussian basis sets and draw some conclusions for real-space, basis-sets, and plane-waves calculations. (C) 2016 AIP Publishing LLC.

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A water soluble `molecular dice' was synthesised via coordination driven self-assembly of a Pd(II) ion with a flexible cationic tritopic donor and was fully characterised using NMR, ESI-MS and single crystal X-ray diffraction analysis. The donor-inherited redox active nature of the `molecular dice' was studied using cyclic voltammetry.

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Epoxy resin GY250 representing diglycidyl ethers of bisphenol-A (DGEBA) was reinforced with 1, 3 and 5 wt % of surface functionalized silver nanoparticles (F-AgNPs) which were synthesized using Couroupita guianensis leaves extract with a view of augmenting the corrosion control property of the epoxy resin and also imparting antimicrobial activity to epoxy coatings on mild steel. Corrosion resistance of the coatings was evaluated by EIS, potentiodynamic polarization studies and cross scratch tests. AFM, SEM, HRTEM and EDX were utilized to investigate the surface topography, morphology and elemental composition of the coatings on MS specimens. Results showed that the corrosion resistance, hardness and T-g of the DGEBA/F-AgNPs coatings increased at 1 wt % of F-AgNPs. The DGEBA/F-AgNPs coatings also offered manifold antimicrobial protection to the MS surfaces by inhibiting the growth of biofilm forming bacteria like P. aeruginosa, B. subtilis, the most common human pathogen E. coli and the most virulent human pathogenic yeast C. albicans.