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61.
Ab initio energetic calculations based on the density functional theory (DFT) and projector augmented wave (PAW) pseudo-potentials method were performanced to determine the crystal structural parameters and phase transition data of the polymorphic rare-earth sesquioxides Ln2O3 (where Ln=La-Lu, Y, and Sc) with A-type (hexagonal) and B-type (monoclinic) configurations at ground state. The calculated results agree well with the limited experimental data and the critically assessed results. A set of systematic and self-consistent crystal structural parameters, energies and pressures of the phase transition were established for the whole series of the A- and B-type rare-earth sesquioxides Ln2O3. With the increase of the atomic number, the ionic radii of rare-earth elements Ln and the volumes of the sesquioxides Ln2O3 reflect the so-called “lanthanide contraction”. With the increase of the Ln3+-cation radius, the bulk modulus of Ln2O3 decreases and the polymorphic structures show a degenerative tendency. 相似文献
62.
Ummadisetty Subramanyam Swaminathan Sivaram 《Journal of polymer science. Part A, Polymer chemistry》2007,45(2):191-210
Homopolymerization of octadecene‐1 at different reaction conditions has been studied. Significant chain running can be seen at higher polymerization temperatures. Interestingly, insertion of octadecene‐1 into a sterically hindered nickel‐cation/carbon (secondary) bond is observed. The microstructure of the polymer was established using NMR spectroscopy. The effects of chain running on polymer melting, crystallization behavior, and dynamic mechanical thermal properties were studied using DSC and DMTA. The extent of chain running (i.e., 2,ω‐, 1,ω‐enchainments) decreases with an increase in the carbon number of α‐olefins. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 191–210, 2007 相似文献
63.
A. Hansen M.H. Jensen K. Sneppen G. Zocchi 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,6(1):157-161
We present a statistical mechanics treatment of the stability of globular proteins which takes explicitly into account the
coupling between the protein and water degrees of freedom. This allows us to describe both the cold and the warm unfolding,
thus qualitatively reproducing the known thermodynamics of proteins.
Received: 19 March 1998 / Revised and Accepted: 25 May 1998 相似文献
64.
The solvent extraction of cobalt(II), nickel(II) and copper(II) using 2,4-pent-dione (Hacac) and 4-phenyl-2, 4-but-dione (Hbzac)
is carried out by varying the reagent concentration and pH of the aqueous phase. Each of these metals is quantitatively separated
(≈ 98%) from their binary mixtures with monovalent (Ag), divalent (Mn, Zn, Cd, Hg, Mg, Sn, Pb) and trivalent (Cr, Fe) metals.
The extraction constants are calculated from the metal distribution data using linear regression analysis. The extracted species
is MA2 in each case. A most significant result is separation of copper(II) from iron(III) which otherwise interferes when extracted
from the acidic medium. 相似文献
65.
Bryan B. Sauer Richard Beckerbauer Lixiao Wang 《Journal of Polymer Science.Polymer Physics》1993,31(12):1861-1872
The high sensitivity of the thermally stimulated current, thermal sampling (TS) method is emphasized in a study of the breadth of the glass transition in several liquid-crystalline polymers (LCPs). Differential scanning calorimetry (DSC) was performed on all samples to further quantify the glass transition regions. For “random” copolyester LCPs with widely varying degrees of crystallinity, including highly amorphous samples, very broad glass tran-sition regions were observed. One semicrystalline alternating copolyester and a series of semicrystalline azomethine LCPs were studied as examples of structurally regular polymers. These exhibited relatively sharp glass transitions more comparable to ordinary isotropic amorphous or semicrystalline polymers. The broad glass transitions in the random copolyesters are attributed to structural heterogeneity of the chains. In one example of a moderate-crystallinity random copolyester LCP (Vectra), glass transitions ranging up to ca. 150°C in breadth were determined by the thermal sampling (TS) method and DSC. In other lower crystallinity copolyester LCPs, the main glass transition temperature as determined by DSC was comparable to that determined by TSC although cooperative relaxations of a minor fraction of the overall relaxing species were detected well below the main Tg, by the TS method and not by DSC. Rapid quenches from the isotropic melt to an isotropic glass were possible with one LCP. The anisotropic and isotropic glassy states for this LCP were found to have the same breadth of the glass transition as was determined by the TS method, although TSC and DSC show that Tg is shifted downward by ca. 15°C in the anisotropic glass as compared to the isotropic glass. © 1993 John Wiley & Sons, Inc. 相似文献
66.
We study a generalization of the analytic theory of first-order phase transitions to the cases of arbitrary droplet growth, of nonisothermal processes, and of heterogeneous centers in the system. We show that in all these cases, the spectra of droplet dimensions are similar. The same forms of the spectra are also obtained for the stationary condensation process in a spatially inhomogeneous system. 相似文献
67.
Perfect information two-person zero-sum markov games with imprecise transition probabilities 总被引:1,自引:0,他引:1
Hyeong Soo Chang 《Mathematical Methods of Operations Research》2006,64(2):335-351
Based on an extension of the controlled Markov set-chain model by Kurano et al. (in J Appl Prob 35:293–302, 1998) into competitive two-player game setting, we provide a model of perfect information two-person zero-sum Markov games with imprecise transition probabilities. We define an equilibrium value for the games formulated with the model in terms of a partial order and then establish the existence of an equilibrium policy pair that achieves the equilibrium value. We further analyze finite-approximation error bounds obtained from a value iteration-type algorithm and discuss some applications of the model. 相似文献
68.
P. Deepa K. Divya M. Jayakannan 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):42-52
New series of cycloaliphatic poly(ester‐amide)s, poly(1,4‐cyclohexanedimethyleneterephthalate‐co‐1,3‐cyclohexanedimethylene terephthalamide), were synthesized through solution polymerization route. The compositions of ester/amide units in the copolymers were varied from 0 to 100% by varying the amount of 1,4‐cyclohexanedimethanol and 1,3‐cyclohexanebis(methylamine) in the feed. The structures of the polymers were confirmed by NMR and FTIR, and the molecular weights were determined by inherent viscosity. The composition analysis by NMR reveals that the reactivity of the diamine toward the acid chlorides is lowered than that of diol, which results in the formation of more ester content in the poly (ester‐amides). The thermal analysis indicate that the new poly(ester‐amide)s having less than 10 mol % of amide linkages are thermotropic liquid crystalline from 200 to 250 °C and a thread like nematic phases are observed under the polarizing microscope. WXRD studies suggest that the liquid crystalline domains promote the nucleation process in the polyester chains and increases the percent crystallinity of the poly(ester‐amide)s. The glass transition temperature of the copolymers initially increases with increase in amide units because of the presence of nematic phases and subsequently follows the Flory–Fox behavior. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 42–52, 2006 相似文献
69.
H. Huth A. A. Minakov C. Schick 《Journal of polymer science. Part A, Polymer chemistry》2006,44(20):2996-3005
A differential AC-chip calorimeter capable of measuring the step in heat capacity at the glass transition in nanometer-thin films is described. Because of the differential setup, pJ/K sensitivity is achieved. Heat capacity can be measured for sample masses below 1 ng in broad temperature range as needed for the study of the glass transition in nanometer-thin polymeric films. Relative accuracy is sufficient to investigate the changes in heat capacity as the step at the glass transition of polystyrene. The step is about 25% of the total heat capacity of polystyrene. The calorimeter allows for the frequency dependent measurement of complex heat capacity in the frequency range from 1 Hz to 1 kHz. The glass transition in thin polystyrene films (50–4 nm) was determined at well-defined experimental time scales. No thickness dependency of the glass transition temperature was observed within the error limits (±3 K)—neither at constant frequency (40 Hz) nor for the trace in the activation diagram (1 Hz–1 kHz). © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2996–3005, 2006 相似文献
70.