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81.
Ionela Carazeanu Popovici Gabriel Prodan 《Journal of Sol-Gel Science and Technology》2012,63(3):457-462
Fresnoite (Ba2TiSi2O8, BTS) nano-particles were successfully synthesized at a low temperature of 900?°C by a modified Pechini sol?Cgel process with starting materials of Ba(NO3)2, Si(OC2H5)4 and Ti(OC3H7)4. The structural characterization of the precursors and derived synthesized oxide powders is done by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermal analysis (TG-DTG) and electron microscopy (SEM, EDX and TEM) studies. The effect of heat-treating temperature on the crystallinity of the fresnoite was investigated. Combined the XRD data and the strong FTIR peaks assigned to Ti?CO and Si?CO vibration, indicate the formation of fresnoite phase at a temperature of 900?°C. Also the nano-crystals size distribution was studied and the main diameter of nanoparticles was about 47?nm. 相似文献
82.
Roberto Andreani Gabriel Haeser María Laura Schuverdt Paulo J. S. Silva 《Mathematical Programming》2012,135(1-2):255-273
In this work we introduce a relaxed version of the constant positive linear dependence constraint qualification (CPLD) that we call RCPLD. This development is inspired by a recent generalization of the constant rank constraint qualification by Minchenko and Stakhovski that was called RCRCQ. We show that RCPLD is enough to ensure the convergence of an augmented Lagrangian algorithm and that it asserts the validity of an error bound. We also provide proofs and counter-examples that show the relations of RCRCQ and RCPLD with other known constraint qualifications. In particular, RCPLD is strictly weaker than CPLD and RCRCQ, while still stronger than Abadie’s constraint qualification. We also verify that the second order necessary optimality condition holds under RCRCQ. 相似文献
83.
Barbora Benešová Martin Kružík Gabriel Pathó 《Continuum Mechanics and Thermodynamics》2014,26(5):683-713
We design a new mesoscopic thin-film model for shape-memory materials which takes into account thermomechanical effects. Starting from a microscopic thermodynamical bulk model, we guide the reader through a suitable dimension reduction procedure followed by a scale transition valid for specimen large in area up to a limiting model which describes microstructure by means of parametrized measures. All our models obey the second law of thermodynamics and possess suitable weak solutions. This is shown for the resulting thin-film models by making the procedure described above mathematically rigorous. The main emphasis is, thus, put on modeling and mathematical treatment of joint interactions of mechanical and thermal effects accompanying phase transitions and on reduction in specimen dimensions and transition of material scales. 相似文献
84.
85.
Dorin Ervin Dutkay Gabriel Picioroaga Myung-Sin Song 《Journal of Mathematical Analysis and Applications》2014
We show how some orthonormal bases can be generated by representations of the Cuntz algebra; these include Fourier bases on fractal measures, generalized Walsh bases on the unit interval and piecewise exponential bases on the middle third Cantor set. 相似文献
86.
87.
Herbert Hommer Gabriel Cuevas Barbara Gordillo 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):2421-2437
By following a previously reported method,1 the synthesis of r-2-alkoxy-cis-4-cis-5-dimethyl-1,3,2-λ3-dioxaphospholanes ligands (1 and 3) was carried out. The purpose of this work is the kinetic study of the inversion barrier at phosphorus for 1 and 3 and the comparison with the already informed dioxaphospholane 2. The kinetic measurements of the thermal isomerization cis-to-trans were performed by 31P NMR spectroscopy, observing a first order kinetics for both compounds. The energy of activation (Ea) for the epimerization of compounds cis-1 and cis-3 was calculated to be 16.0 ± 0.6 and 11.8 ± 0.8 kcal/mol, respectively. The values of the thermodynamic parameters of the transition state (Δ H≠, Δ S≠, Δ G≠) suggest that the inversion at phosphorus not only depends on the spatial requirements of the alkoxy substituent but also on entropic effects. The thermodynamic parameters Δ H°, Δ S°, and Δ G° were also evaluated and they show that the cis isomers are preferred from enthalpic point of view, but entropic effects dominate the equilibrium trans ? cis leading to the entropically favored trans isomers. Furthermore, the results are supported by density functional theory calculations of 1–4 at the B3LYP/6-31G** level. 相似文献
88.
Zaira Domínguez Javier Hernández Lorena Silva-Gutiérrez Magali Salas-Reyes Mario Sánchez Gabriel Merino 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4):772-784
The effect of electron-withdrawing (EW) and electron-releasing (ER) substituents on the 31P NMR chemical shifts and the structural parameters of a series of tris-(p-X-aryl)selenophosphates is reported in this article. Similarly to O-aryl phosphates and O-aryl thiophosphates, EW groups attached to aromatic rings induce a shielding effect on the 31P NMR signal. After a detailed experimental and theoretical analysis, we confirmed that the selenium atom is the main part responsible for the charge density transfer toward phosphorus through a back-bonding effect. The obtained 1JP-Se values for the complete series agree with this observation. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. 相似文献
89.
Abstract The distribution of the alkoxide groups obtained in the metallation of starch in dimethyl sulfoxide solution by alkali metal naphthalenes was studied. The starch alkoxide was reacted with methyl iodide, and the methylated starch was hydrolyzed and analyzed for glucose and O-methyl glucose derivatives. The metallation reaction was found to be random, as seen from the fact that at low alkoxide concentration (D.S = 0.6), 2,3,6-tri-O-methyl glucose was formed, while at relatively high alkoxide concentration (D.S. = 1.5) unreacted glucose was still present. At low alkoxide concentration (D.S. ? 0.6) there was, to a certain extent, preferential metallation at the C2 hydroxyl groups, and to a lesser extent at the C6 hydroxyl groups, as seen from the relative molar ratios of about 10:4:1 of the 2-, 6-, and 3-O-methyl glucose derivatives obtained, respectively. An increase in the metallation at the C3 hydroxyl occurred with increasing alkoxide concentration. The distribution of the methoxyl groups with the three alkali metals potassium, sodium, and lithium was similar; there were differences only in the ease of metallation of the starch by the various alkali metal naphthalenes and in the efficiency of the coupling reaction with methyl iodide. 相似文献
90.
The signatures of nanosolvation on the one‐ and two‐dimensional (1D and 2D) IR spectra of a proton‐transfer mode in a hydrogen‐bonded complex dissolved in polar solvent molecule nanoclusters of varying size are elucidated by using mixed quantum–classical molecular dynamics simulations. For this particular system, increasing the number of solvent molecules successively from N=7 to N=9 initiates the transition of the system from a cluster state to a bulk‐like state. Both the 1D and 2D IR spectra reflect this transition through pronounced changes in their peak intensities and numbers, but the time‐resolved 2D IR spectra also manifest spectral features that uniquely identify the onset of the cluster‐to‐bulk transition. In particular, it is observed that in the 1D IR spectra, the relative intensities of the peaks change such that the number of peaks decreases from three to two as the size of the cluster increases from N=7 to N=9. In the 2D IR spectra, off‐diagonal peaks are observed in the N=7 and N=8 cases at zero waiting time, but not in the N=9 case. It is known that there are no off‐diagonal peaks in the 2D IR spectrum of the bulk version of this system at zero waiting time, so the disappearance of these peaks is a unique signature of the onset of bulk‐like behavior. Through an examination of the trajectories of various properties of the complex and solvent, it is possible to relate the emergence of these off‐diagonal peaks to an interplay between the vibrations of the complex and the solvent polarization dynamics. 相似文献