Network topology and the theory of rubber elasticity

The earliest investigations on rubber elasticity, commencing in the 19th century, were necessarily limited to phenomenological interpretations. The realisation that polymers consist of very long molecular chains. commencing c. 1930, gave impetus to the molecular theory of rubber elasticity (1932-). according to which the high deformability of an elastomer, and the elastic force generated by deformation, stem from the configurations accessible to long molecular chains. Theories of rubber elasticity put forward from 1934-1946 relied on the assumption that the junctions of the rubber network undergo displacements that are affine in macroscopic strain. The theory of James and Guth (1947) dispensed with this premise, and demonstrated instead that the mean positions of the junctions of a ‘phantom’ network consisting of Gaussian chains devoid of material properties are affine in the strain. The vital significance of the distinction between the actual distribution of chain vectors in a network and their distribution if the junctions would be fixed at their mean positions went unnoticed for nearly 30 years. Experimental investigations, commencing with the incisive work of Gee in 1946. revealed large departures from the relationship of stress to strain predicted by the theories cited. This discrepancy prompted extensive studies, theoretical and experimental, during succeeding years. Inquiry into the fundamentals of polymer networks, formed for example by interlinking very long polymer molecules, exposed the need to take account of network imperfections, typically consisting of chains attached at only one end to a network junction. Various means were advocated to make corrections for these imperfections. The cycle rank ζ of the network has been shown (1976) to be the fundamental measure of its connectivity, regardless of the junction functionality and pattern of imperfections. Often overlooked is the copious interpenetration of the chains comprising typical elastomeric networks. Theories that attempt to represent such networks on a lattice are incompatible with this universal feature. Moreover, the dense interpenetration of chains may limit the ability of junctions in real networks to accommodate the fluctuations envisaged in the theory of phantom networks. It was suggested in 1975 that departures from the form predicted for the elastic equation of state are due to constraints on the fluctuations of junctions whose effect diminishes with deformation and with dilation. Formulation of a self-consistent theory based on this suggestion required recognition of the non-affine connection between the chain vector distribution function and the macroscopic strain in a real network, which may partake of characteristics of a phantom network in some degree. Implementation of the idea was achieved through postulation of domains of constraint affecting the equilibrium distribution of fluctuations of network junctions from their mean positions. This led in due course to a theory that accounts for the relationship of stress to strain virtually throughout the ranges of strain accessible to measurement. The theory establishes connections between structure and elastic properties. This is achieved with utmost frugality in arbitrary parameters.     

贵欧泊合成的某些方面

描述了在俄罗斯Dubna应用研究中心合成全硅欧泊的开发研究以及基本步骤. 阐述了这种漂亮的、相对无孔隙的合成欧泊的结构和基本特征以及这种合成欧泊切磨和抛磨的例子.     

Symmetry-breaking transitions in equilibrium shapes of coherent precipitates: Effect of elastic anisotropy and inhomogeneity

We examine the symmetry-breaking transitions in equilibrium shapes of coherent precipitates in two-dimensional (2-D) systems under a plane-strain condition with the principal misfit strain components ε* _xx and ε* _yy . For systems with cubic elastic moduli, we first show all the shape transitions associated with different values of t=ε* _yy /ε* _xx . We also characterize each of these transitions, by studying its dependence on elastic anisotropy and inhomogeneity. For systems with dilatational misfit (t=1) and those with pure shear misfit (t=−1), the transition is from an equiaxed shape to an elongated shape, resulting in a break in rotational symmetry. For systems with nondilatational misfit (−1<t<1; t ≠ 0), the transition involves a break in mirror symmetries normal to the x- and y-axes. The transition is continuous in all cases, except when 0<t<1. For systems which allow an invariant line (−1≤t<0), the critical size increases with an increase in the particle stiffness. However, for systems which do not allow an invariant line (0<t≤1), the critical size first decreases, reaches a minimum, and then starts increasing with increasing particle stiffness; moreover, the transition is also forbidden when the particle stiffness is greater than a critical value.     

Investigation of the action of flame retardants in cellulose. I. Investigation of the flame retardant action of 2,2′-oxybis(5,5-dimethyl-1,3,2-dioxaphosphorinane-2,2′-disulfide) in cellulose

Pyrolysis experiments were performed in high vacuum and under reduced air pressure (100 Pa). The volatile products of pure cellulose and cellulose containing various amounts of flame retardant 2,2′-oxybis (5,5-dimethyl-1,3,2-dioxaphosphorinane-2,2′-disulfide), i.e., Sandoflam 5060 of Sandoz AG, were studied by means of gas chromatography in combination with mass spectroscopy. The volatile products were characterized with infrared spectroscopy. The studied revealed that the incorporation of the flame retardant enhanced the water release and shifted the onset of this reaction to lower temperature. On the basis of these findings an explanation for the mechanism of flame retardancy in generated cellulose fibers modified with this particular flame retardant is attempted. From experiments with different residual air pressure the influence of oxygen on the primary processes of the pyrolytic degradation of cellulose is being discussed.     

Continuous phase quadrature phase shift keyed signaling techniquewith coding

A continuous phase quadrature phase shift keyed (CPQPSK) modulation technique is presented. This method utilizes a conventional QPSK modulator and a phase trajectory converter to approximate M=4, h=1/4 continuous phase signal and allows low cost, low complexity, and high rate (>1 Gbit/s) CPM modem implementation for bandwidth efficient transmission through nonlinear satellite channels. Using a communications analysis computer program it has been found that CPQPSK has 99 percent out-of-band power of 0.8R (MSK has 99 percent out-of-band power of 1.2 R where R is defined as bit rate), continuous phase trajectories, and nearly constant envelope amplitude. Simulation of realistic hardware designs indicate that the CPQPSK will require an Eb/No of 14 dB to achieve a bit error rate (BER) of 10^-6. Forward error correcting techniques using block codes with an overhead of 10 percent indicate that the Eb/No requirements can be reduced to 11.2 dB for 10^-6 BER     

Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.