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61.
Poly (n-butylisocyanate)-benzene solutions prepared by solubilization at 45°C, followed by aging at room temperature were found to be metastable for months, although, eventually, they separated into a birefringent polymer-rich phase and an isotropic solution. These metastable solutions, as well as isothermally phase-separated biphasic samples, flowed and exhibited dynamic moduli indicative of low polymer connectivity. By contrast samples prepared by a freeze-thaw cycle were uniformly and highly birefringent and showed network (gel) behavior at room temperature. The mechanism of gel formation is most likely the exclusion of the polymer from the benzene crystal during crystallization, forcing the polymer to align and exist at grain boundaries. Films formed from solutions have different moduli than those formed from gels, and are consistent with the proposed mechanism. 相似文献
62.
Timur Zharnikov Alexander Yakovlev Semion Kuchanov 《Journal of Polymer Science.Polymer Physics》2003,41(9):892-902
The problem of finding conditions of the loss of thermodynamic stability by the reaction system was solved on the basis of the developed theory of living free‐radical copolymerization. The spinodal's calculations were carried out for a significant number of systems differing in the values of kinetic, stoichiometric, and thermodynamic parameters. Analysis of the results of such calculations revealed some regularities in the spinodal curves' behavior and permitted us to classify their possible topological types. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 892–902, 2003 相似文献
63.
G. N. Merrill 《Journal of Physical Organic Chemistry》2007,20(1):19-29
Ab initio molecular orbital calculations were carried out on epibromohydrin (EBH) and epichlorohydrin (ECH) in an attempt to elucidate their reactivity with respect to a hard nucleophile, hydroxide. These systems were modeled in both the gas phase and a polar solvent under basic conditions. In the gas phase, it was determined that a direct displacement mechanism (nucleophilic attack at the C1 position) was operative for EBH, while an indirect pathway (nucleophilic attack at the C3 position and subsequent intramolecular displacement) was followed for ECH. In an acetone solution, only the indirect displacement mechanism was found to occur. An electrostatic argument is advanced to account for this behavior in polar solution. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
64.
T. K. Melik-Barkhudarov 《Journal of Contemporary Physics (Armenian Academy of Sciences)》2007,42(5):173-177
An approach is discussed which allows one to describe within the framework of the single model the aggregative states of a system of atoms obeying the Fermi statistics. A phase diagram is obtained containing both the critical point where the distinctions between the liquid and vapor vanish and the triple point where the liquid, vapor, and crystal are in equilibrium. 相似文献
65.
We study phase separation in a system of hard-core particles driven by a fluctuating two-dimensional self-affine potential landscape which evolves through Kardar–Parisi–Zhang (KPZ) dynamics. We find that particles tend to cluster together on a length scale which grows in time. The final phase-separated steady state is characterized by an unusual cusp singularity in the scaled correlation function and a broad distribution for the order parameter. Unlike the one-dimensional case studied earlier, the cluster-size distribution is asymmetric between particles and holes, reflecting the broken reflection symmetry of the KPZ dynamics, and has a contribution from an infinite cluster in addition to a power law part. A study of the surface in terms of coarse-grained depth variables helps understand many of these features. 相似文献
66.
Small‐Angle Neutron Scattering has been performed from poly(ethylene oxide) in deuterated water at temperature ranging from 10 to 80 °C. A simple fitting model was used to obtain a correlation length and a Porod exponent. The correlation length L characterizes the average distance between entanglements in the semidilute region and is proportional to the individual coil sizes in the dilute region. L was found to increase with temperature in the semidilute region but it decreases with temperature in the dilute region. This decrease is the precursor to the single‐chain collapse which applies to very dilute polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2196–2200, 2007 相似文献
67.
张国胜 《数学的实践与认识》2006,36(7):356-367
设W(1n)W2(n)…W(nn)是严平稳随即序列{Xn,n 1}的前几个变量的顺序统计量,Nn Mn是两正整值r.v,n 1.在较弱一些的混合条件下,本文给出了W(NMn)n标准化后的极限分布,从而使一些提法更趋一般化,主要结果推进了Rao(1984)和张国胜(1993)的工作.由于混合条件的减弱,使得对m-相关和正态平稳过程的具体应用讨论更加充分. 相似文献
68.
Chenghang Wang 《Applied Surface Science》2006,253(4):2282-2288
In this paper, thin films of titanium oxide imprinted with O,O-dimethyl-(2,4-dichlorophenoxyacetoxyl)(3′-nitrobenyl) methinephosphonate (Phi-NO2) were prepared via liquid phase deposition (LPD) method on a glassy carbon electrode. The imprinted molecular in the films was removed by treatment with immersion in CH2Cl2. X-ray diffraction (XRD) and electrochemical methods were introduced to show the evidence of the molecular imprinting phenomenon. It was also found that the recognition ability of the sensor depended on the substituents associated with tridimensional structures of the nitro-compounds. Under the optimized condition, the sensor showed better sensitivity, selectivity and reproducibility to the imprinted molecule and the linear relationship between the current and the concentration of analyte in the range of 0.1-50 μM was obtained. LPD proved to be a powerful method for imprinting titanium oxide thin sense films. 相似文献
69.
This work reports a new synthetic approach for single‐phase TiO2 nanomaterials by solvothermal treatment of titanium tetrachloride in acetone at 80–110 °C. Small, uniform, and yet size‐tunable (5–10 nm) anatase titania nanocrystallites were obtained using a low concentration of TiCl4 in acetone (i.e., at molar ratios of TiCl4/acetone ≤ 1:15) in the temperature range of 80–110 °C, while rutile nanofibers were synthesized using a high concentration of TiCl4 (e.g., TiCl4/acetone = 1:10) at 110 °C. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
70.
In this article a stability result for the Falk model system is proven. The Falk model system describes the martensitic phase transitions in shape memory alloys. In our setting, the steady state is a nonlocal elliptic problem. We show the dynamical stability for the linearized stable critical point of the corresponding functional. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献