906 resultados para Thermal and photochemical transformations


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The superconducting magnet of the LPT (Lanzhou Penning trap) consists of nine coaxial coils. The maximum magnetic field is 7 T and thus results in a large magnetic force. In order to assure the mechanical stability, it is necessary to do the stress analysis of the magnet system. The 3D Finite Element Analysis of thermal and mechanical behavior was presented in this paper. For the numerical simulation and analysis of the phenomena inside the structure, the ADINA and TOSCA code were chosen right from start. The ADINA code is commonly used for numerical simulations of the structure analysis [1] and the TOSCA code is professional software to calculate the magnetic field and Lorentz Forces. The results of the analysis were evaluated in terms of the stress and deformation.

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A new poly(fullerene oxide) thin film material has been fabricated by thermal activation and electron bombardment on hexanitro[60]fullerene (HNF) film deposited on a An substrate, all under vacuum conditions. The reaction products in the polymerization process are analyzed by XPS, UPS, IR, TGA-MS and LDI-MS techniques. It is found that the main effect of thermal and radiation treatments is to induce cleavage of -NO bonds from HNF molecules resulted in the release of nitric oxide gas and the formation of fullerene-bound oxyradicals, C-60-C-6. Spectroscopic evidence strongly suggests that rearrangement of fullerenic nitro moieties into nitrito groups is involved in the HNF decomposition process prior to the generation of reactive oxyradical intermediates. Consequently, the intermolecular coupling reaction of these oxyradicals leads to carbon polymer networks containing oxygen-bridged fullerenes. The thermally generated polymeric thin film is stable up to 900 K. Electron bombardment is also effective in both the decomposition of -NO2 groups and the removal of -OH groups present in HNF films. UV irradiation at 365 nm alone is shown to be not as efficient for the polymer formation. (C) 2003 Elsevier Ltd. All rights reserved.

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A central challenge to the semiclassical description of quantum mechanics is the quantum phenomenon of "deep" tunneling. Here we show that real time classical trajectories suffice to account correctly even for deep quantum tunneling, using a recently formulated semiclassical initial value representation series of the quantum propagator and a prefactor free semiclassical propagator. Deep quantum tunneling is effected through what we term as coherent classical paths which are composed of one or more classical trajectories that lead from reactant to product but are discontinuous along the way. The end and initial phase space points of consecutive classical trajectories contributing to the coherent path are close to each other in the sense that the distance between them is weighted by a coherent state overlap matrix element. Results are presented for thermal and energy dependent tunneling through a symmetric Eckart barrier.

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Feature-based image watermarking schemes, which aim to survive various geometric distortions, have attracted great attention in recent years. Existing schemes have shown robustness against rotation, scaling, and translation, but few are resistant to cropping, nonisotropic scaling, random bending attacks (RBAs), and affine transformations. Seo and Yoo present a geometrically invariant image watermarking based on affine covariant regions (ACRs) that provide a certain degree of robustness. To further enhance the robustness, we propose a new image watermarking scheme on the basis of Seo's work, which is insensitive to geometric distortions as well as common image processing operations. Our scheme is mainly composed of three components: 1) feature selection procedure based on graph theoretical clustering algorithm is applied to obtain a set of stable and nonoverlapped ACRs; 2) for each chosen ACR, local normalization, and orientation alignment are performed to generate a geometrically invariant region, which can obviously improve the robustness of the proposed watermarking scheme; and 3) in order to prevent the degradation in image quality caused by the normalization and inverse normalization, indirect inverse normalization is adopted to achieve a good compromise between the imperceptibility and robustness. Experiments are carried out on an image set of 100 images collected from Internet, and the preliminary results demonstrate that the developed method improves the performance over some representative image watermarking approaches in terms of robustness.

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Novel water resistant sulfonated poly[bis(benzimidazobenzisoquinolinones)] (SPBIBIs) were synthesized from 6,6'-disulfonic-4,4'-binaphthy]-1,1',8,8'-tetracarboxylic dianhydride (SBTDA) and various aromatic ether tetraamines. The resulting polymers with IEC in the range of 2.17-2.87 mequiv g(-1) have a combination of desired properties such as high solubility in common organic solvents, film-forming ability, and excellent thermal and mechanical properties. Flexible and tough membranes, obtained by casting from m-cresol solution, had tensile strength, elongation at break, and tensile modulus values in the range of 87.6-98.4 MPa, 35.8-52.8%, and 0.94-1.07 GPa. SPBIBI membranes with a high degree of sulfonation displayed high proton conductivity and a good resistance to water swelling as well. SPBIBI-b with IEC of 2.80 mequiv g(-1) displayed the conductivity of 1.74 x 10(-1) S cm(-1) at 100 degrees C, which was comparable to that of Nafion (R) 117 (1.78 x 10(-1) S cm(-1), at 100 degrees C).

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Inorganic nanoparticles (NPs) with attractive electronic, optical, magnetic, thermal and catalytic properties have attracted great interest due to their important applications in physics, chemistry, biology, medicine, materials science and interdisciplinary fields. Biomolecule-NP hybrid systems, which combine recognition and catalytic properties of biomolecules with electronic, optical, magnetic and catalytic properties of NPs, are particularly new materials with synergistic properties originating from the components of the hybrid composites. The biomolecule-NP hybrid system has excellent prospects for interfacing biological recognition events with electronic signal transduction so as to design a new generation of bioelectronic devices with high sensitivity.

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The synthesis, thermal and emission properties of an electrophosphorescent platinum(II) metallopolyyne polymer consisting of 9-butylcarbazole-2,7-diyl spacer P1 are described. The optical and electronic properties of P1 are compared to their molecular diplatinum(II) and digold(I) model complexes. The photophysical properties of P1 are somehow analogous to its 2,7-fluorene-linked congener but differs significantly from that for the 3,6-carbazole derivative. Its optical band gap is notably reduced as compared to that for the 3,6-carbazole analog. Multi-layer polymer light-emitting diodes (PLEDs) were fabricated with P1 as the emitting layer which gave a strong green-yellow electrophosphorescence. The best PLED can reach the maximum current efficiency of 4.7 cd . A(-1) at 5 wt.-% doping level, corresponding to an external quantum efficiency of 1.5%. This represents the first literature example of efficient PLEDs exhibiting pure triplet emission under electrical excitation for metallopolyynes without the concomitant singlet emission.

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A fully diarylmethylene-bridged triphenylamine derivative is efficiently synthesized. It has an almost planar triphenylamine (TPA) skeleton and exhibits excellent thermal and morphological stability. Devices with the novel TPA derivative as host material and Ir(ppy)(3) as triplet emitter show a maximum current efficiency of 83.5 cd/A and a maximum power efficiency of 71.4 Im/W for green electrophosphorescence.

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Poly(propylene carbonate) (PPC) showed predominantly degradation under electron-beam irradiation, accompanied by deterioration of its mechanical performance due to sharp decrease of the molecular weight. Crosslinked PPC was prepared by addition of polyfunctional monomer (PFM) to enhance the mechanical performance of PPC. When 8 wt% of PFM like triallyl isocyanurate (TAIL) was added, crosslinked PPC with a gel fraction of 60.7% was prepared at 50 kGy irradiation dose, which showed a tensile strength at 20 degrees C of 45.5 MPa, whereas it was only 38.5 MPa for pure PPC. The onset degradation temperature (T-i) and glass transition temperature (T-g) of this crosslinked PPC was 246 degrees C and 45 degrees C, respectively, a significant increase related to pure PPC of 211 degrees C and 36 C. Therefore, thermal and mechanical performances of PPC could be improved via electron-beam irradiation in the presence of suitable PFM.

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This review deals with polyimides based on isomeric dianhydrides and diamines, and with chiral polyimides. First, however, a summary is presented of recent work on the synthesis of isomeric dianhydrides, the reaction of mellophanic dianhydride with diamines, and the tendency toward cyclization in reactions of some dianhydrides and diamines. Then turning to polymers, the discussion covers solubility, thermal and dielectric properties, permeability and permselectivity for gas separation, and rheology of isomeric polyimides. Several useful general rules have been found: i.e. the glass transition temperature of polyimides based on isomeric dianhydrides with a given diamine decreases in the order 3,3'- > 3,4'- > 4,4-dianhydride if the polymers are of comparable molecular weight, whereas the thermal stability and the T-beta/T-g ratio (in absolute temperatures) increase in the order of 3,3'- < 3,4'- < 4,4'-dianhydride. Polyimides from 3,3'- or 3,4'-dianhydride have higher solubility than those from 4,4'-dianhydride. Polyimides from 3,4'-dianhydrides exhibit much lower melt viscosity than those from the other isomeric anhydrides. The dielectric constants of polyimides derived from m,m'-diamines are lower than those from p,p'-diamines. Polyimides based on 3,3'- or 3,4'-dianhydrides have higher permeability and slightly lower permselectivity than polyimides based on 4,4'-dianhydrides.

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3,3',4,4'-Diphenylthioether dianhydride (4,4'-TDPA), 2,3,3',4'-diphenylthioether dianhydride (3,4'-TDPA), and 2,2',3,3-diphenylthioether dianhydride (3,3'TDPA) were synthesized from 3-chlorophthalic anhydride and 4-chlorophthalic anhydride. A series of polyimides derived from the isomeric diphenylthioether dianhydrides with several diamines were prepared. The properties, such as the solubility, thermal and mechanical behavior, dynamic mechanical behavior, wide-angle X-ray diffraction, and permeability to some gases, were compared among the isomeric polyimides. Both 3,3'-TDPA- and 3,4-TDPA-based polyimides had good solubility in polar aprotic solvents and phenols. The 5% weight loss temperatures of all the obtained polyimides was near 500 degrees C in nitrogen. The glass-transition temperatures decreased according to the order of the polyimides based on 3,3'-TDPA, 3,4'-TDPA, and 4,4'-TDPA. The 3,4'-TDPA-based polyimides had the best permeability and lowest permselectivity, whereas the 4,4'-TDPA-based polyimides had the highest permselectivity and the lowest permeability of the three isomers. Furthermore, the rheological properties of thermoplastic polyimide resins based on the isomeric dipbenylthioether dianhydrides were investigated, and they showed that polyimide 3,4'-TDPA/4,4-oxydianiline had the lowest melt viscosity among the isomers; this indicated that the melt processibility had been greatly improved.

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Poly(propylene carbonate) (PPC) with number average molecular weight (M-n) higher than 200 kg/mol was prepared via the terpolymerization of carbon dioxide, propylene oxide and diepoxide using Y(CCl3OO)(3)-ZnEt2-glycerine coordination catalyst. When equimolar ZnEt2 and diepoxide were used, double propagation active species were generated in situ by nucleophilic attack of metal alkoxide on diepoxide, leading to PPC of doubled M-n value. The molecular weight of PPC has dramatic influence on its thermal and mechanical performances. PPC with M of 227 kg/mol showed modulus of 6900 MPa, while the modulus of PPC with M-n of 109 kg/mol was only 4300 MPa. Moreover, when M-n increased from 109 to 227 kg/mol, a 37 degrees C increase of the onset degradation temperature was observed.

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The thermal and chemical stabilities of Mo/Si multilayer structure used in Bragg-Fresnel optics were studied to get optimal technological parameters of pattern generation. Mo/Si multilayers were annealed at temperature ranging from 360 to 770 K, treated with acetone and 5 parts per thousand NaOH solution, and characterized by small-angle x-ray diffraction technique as well as x-ray photoelectron spectroscopy, and Olympus microscopy.

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A new solid polymer electrolyte has been prepared using NaClO4 and a comb-branch polymer with oligo(ethylene oxide) side chains. The thermal and ionic conductive properties of the electrolytes were investigated. The profile of conductivity at various temperatures follows the VTF plots.

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The transformation field method (TFM) originated from Eshelby's transformation field theory is developed to estimate the effective permittivity of an anisotropic graded granular composite having inclusions of arbitrary shape and arbitrary anisotropic grading profile. The complicated boundary-value problem of the anisotropic graded composite is solved by introducing an appropriate transformation field within the whole composite region. As an example, the effective dielectric response for an anisotropic graded composite with inclusions having arbitrary geometrical shape and arbitrary grading profile is formulated. The validity of TFM is tested by comparing our results with the exact solution of an isotropic graded composite having inclusions with a power-law dielectric grading profile and good agreement is achieved in the dilute limit. Furthermore, it is found that the inclusion shape and the parameters of the grading profile can have profound effect on the effective permittivity at high concentrations of the inclusions. It is pointed out that TFM used in this paper can be further extended to investigate the effective elastic, thermal, and electroelastic properties of anisotropic graded granular composite materials.