Linear dynamic mechanical properties of an SBS block copolymer

Dynamic viscosity and elastic modulus for a low molecular weight styrene-butadiene-styrene (SBS) block copolymer ate measured as a function of temperature (80-170°C) and frequency using the eccentric rotating disc geometry. These linear properties are superimposed to yield master curves each of which exhibits two branches below different (critical) reduced frequencies. At lower temperatures, the non-Newtonian behavior characteristic of SBS block copolymers is observed. In contrast, Newtonian response occurs at higher temperatures. As a consequence, plots of the viscoelastic properties vs temperature exhibit discontinuities below the critical frequencies, reflecting a narrow transition at about 142°C. Above this temperature, it is inferred, consistent with the equality of dynamic and steady state viscosities, that the polystyrene (S) blocks, existent in dispersed domains at low temperatures, exceed a critical degree of compatibility with the continuous polybutadiene phase. The activation energies indicate that the S blocks affect the temperature dependence of the dynamic properties in proportion to their presence in an interphase which is assumed to continuously grow in size as temperature is raised to the transition temperature. Below the critical reduced frequencies, it is inferred that S domain disruption may increasingly occur in conjunction with the observed property enhancement due to these domains, relative to the miscible blocks, as reduced frequency is lowered. However, above these frequencies, the presence of frequency-temperature superposition implies that the S domains and the miscible blocks are equivalent in their effects on properties. At still higher reduced frequencies, the domains present at the low temperatures studied are assumed to remain intact, but plateau behavior similar to the response characteristic of homopolymers is observed.     

Packing Density of Composite Powder Mixtures

A model of particle packing in binary composite systems is developed. The effects of both inclusion surfaces and touching inclusions on the packing density are taken into account. To implement the model, a statistical approach is used to determine the number of inclusion contacts as a function of inclusion content. The statistical approach indicates that the average number of inclusion contacts is a linear function of the inclusion volume fraction, a result which agrees very well with independent computer simulations. The model suggests that the packing efficiency, defined by the ratio of the packing density to the ideal packing density (as originally derived by Furnas), is governed by the inclusion volume fraction ( f_i ) and the particle to inclusion size ratio ( r ). Good agreement is obtained between the theory and experimental literature data.     

Microstructure of high modulus solid state extruded polyethylene: 2. X-ray scattering studies of 12, 24 and 36 extrusion draw ratio

The microstructure of a series of solid state extruded polyethylene fibres was examined by wide- and small-angle X-ray scattering. By measuring absolute intensities using a two dimensional position sensitive detector, accurate values of the small-angle invariant for anisotropic samples were obtained. This measurement coupled with wide-angle X-ray scattering and d.s.c. permitted determination of the density of the noncrystalline component. The use of a two phase model for solid state extruded polyethylene is justified if consideration is given to the effective densities of the crystalline and noncrystalline phases, which change with deformation. The effective density of the crystalline phase decreases by 1% (0.999–0.990 g cm^?3) from the unextruded billet compared to a 36 draw ratio extrudate, while the noncrystalline phase density increases by 6% (0.84–0.89 g cm^?3). These changes lead to an overall decrease in the mean squared electron density fluctuation of 63%. The average axial crystallite length measured by wide-angle X-ray scattering increases with extrusion draw ratio while the SAXS long period decreases and weakens considerably. These observations and the electron microscopy results from the previous paper, (Polymer, 1982, 23, 1069), are fully consistent with the key features of the Peterlin model of fibre microstructure.     

Effect of variety and stage of growth on potential allelochemic compounds in soybean roots

HPLC was used to obtain fingerprint patterns of organic compounds extracted from roots of five soybean varieties at seven stages of growth. Fifteen major peaks were observed in all varieties at most growth stages. With increasing stage of growth, the less polar compounds accounted for a greater relative percentage of total peak area. Concentration of compounds extracted from roots increased dramatically as plants approached nodulation and flowering and then decreased to initial levels as plants matured.     

Higher Purity Ingot Cerium from Molten Salts

Based on the experimental results obtained at the Reno Metallurgy Research Center of the US Bureau of Mines, an evaluation of several critical factors in the electrowin-ning of cerium from molten salts is presented.     

Structural characterization of vulcanizates. Part VI. The 2-mercaptobenzothiazole-accelerated natural rubber–sulfur system

The crosslinking efficiency of sulfur in the vulcanization of natural rubber in the presence of 2-mercaptobenzothiazole, zinc oxide, and lauric acid has been determined as a function of cure time, cure temperature, and lauric acid concentration. With a low concentration of lauric acid structurally complex networks are formed, which contain 11–19 combined sulfur atoms per chemical crosslink present. The complexity increases with time of vulcanization. With a high lauric acid concentration much simpler networks are formed, which become progressively more simple as reaction proceeds (6 network-combined sulfur atoms per chemical crosslink, decreasing to 2.4 with time). Increasing the cure temperature from 100 to 140°C. reduces the efficiency of crosslinking in both cases. The changes in efficiency are attributed to the influences of the reaction variables (in particular, the concentration of rubber-soluble complexes of the zinc laurate with zinc benzothiazolyl mercaptide) on the structure and subsequent reactions of initially formed polysulfidic crosslinks.     

The source of degradation during extrusion of polystyrene

The nature and magnitude of mechanical reactions of polystyrene in capillary flow has been examined in a model extrusion process. Studies on polystyrene quantify the sensitive increase in shear degradation tendency with increasing polymer molecular weight. A molecular weight spectrum caused by the shear stress profile was measured across the extrudate radius by the new technique of solvent coring. It was further determined that an appreciable fraction of the mechanical reaction is shear induced in the capillary reservoir. This is confirmed by precision determinations of molecular weights and distributions by gel permeation chromatography on samples taken from concentric layers in the capillary reservoir after 50% sample extrusion. These results, involving traces of oxygen as a chemical probe, describe the stress profile in the reservoir and in the capillary during the pressure extrusion of high molecular weight polystyrene. Thus, changes in molecular weight and distribution may be attributable to changes in different portions of the shear geometry rather than the uniform changes generally considered. Clear evidence is also presented showing the dramatic effects of oxygen on these shear-induced changes in molecular weight and distribution.     

The adsorption of coumarin at solid metal electrodes

The effect of coumarin on the “deposition potential” of a number of metals at solid metal surfaces has been compared with that at a dropping mercury electrode. These results have been used to interpret the adsorption of coumarin on different metal surfaces and to suggest that Tl⁺ and Pb²⁺ ions are specifically adsorbed on mercury and that Tl⁺, Co²⁺, Fe²⁺, Ni²⁺ and Zn²⁺ are specifically adsorbed on their parent metals.     

Polymer degradation. V. Changes in molecular weight distributions during sonic irradiation of polyisobutene

Gel permeation chromatography was used to follow changes in the molecular weight distribution of a polyisobutene, initial M _v = 466,000, during degradation induced by sonic irradiation. Seven samples taken at times of 200–163,500 sec. were studied. In general, a steady decrease in molecular weight was observed, although a bimodal distribution was present after 20,000 sec. irradiation. Various measures of inhomogeneity, M _w/M _n, U, etc., were examined. The function, σ_n/M _w, where σ_n is the standard deviation of the number distribution, is considered as a measure of the relative distribution. It is shown to be almost constant throughout the degradation.     

Estimation of wall effects on floating cylinders

Under the assumptions of classical linearised water-wave theory, the time-harmonic two-dimensional motion of a rigid body floating in the surface of a fluid may be characterised by various coefficients which express components of the hydrodynamic forces acting on that body. For a single body in isolation, these are relatively simple to calculate. For bodies placed next to a vertical wall, the corresponding calculations are often much more complicated. In this paper the well-known wide-spacing approximation is used to develop approximations to the hydrodynamic coefficients for a body having a vertical plane of symmetry, but otherwise of arbitrary cross-section, next to a wall solely in terms of the results for an isolated body. Exact results are compared with the wide-spacing approximations for semi-immersed circular cylinders and cylinders of rectangular cross-section. They show that the approximation works remarkably well over all frequency ranges and even when the cylinders are very close to the wall.