Dynamical considerations of network properties

Elasticity is discussed as an aspect of viscoelasticity, which is described by the tube model. The effects of both crosslinks and entanglements contribute to this model and a discussion of how these effects can be quantified is given. At high enough concentration, entanglements ensure the existence of elastic effects even without crosslinks, and a theory is presented on how this dynamical phase change comes about.     

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.     

Some factors affecting the electrical properties of carbon-black-loaded butyl rubber during vulcanization

Butyl rubber mixtures loaded with 70 phr general purpose furnace black (GPF) and tetramethyl thiuram disulphide (TMTD)/S as vulcanizing system were prepared. The kinetics of their electrical conductivity development during the vulcanization process were followed by using an especially devised system. It was found that the increase in the electrical conductivity during vulcanization obeys an exponential growth function with time constant τ, which markedly decreases with increasing vulcanization temperature as well as with the efficiency of the vulcanizing system. After completion of the vulcanization process, about 80 min, the samples obtained possess reasonable stability and reproducibility of electrical conductivity.     

Stabilization of bioethanol recovery with silicone rubber‐coated ethanol‐permselective silicalite membranes by controlling the pH of acidic feed solution

In order to produce highly concentrated bioethanol by pervaporation using an ethanol‐permselective silicalite membrane, techniques to suppress adsorption of succinic acid, which is a chief by‐product of ethanol fermentation and causes the deterioration in pervaporation performance, onto the silicalite crystals was investigated. The amount adsorbed increased as the pH of the aqueous succinic acid solution decreased. The pervaporation performance also decreased with decreasing pH when the ternary mixtures of ethanol/water/succinic acid were separated. Using silicalite membranes individually coated with two types of silicone rubber, pervaporation performance was significantly improved in the pH range of 5 to 7, when compared with that of non‐coated silicalite membranes in ternary mixtures of ethanol/water/succinic acid. Moreover, when using a silicalite membrane double‐coated with the two types of silicone rubber, pervaporation performance was stabilized at lower pH values. In the separation of bioethanol by pervaporation using the double‐coated silicalite membrane, removal of accumulated substances having an ultraviolet absorption maximum at approximately 260 nm from the fermentation broth proved to be vital for efficient pervaporation. Copyright © 2005 Society of Chemical Industry     

Microstructure-related fracture toughness and fatigue crack growth behaviour in toughened, anhydride-cured epoxy resins

Fracture toughness and fatigue crack propagation (FCP) of plain and modified anhydride-cured epoxy resin (EP) were studied at ambient temperature. Liquid carboxyl-terminated acrylonitrile-butadiene (CTBN) and silicon (SI) rubber dispersions were used as tougheners for the EP. The morphology of the modified EP was characterized by dynamic mechanical analysis (DMA) and by scanning electron microscopy (SEM). The fracture toughness, K_c, of the compositions decreased with increasing deformation rate. K_c of the EP was slightly improved by CTBN addition and practically unaffected by incorporation of the SI dispersion when tests were performed at low cross-head speed, v. Both modifiers improved K_c at high v, and also the resistance to FCP, by shifting the curves to higher stress intensity factor ranges, ΔK, by comparison with the plain EP. It was established that both fracture and fatigue performance rely on the compliance, J_R, at the rubbery plateau, and thus on the apparent molecular mass between crosslinks, M_c. The failure mechanisms were less dependent upon the loading mode (fracture, fatigue), but differed basically for the various modifiers. Rubber-induced cavitation and shear yielding of the EP were dominant for CTBN, whereas crack bifurcation and branching controlled the cracking in SI-modified EP. The simultaneous use of both modifiers resulted in a synergistic effect for both the fracture toughness at high deformation rate and the FCP behavior.     

影响喷气燃料与橡胶相容性的因素

采用几种具有不同初始物理性能及不同丙烯腈含量、不同硫化剂和硫化程度的丁腈橡胶，考察了其配方和物理性能对采用不同工艺条件生产的喷气燃料的相容性。结果表明，喷气燃料与橡胶的相容性不仅与喷气燃料的加工工艺有关，而且与橡胶的组成及其制备工艺有关。采用非加氢工艺生产的喷气燃料与橡胶的相容性好于采用加氢工艺(特别是加氢裂化工艺)生产的喷气燃料。橡胶材料的初始力学性能的好坏并不完全决定其与喷气燃料相容性的好坏，橡胶材料的耐过氧化物侵蚀能力才是影响相容性好坏的主要因素。橡胶的组成和其制备工艺决定了橡胶在喷气燃料中萃取物的数量和组成，不同萃取物的综合作用给相容性带来不同程度的影响。用硫作硫化剂的橡胶虽然原始强度低于用过氧化物作硫化剂的橡胶，但前者与喷气燃料的相容性却远好于后者。     

A comparative study of short nylon fiber—Natural rubber composites prepared from dry rubber and latex masterbatch

A novel method for the preparation of short nylon fiber–natural rubber composites was developed in which short fibers chopped to approximately 6 mm were incorporated in the latex stage and processed into sheet form. By this method, mixing cycle time was reduced without compromising the fiber dispersion. Fiber breakage during mixing was reduced. The new composites when compounded with a dry bonding system based on hexamethylenetetramine, resorcinol and hydrated silica (HRH) showed improved modulus, tensile strength and abrasion resistance compared to conventional composites. Tear strength, resilience, and compression set were similar to the conventional composites. SEM analysis indicated better interaction between matrix and fibers in the case of latex master batch. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Prediction of the twisting moment and axial force in a circular rubber cylinder for combined extension and torsion based on the logarithmic strain approach

The scope of the present work is the application of a particular class of strain energy function, based on the logarithmic strain, for the prediction of the twisting moment and axial force of a rubber circular cylinder under combined extension and torsion. The strain energy function involves four material parameters three of which are determined by fitting published experimental data from simple tensile and compression tests of natural rubber. One of the parameters of the proposed model has physical meaning, and it is equal to one ninth of the initial modulus of elasticity of the material. Hence, the number of unknown parameters is reduced to three. The logarithmic strain energy function is then applied to a combined extension and torsion problem of a rubber circular cylinder to check its performance for more complicated deformations. The results are compared with corresponding experimental and theoretical solutions available in the literature to validate the proposed model. It is found that the proposed strain energy function apart from predicting the common modes of deformations is also capable to determine more complicated types of deformation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008