Thermal Analysis of the Conformational Disorder in SCLC Polymers with Rigid Backbone Glass transition studies

Bis [(ω-(4′-cyanobiphenyl)-4-yl)oxy-n-alkyl]norborn-5-ene-2,3-dicarboxylate was polymerised via ring opening metathesis polymerisation (ROMP). Two disubstituted polynorbornene derivatives both of cis configuration with different length of the side-chain were studied. Differential scanning calorimetry (DSC) was used to study the effect of thermal history on the assignment of the glass transition event associated with the biaxial orientation of a smectic phase. Glass transition temperatures, the change of isobaric specific heats at T_g and the enthalpies of isotropisation were calculated. The DSC traces only show the classic step-wise change in T_g in some cases, giving the evidence that the amorphous domains are constrained and highly restricted in movement due to the morphology developed as a result of the biaxial stretching. Based on the literature data of mono- and disubstituted polynorbornene derivatives and our calorimetric experiments, the shape of T_g dependence on number of (CH₂) units is interpreted. The origin of this shape is discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

低密度聚乙烯光引发交联机理——Ⅱ.BNB自旋捕捉ESR研究

在光引发剂二苯甲酮(BP)存在下,紫外光辐照低密度聚乙烯(LDPE)所形成的自由基中间体已被自旋捕捉剂2,4,6-三特丁基亚硝基苯(BNB)所捕捉,其自旋加合物自由基已为电子自旋共振(ESR)所特征。现已检测和鉴定到二种自旋加合物:一种是叔碳自由基;另一种是仲碳自由基。它们分别是由BP的激发三重态从LDPE链的支化点和亚甲基团上夺氢所形成的自由基中间体同自旋捕捉剂BNB反应生成的。上述的证据表明:LDPE的光引发交联点主要发生在叔碳和仲碳原子上,且H-型交联点占主导地位。     

Viscoelasticity and birefringence of polyisoprene

The complex Young's modulus, E^*(ω), and the complex strain-optical coefficient, O^*(ω), which is the ratio of the birefringence to the strain, were measured for polyisoprene (PIP) over a frequency range of 1 ～ 130 Hz and a temperature range of 22 ～ ?100°C. The imaginary part of O^*, O″, was positive at low frequencies and negative at high frequencies. The real part, O′, was always positive and showed a maximum. The complicated behavior of O^* could be understood by the assumption that E^* = E_R^* + E_G^* and O^* = C_RE_R^* + C_GE_G^*, where E_R^* and E_G^* were complex quantities and C_R and C_G were constants. The C_R value, equal to the ordinary stress-optical coefficient measured in the rubbery plateau zone, was 2.0 × 10^?9 Pa^?1. The C_G value, defined as the ratio O″/E″ in the glassy zone, was ?1.1 × 10^?11 Pa^?1. The E_G^*, which was the major component of E^* in the glassy zone, showed almost the same frequency dependence as that of polystyrene and polycarbonate. The E_R^*, which was dominant in the rubbery zone, was described well by the bead-spring theory. The temperature dependence of the E_G^* was stronger than that of the E_R^*. This difference caused the breakdown of the thermorheological simplicity for E^* and O^* around the glass-to-rubber transition zone. © 1995 John Wiley & Sons, Inc.     

A complementary thermodynamic limit for classical Coulomb matter

The canonical equilibrium measure of classical two-component Coulomb matter with regularized interactions is analyzed in a finite volume. It is shown that, in the mean-field regime, the one-particle density is inhomogeneous on a new characteristic length scale _inh. For a system ofN positive andN negative particles, _inh and the characteristic length scale of correlations _corr (=Debye screening length) are related via _inh=(2N)^1/2 _corr. The major conceptual conclusion that is drawn from this is that one needs two nontrivial complementary thermodynamic limits to define the equilibrium thermodynamics of two-component Coulomb systems. One of them is the standard thermodynamic limit (infinite volume), where one takesN, _corr fixed. Its complementary limit is characterized byN, _inh fixed, and is a finite-volume inhomogeneous mean-field limit. The most prominent new feature in the mean-field thermodynamic limit, which is absent in the standard thermodynamic limit, is an anomalous first-order phase transition where the Coulomb system explodes or implodes, respectively. The phase transition is connected with the existence of a metastable plasma phase far below the ionization temperature.     

Infinite-order phase transition in a classical spin system

For an exactly soluble classical spin model with long-range inhomogeneous coupling it is proved that in the absence of external magnetic field the free energy is aC function of the temperature at the critical point.     

Solvable isotherms for a two-component system of charged rods on a line

The Coulomb system consisting of an equal number of positive and negative charged rods confined to a one-dimensional lattice is studied. The grand partition function can be calculated exactly at two values of the coupling constant=q ²/k _B T (q denoting the magnitude of the charges). The exact results lead to the conjecture that in the complex scaled fugacity plane, all the zeros of the grand partition function lie on the negative real axis for<2, on the point=–1 for=2, and on the unit circle for>2. In addition, for>4, we conjecture in general and prove at=4 that the zeros pinch the real axis in the thermodynamic limit, with an essential singularity in the pressure at the reduced density 1/2.     

Spatial fluctuations in reaction-limited aggregation

A general method is used for describing reaction-diffusion systems, namely van Kampen's method of compounding moments, to study the spatial fluctuations in reaction-limited aggregation processes. The general formalism used here and in subsequent publications is developed. Then a particular model is considered that is of special interest, since it describes the occurrence of a phase transition (gelation). The corresponding rate constants for the reaction between two clusters of sizei and sizej areK _ij=ij (i, j=1, 2,). For thediffusion constants D _j of clusters of sizej the following class of models is considered:D _j=D if 1Js andD _j=0 ifj>s. The casess= ands< are studied separately. For the models= the equal-time and the two-time correlation functions are calculated; this modelbreaks down at the gel point. The breakdown is characterized by a divergence of the density fluctuations, and is caused by the large mobility of large clusters. For all models withs< the density fluctuations remain finite att _c, and the equal-time correlation functions in the pre- and in the post-gel stage are calculated. Many explicit and asymptotic results are given. From the exact solution the upper critical dimension in this gelling model isd _c=2.     

钢中Si、Mn的电子探针定量分析与标样

采用特制的Fe-Si、Fe-Mn合金系列标样，用电子探针测定了钢或铁基合金中低含量的Si和Mn元素、与用纯元素作标样、经ZAF修正的结果相比较，提高了分析准确度．