Thickening process of polyethylene single crystals at an early stage of annealing

The thickening process of polyethylene single crystals was simulated with computer by the Monte Carlo method. According to the experimental results in the previous report, the time dependence of the long period changed greatly with annealing temperature; at lower temperatures the long period increased gradually, while at high temperatures the long period rapidly increased at a very early stage of annealing and then increased gradually after passing through a plateau. Through computer simulation, it was shown that such a great change in the time dependence of the long period with annealing temperature can be explained by combining two mechanisms: (A) sliding diffusion of molecular segments along the chain axis and (B) local melt-recrystallization (namely, local melting followed by recystallization).     

SELF-ASSEMBLING AMPHIPHILIC POLYELECTROLYTES AND THEIR NANOSTRUCTURES

The self-assembling behavior of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate (AMPS)and hydrophobic comonomers possessing dodecyl groups linked by various spacer bonds was discussed with a focus on theeffect of the spacer. The characterization of association behavior of such polymers in water using quasielastic light scattering,capillary electrophoresis, NMR relaxation, various fluorescence, and viscoelastic methods was described. These copolymersform a variety of self-assembled nanostructures depending on the type of the spacer. Random copolymers of AMPS and N-dodecylmethacrylamide show a strong preference for intrapolymer self-association even in concentrated aqueous solutionsforming single-macromolecular self-assemblies (unimolecular micelles). In contrast, random copolymers of AMPS anddodecyl methacrylate are prone to undergo interpolymer associations yielding multipolymer micelles. In random copolymersof AMPS and a methacrylate substituted a nonionic surfactant (HO(CH_2CH_2O)_(25)C_(12)H_(25)) (C_(12)E_(25)), dodecyl groups are muchless restricted by the polymer backbone because they are linked via a long, flexible hydrophilic spacer. Thus, the polymer-bound C_(12)E_(25) surfactant moieties form micelles similar to those formed by discrete surfactants, but they are bridged bypolymer chains forming a network structure.     

Modulating the rheological response of shear thickening fluids by variation in molecular weight of carrier fluid and its correlation with impact resistance of treated p-aramid fabrics

The present study deals with the effect of molecular weight of carrier fluid on the rheological behaviour of shear thickening fluid (STF) and impact energy absorption by treated p-aramid fabrics. High molecular weight polyethylene glycols (HMW-PEG: 1000, 3000 and 6000 g mol⁻¹) were individually added to a mixture of PEG 200 and PEG 600 to prepare ternary mixtures of carrier fluids. Increase in average molecular weight of the carrier fluid via addition of PEG 1000 and PEG 3000 enhanced the dilatant behaviour of STF. On the other hand, addition of PEG 6000 led to a rheological response inferior to that obtained via addition of PEG 3000 owing to solidification of the former at room temperature resulting in fusion of silica particles. However, an inverse relation was observed between the rheological behaviour of HMW-PEG based STFs and impact resistance of p-aramid fabrics treated with them. The diminution in impact energy absorption occurred due to lubrication effect caused by long polymer chains of HMW-PEG. On the other hand, fusion of solidified PEG 6000 and silica particles created rough microstructures over the yarn surface, which enhanced inter-yarn friction, resulting in improved impact energy absorption.     

Negative thixotropy of solutions of partially hydrolyzed polyacrylamide

We found that the character of negative thixotropy of partially hydrolyzed polyacrylamide in aqueous glycerol strongly depends on polymer concentration, glycerol content and shear rate applied. At low polymer and glycerol concentrations, shear stress and viscosity slowly increased during shearing to a limiting value. In addition to this behavior, a steep increase in shear stress as well as normal stress followed by their pronounced oscillations occurred at higher concentrations of both components and at higher shear rates. Similarly to the negative thixotropic effect in solutions of other polymers in organic solvents, the hydrodynamic conditions in which the effects set in seem to be controlled by the shear stress acting in the flowing solution; initial kinetics of the effect depends on solvent viscosity and shear stress applied. To explain the influence of the glycerol content and degree of ionization of the polymer on the minimum shear stress at which the effect sets in, a decisive role of intermolecular electrostatic repulsions in association of the polymer molecules in shear field is assumed.     

Rheological properties of hydrophobically modified alkali-soluble polymers—effects of ethylene–oxide chain length

The rheological properties of hydrophobic alkali-soluble associative polymers (HASE) were studied using controlled rate (Mettler LS40) and controlled stress (TA CSL 500) rheometers. The effects of pH and polymer concentrations on the rheological properties of three HASE model polymer systems (i.e., HASE 5141, 5134, and 5142, with a degree of ethoxylation of 2.5, 10, and 40 mol, respectively) and a reference polymer without associative hydrophobes (MAAEA) were examined. As the pH is increased by addition of ammonia to greater than 5–6, the carboxyl groups ionize to carboxylate ions and the polymers become water soluble. The HASE polymers thicken mainly by hydrophobic association. Viscosity can increase by two to three orders of magnitude as pH is raised to 9. The degree of ethoxylation in the macromonomer controls the nature of the hydrophobic association junctions by altering the flexibility and hydrophobicity of the macromonomer. Optimum thickening efficiency is observed in the system with approximately 10 mol of an ethylene–oxide spacer between the polymer backbone and the macromonomer. Viscoelastic study shows that the maximum thickening efficiency also corresponds to the dominant elastic property observed in the system with 10 mol of EO. All the model systems except the control system without hydrophobe exhibit strain thickening of the viscous and elastic components. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2275–2290, 1998     

Growth by Ledges

The prediction and observation of growth ledges at various moving interphase boundaries in solid-solid phase transformations has become increasingly widespread since first proposed in the early 1960's by Aaronson. The role of steps at the growth interfaces in several phase transformations is reviewed. For precipitate plates emphasis is placed on rationalizing experimental growth kinetics with mathematical models developed for the migration rate of a ledge. More complex transformations are employed to examine the possible role of growth ledges to account for microstructure development. In all cases, the growth ledge is shown to be necessary to fully understand solid-solid phase transformations.     

The compositional structure of highly turbulent piloted premixed flames issuing into a hot coflow

Simultaneous line measurements of major species and temperature by the Raman–Rayleigh technique, combined with CO two-photon laser-induced fluorescence and crossed-plane OH planar laser-induced fluorescence have been applied to a series of flames in the Piloted Premixed Jet Burner (PPJB). The PPJB is capable of stabilizing highly turbulent premixed jet flames through the use of a stoichiometric pilot and a large coflow of hot combustion products. Four flames with increasing jet velocities and constant jet equivalence ratios are examined in this paper. The characteristics of these four flames range from stable flame brushes with reaction zones that can be described as thin and “flamelet-like” to flames that have thickened reaction zones and exhibit extinction re-ignition behaviour. Radial profiles of the mean temperature are reported, indicating the mean thermal extent of the pilot and spatial location of the mean flame brush. Measurements of carbon monoxide (CO) and the hydroxyl radical (OH) reveal a gradual decrease in the conditional mean as the jet velocity is increased and the flame approaches extinction. Experimental results for the conditional mean temperature gradient show a progressive trend of reaction zone thickening with increasing jet velocities, indicating the increased interaction of turbulence with the reaction zone at higher turbulence levels. For the compositions examined, the product of CO and OH mole fractions ([CO][OH]) is shown to be a good qualitative indicator for the net rate of production of carbon dioxide. The axial variation of [CO][OH] is shown to correlate well with the mean chemi-luminescence of the flames including the extinction re-ignition regions. The experimental findings reported in this paper further support the hypothesis of an initial ignition region followed by extinction and re-ignition regions for certain PPJB flames.     

A new type of visco-plastic flow curve observed in certain concentrated diblock copolymer solutions

A diblock copolymer of styrene and isoprene (hydrogenated) is dissolved in C₁₁/C₁₂ n-paraffins and o-xylene (or cyclohexane) mixtures. An unusual type of flow curve is obtained in certain ranges of composition and under certain conditions of preparation. With increasing shear rates, the flow curve is first of the Bingham type, followed by a sudden shear thickening at almost discrete rate of shear and then by a second branch of almost linear increase. Time independent and reproducible behaviour can be achieved. A linear model is proposed and the possible molecular arrangement that corresponds to this model is discussed.Partly presented at the Annual Meeting of the Deutsche Rheologische Gesellschaft, May 13–15, 1985 in Berlin, FRG     

Viscoplastic flow and shear thickening in concentrated diblock copolymer solutions

Concentrated (typically 6%) solutions of a polystyrene-polyisoprene diblock copolymer in low viscosity paraffinic solvents form a micelle system by precipitating the polystyrene blocks, whereas the polyisoprene blocks are in solution. Besides viscoplastic behavior without thixotropy, this system exhibits a pronounced shear thickening in steady-state shear flow. The micelles are stable up to shear rates of more than 10⁵ s^–1. The properties of the solutions, especially the shear-thickening behavior, depend on the thermal history of the samples as well as on the solvent properties and are sensitive to flow field disturbances occurring in rotational viscometer devices with a profiled surface structure as commonly used to avoid wall slip in dispersed materials. The shear thickening is found to be related to the formation of a long-range ordered structure which also gives rise to the yield point. This long-range order enables aggregate flow with less energy dissipation at low shear rates. Shear-induced break-up of the aggregates appears as a shear-thickening transition which is observed in different types of flow fields.