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.     

Municipal solid waste conversion to energy

In recent years it has been recognised by an increasing number of nations that there is considerable energy potential within MSW. As a result many countries have established R,D& D programmes to examine methods of exploiting this potential. The IEA's MSW Conversion Activity was set up in 1986 to provide an infrastructure for sharing information and co-ordinating work in this area internationally. This Activity was extended in 1989 and currently a total of 9 nations participate in it.

To cope with the wide scope of the area (encompassing both biological and thermal processing of MSW) the Activity was divided into three subgroups or Expert Working Groups (EWGs). Each of these dealt with a distinct area of expertise:

1. •Downstream effects of source separation and screening of MSW

2. •Sampling and analytical protocols

3. •Landfill gas

In addition to these groups a central secretariat based at Harwell (UK) has provided guidance, established and administered databases of contacts and produced a series of national reports.

This paper describes the achievements of the Activity and discusses work proposed for the future.     

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.     

Thermal and thermoelastic properties of fast extrusion furnace (FEF) carbon black loaded SBR vulcanizates

The effect of FEF carbon black as filler on the thermal capacity c, diffusivity a, and thermal conductivity λ, of styrene butadiene rubber (SBR) composites in the temperature range 300–420 K was studied. The filler strongly increases the thermal diffusivity, whilst strongly decreasing the thermal capacity and the thermal conductivity (except at high FEF content ≥80 phr). The influence of the filler on the thermoelastic behaviour of the same composites was also investigated. It was found that the thermoelastic temperature change (ΔT) increased with carbon black concentration as well as the entropy change per unit extension.     

Effect of harvesting time and fruit size on titratable acidity, soluble solid and distribution of limonin in Thai tangerine juice

The effect of fruit size and harvesting of Thai tangerine fruit ( Citrus reticulata , Blanco) at different growth stages, 8–12 months after fruit set, on the distribution of limonin in whole fruit as well as in the individual fruit parts and extracted juice was investigated. The highest limonin concentration was observed in seed, followed by albedo, flavedo, segment membrane and juice sacs in decreasing order. The limonin concentration in juice as well as in whole fruit was decreased when fruit was harvested 8–12 months of fruit set. Increasing harvesting time from 8 to 12 months showed corresponding decreases in the amount of limonin in flavedo, albedo and seed. There was a decrease in titrable acidity and increase in total soluble solid and total soluble solid/titrable acidity ratio of juice with a later than normal harvesting time. However, fruit size showed no effect on limonin content and other properties of juice extracted from tangerine.     

CR／MMA乳液接枝共聚物的研制

用乳液接枝共聚法制备ＣＲ／ＭＭＡ共聚物，讨论ＣＲ乳液、引发剂、接枝温度、ＭＭＡ用量对接枝共聚转化率，接枝ＭＭＡ含量、ＭＭＡ接枝效率和粘接性能的影响，用红外光谱对接枝共聚物进行表征，该共聚物具有较好的粘接性能。     

SO_4~（2－）／ZrO_2固体超强酸的失活与再生

初步探索了ＳＯ_４~２－／ＺｒＯ２固体超强酸的失活机理．并着重研究了催化剂的两种再生方法：灼烧法和溶剂洗涤法。催化剂主要是因结焦而失活，高温灼烧能基本恢复催化剂原有活性．且再生效果与灼烧温度有关。溶剂洗涤法有一定的再生能力，但不显著．