977 resultados para Solvent-free
Resumo:
Combination of femtosecond Kerr, two photon absorption, and impulsive stimulated Raman scattering (ISRS) experiments have been carried out to investigate the effect of pulse energy and crystal temperature on the generation of coherent polaritons and phonons in 〈110〉 cut ZnTe single crystals of three different resistivities. We demonstrate that the effect of two photon induced free carriers on the creation of both the polaritons and phonons is largest at 4 K where the free carrier lifetime is enhanced. The temperature dependant ISRS on high and low purity ZnTe crystals allows us to unambiguously assign the phonon mode at 3.5 THz to the longitudinal acoustic mode at X-point in the Brillouin zone, LA(X).
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This paper presents a new algorithm for extracting Free-Form Surface Features (FFSFs) from a surface model. The extraction algorithm is based on a modified taxonomy of FFSFs from that proposed in the literature. A new classification scheme has been proposed for FFSFs to enable their representation and extraction. The paper proposes a separating curve as a signature of FFSFs in a surface model. FFSFs are classified based on the characteristics of the separating curve (number and type) and the influence region (the region enclosed by the separating curve). A method to extract these entities is presented. The algorithm has been implemented and tested for various free-form surface features on different types of free-form surfaces (base surfaces) and is found to correctly identify and represent the features irrespective of the type of underlying surface. The representation and extraction algorithm are both based on topology and geometry. The algorithm is data-driven and does not use any pre-defined templates. The definition presented for a feature is unambiguous and application independent. The proposed classification of FFSFs can be used to develop an ontology to determine semantic equivalences for the feature to be exchanged, mapped and used across PLM applications. (C) 2011 Elsevier Ltd. All rights reserved.
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The gamma-phase poly (vinylidene fluoride) (PVDF) films are usually prepared using dimethyl sulfoxide (DMSO) solvent, regardless of preparation temperature. Here we report the crystallization of both alpha and gamma-phase PVDF films by varying preparation temperature using DMSO solvent. The gamma-phase PVDF films were annealed at 70, 90, 110, 130 and 160 degrees C for five hours. The changes in the phase contents in the PVDF at different annealing conditions have been described. When thin films were annealed at 90 degrees C for 5 h, maximum percentage of beta-phase appears in PVDF thin films. The gamma-phase PVDF films completely converted to alpha-phase when they were annealed at 160 degrees C for 5 h. From X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), differential scanning calorimetry (DSC) and Raman studies, it is confirmed that the PVDF thin films, cast from solution and annealed at 90 degrees C for 5 h, have maximum percentage of beta-phase. The beta-phase PVDF shows a remnant polarization of 4.9 mu C/cm(2) at 1400 kV/cm at 1 Hz.
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In order to overcome the interference of the model mounting system with the external aerodynamics of the body during shock tunnel testing, a new free floating internally mountable balance system that ensures unrestrained model motion during testing has been designed, fabricated and tested. Minimal friction ball bearings are used for ensuring the free floating condition of the model during tunnel testing. The drag force acting on a blunt leading edge flat plate at hypersonic Mach number has been measured using the new balance system. Finite element model (FEM) and CFD are exhaustively used in the design as well as for calibrating the new balance system. The experimentally measured drag force on the blunt leading edge flat plate at stagnation enthalpy of 0.7 and 1.2 MJ/kg and nominal Mach number of 5.75 matches well with FEM results. The concept can also be extended for measuring all the three fundamental aerodynamic forces in short duration test facilities like free piston driven shock tunnels.
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The planform structure of turbulent free convection over a heated horizontal surface has been visualized and analyzed for different boundary conditions at the top and for different aspect ratios, for flux Rayleigh numbers ranging from 10 exp 8 - 10 exp 10. The different boundary conditions correspond to Rayleigh-Benard convection, open convection with evaporation at the top and with an imposed external flow on the heated boundary. Without the external flow the planform is one randomly oriented line plume. At large Ra, these line plumes seem to align along the diagonal, persumably due to a large-scale flow along as visualized in the side view. When the external flow is imposed, the line plumes clearly align in the direction of external flow. Flow visualization reveals that at these Ra, the shear tends to break the plumes which otherwise would reach the opposite boundary. (Author)
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Carbon nanosheets (CNSs) have been synthesized by electron cyclotron resonance (ECR) plasma enhanced chemical vapor deposition (PECVD) using a mixture of acetylene and argon gases on copper foil as the substrate. Micrometer-wide carbon sheets consisting of several atomic layers thick graphene sheets have been synthesized by controlled decomposition of carbon radicals in ECR-PECVD. Raman spectroscopy of these films revealed characteristics of a disordered graphitic sheet. Thick folded carbon-sheets and a semi transparent freestanding CNSs have been observed by scanning electron microscopy. This is a promising technique to synthesize free standing CNSs and can be used in the fabrication of nanoelecronic devices in future. (C) 2012 Elsevier B.V. All rights reserved.
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Free energy barriers separating interfacial water molecules from the hydration layer at the surface of a protein to the bulk are obtained by using the umbrella sampling method of free energy calculation. We consider hydration layer of chicken villin head piece (HP-36) which has been studied extensively by molecular dynamics simulations. The free energy calculations reveal a strong sensitivity to the secondary structure. In particular, we find a region near the junction of first and second helix that contains a cluster of water molecules which are slow in motion, characterized by long residence times (of the order of 100 ps or more) and separated by a large free energy barrier from the bulk water. However, these ``slow'' water molecules constitute only about 5-10% of the total number of hydration layer water molecules. Nevertheless, they play an important role in stabilizing the protein conformation. Water molecules near the third helix (which is the important helix for biological function) are enthalpically least stable and exhibit the fastest dynamics. Interestingly, barrier height distributions of interfacial water are quite broad for water surrounding all the three helices (and the three coils), with the smallest barriers found for those near the helix-3. For the quasi-bound water molecules near the first and second helices, we use well-known Kramers' theory to estimate the residence time from the free energy surface, by estimating the friction along the reaction coordinate from the diffusion coefficient by using Einstein relation. The agreement found is satisfactory. We discuss the possible biological function of these slow, quasi-bound (but transient) water molecules on the surface.
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Water-ethanol mixtures exhibit many interesting anomalies, such as negative excess partial molar volume of ethanol, excess sound absorption coefficient at low concentrations, and positive deviation from Raoult's law for vapor pressure, to mention a few. These anomalies have been attributed to different, often contradictory origins, but a quantitative understanding is still lacking. We show by computer simulation and theoretical analyses that these anomalies arise from the sudden emergence of a bicontinuous phase that occurs at a relatively low ethanol concentration of x(eth) approximate to 0.06-0.10 (that amounts to a volume fraction of 0.17-0.26, which is a significant range!). The bicontinuous phase is formed by aggregation of ethanol molecules, resulting in a weak phase transition whose nature is elucidated. We find that the microheterogeneous structure of the mixture gives rise to a pronounced nonmonotonic composition dependence of local compressibility and nonmonotonic dependence in the peak value of the radial distribution function of ethyl groups. A multidimensional free energy surface of pair association is shown to provide a molecular explanation of the known negative excess partial volume of ethanol in terms of parallel orientation and hence better packing of the ethyl groups in the mixture due to hydrophobic interactions. The energy distribution of the ethanol molecules indicates additional energy decay channels that explain the excess sound attenuation coefficient in aqueous alcohol mixtures. We studied the dependence of the solvation of a linear polymer chain on the composition of the water-ethanol solvent. We find that there is a sudden collapse of the polymer at x(eth) approximate to 0.05-a phenomenon which we attribute to the formation of the microheterogeneous structures in the binary mixture at low ethanol concentrations. Together with recent single molecule pulling experiments, these results provide new insight into the behavior of polymer chain and foreign solutes, such as enzymes, in aqueous binary mixtures.
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The present paper discusses the flow visualization for turbulent free convection in a tank of water with the bottom surface being a smooth or a grooved surface and the top of the water surface exposed to ambient. The grooved surface is of parallel 90 degrees V-grooves with groove height of 10 mm and groove width of 20 mm. The experiment is carried out with aspect ratio (AR) of 2.9 and Rayleigh number (Ra) in the range, 1.3 x 10(7) - 4 x 10(7). Here AR is the aspect ratio (= width of fluid layer/height of fluid layer). Heat flux at the bottom surface is from electrical heating. From the pH-dye visualization, interesting flow structures are observed and these structures are analyzed with the help of plumes dynamics and temperature variations with time. (C) 2011 Elsevier Ltd. All rights reserved.
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The fluorescence quenching studies of carboxamide namely (E)-N-(3-Chlorophenyl)-2-(3,4,5-trimethoxybenzylideneamino)-4,5,6,7 tetrahydrobenzob]thiophene-3-carboxamide ENCTTTC] by aniline and carbon tetrachloride in six different solvents namely toluene, cyclohexane, n-hexane, n-heptane, n-decane and n-pentane have been carried out at room temperature with a view to understand the quenching mechanisms. The Stern-Volmer (S-V) plots have been found to be nonlinear with a positive deviation for all the solvents studied. In order to interpret these results we have invoked the ground state complex formation and sphere of action static quenching models. Using these models various quenching rate parameters have been determined. The magnitudes of these parameters suggest that sphere of action static quenching model agrees well with the experimental results. Hence the positive deviation is attributed to the static and dynamic quenching. Further, with the use of Finite Sink approximation model, it was possible to check these bimolecular reactions as diffusion-limited and to estimate independently distance parameter R' and mutual diffusion coefficient D. Finally an effort has been made to correlate the values of R' and D with the values of the encounter distance R and the mutual coefficient D determined using the Edward's empirical relation and Stokes Einstein relation. (C) 2011 Elsevier B.V. All rights reserved.
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We construct for free groups, which are codimension one analogues of geodesic laminations on surfaces. Other analogues that have been constructed by several authors are dimension-one instead of codimension-one. Our main result is that the space of such laminations is compact. This in turn is based on the result that crossing, in the sense of Scott-Swarup, is an open condition. Our construction is based on Hatcher's normal form for spheres in the model manifold.
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Degree of branching (DB) describes the level of structural perfection of a hyperbranched polymer when compared to its defect-free analogue, namely the dendrimer. The strategy most commonly used to achieve high DB values, specifically while using AB(2) type self-condensations, is to design an AB2 monomer wherein the reaction of the first B-group leads to an enhancement of the reactivity of the second one. In the present study, we show that an AB2 monomer carrying a dimethylacetal unit and a thiol group undergoes a rapid self-condensation in the melt under acid-catalysis to yield a hyperbranched polydithioacetal with no linear defects. NMR studies using model systems reveal that the intermediate monothioacetal is relatively unstable under the polymerization conditions and transforms rapidly to the dithioacetal; because this second step occurs irreversibly during polymer formation, it leads to a defect-free hyperbranched polydithioacetal. TGA studies of the polymerization process provided some valuable insights into the kinetics of polymerization. An additional virtue of this approach is that the numerous terminal dimethylacetal groups are very labile and can be quantitatively transformed by treatment with a variety of functional thiols; the terminal dimethylacetals were, thus, reacted with various thiols, such as dodecanethiol, benzyl mercaptan, ethylmercaptopropionate, and so on, to demonstrate the versatility of these systems as sulfur-rich hyperscaffolds to anchor different kinds of functionality on their periphery.
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We report the fabrication of free-standing flexible inorganic/organic hybrid structures by exfoliating ZnO nanostructured films from the flat indium tin oxide (ITO)/silicon/sapphire substrates using poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS). Strong interaction between ZnO and PEDOT: PSS and the thermomechanical response of PEDOT: PSS are the key issues for the exfoliation to prevail. The performance of the free-standing hybrid structures as rectifiers and photodetectors is better as compared to ITO supported hybrid structures. It is also shown that device properties of hybrid structures can be tuned by using different electrode materials. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4729550]
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Given a set of points P ⊆ R2, a conflict-free coloring of P w.r.t. rectangle ranges is an assignment of colors to points of P, such that each nonempty axisparallel rectangle T in the plane contains a point whose color is distinct from all other points in P ∩ T . This notion has been the subject of recent interest and is motivated by frequency assignment in wireless cellular networks: one naturally would like to minimize the number of frequencies (colors) assigned to base stations (points) such that within any range (for instance, rectangle), there is no interference. We show that any set of n points in R2 can be conflict-free colored with O(nβ∗+o(1)) colors in expected polynomial time, where β∗ = 3−√5 2 < 0.382.
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Three dimensional digital model of a representative human kidney is needed for a surgical simulator that is capable of simulating a laparoscopic surgery involving kidney. Buying a three dimensional computer model of a representative human kidney, or reconstructing a human kidney from an image sequence using commercial software, both involve (sometimes significant amount of) money. In this paper, author has shown that one can obtain a three dimensional surface model of human kidney by making use of images from the Visible Human Data Set and a few free software packages (ImageJ, ITK-SNAP, and MeshLab in particular). Images from the Visible Human Data Set, and the software packages used here, both do not cost anything. Hence, the practice of extracting the geometry of a representative human kidney for free, as illustrated in the present work, could be a free alternative to the use of expensive commercial software or to the purchase of a digital model.