Theoretical and experimental approaches to kinetics at the collapse transition of a homopolymer

Summary We discuss some recent theoretical studies of the kinetics of the collapse transition in homopolymers. An isolated polymer is modelled using computer simulation, and a time-dependent mean-field theory. The mean-field theory is analysed analytically for early stages, and for short polymers the equations are studied numerically. The results of simulation and theory are compared yielding, we argue, a consistent physical picture. Quantitative comparisons are not yet given, but seem relatively promising. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4– 1994.     

Tunnelling in periodically driven systems

Tunnelling in periodically driven bistable symmetric potential wells is investigated in an analytical approximation in a domain where the driving frequency is large compared to the tunnelling frequency and only the four lowest lying levels contribute significantly. The influence of finite level widths is taken into account, and a smooth variation of the amplitude of the driving field is allowed for.     

On generalized gradients

In this paper we present a concept of the construction of generalized gradients by considering a development of directional derivatives into spherical harmonics. This leads to a derivation system as a system of generalized partial derivatives. Necessary conditions for local extrema for a broad class of not necessarily differentiable function can be given and a characterization of points of differentiability can be proved by using generalized gradients.     

Untersuchung des anisotropen Kriechverhaltens vorgeschädigter Werkstoffe am austenitischen Stahl X8 CrNiMoNb 16 16

Übersicht Ziel der Untersuchung ist es, den Einfluß von Kriechschädigung und Belastungsvorgeschichte auf das weitere Kriechverhalten nach einer Änderung der Belastungsrichtung zu bestimmen. Die ermittelten Kriechbruchzeiten werden stark von der Änderung der Belastungsrichtung beeinflußt. Dieses Verhalten wird mit einer tensoriell nichtlinearen Theorie erklärt, indem man den Einfluß der Vorschädigung mit einem zweistufigen Tensor darstellt.

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Rheology of a mixture of liquid-crystal polymers in solution

The rheological behavior of a mixture of two liquid-crystal polymers, hydroxypropyl cellulose and ethyl cellulose, in acetone solution is studied. The total polymer concentration in the solvent is held constant (40%) as the ratio of the two polymers is varied. The mixtures are anisotropic, isotropic, or biphasic (isotropic/anisotropic), depending on the concentration. Curves of viscosity vs shear rate for all the mixtures studied show three regions of viscosity, as described by Onogi and Asada for liquid-crystal polymers. The viscosity as a function of the weight ratio of the two polymers at constant shear rate exhibits deviations from additivity of viscosities of the two components at all concentrations. In mixtures of two polymers in the melt, deviations are also observed; the negative ones are attributed to phase separation and the positive ones to homogenous mixing (comparison with the phase diagram). All the mixtures studied (anisotropic, isotropic, or biphasic), show ranges of shear rates where the first normal-stress difference is negative, as is generally observed for anisotropic liquid-crystal polymers. It is concluded that the isotropic solutions become anisotropic under shear, as they are not far from the critical concentration. © 1994 John Wiley & Sons, Inc.     

Properties of polystyrene-poly(methylmethacrylate) random and diblock copolymers in dilute and semidilute solutions

Solution properties for random and diblock copolymers of polystyrene (PS) and poly(methyl methacrylate) (PMMA) have been measured by dynamic and total intensity light scattering in solvents of differing quality. The results are compared with the corresponding properties for PS and PMMA homopolymers of similar molecular weight, in order to determine if interactions between unlike monomers are significant. The hydrodynamic radius (R_h) and diffusion second virial coefficient (k_d) for the random copolymer are found to be larger than the corresponding values for the homopolymers in a solvent which is near-theta for the two homopolymers, whereas no such effect is observed for the block copolymer. This suggests that most intrachain interactions occur a relatively short distance along the chain backbone. In a mutual good solvent R_h and k_d of the random copolymer are comparable to the average of the values for the homopolymers, indicating that in a good solvent monomer/solvent interactions dominate over monomer/monomer interactions. For an isolated diblock copolymer in a mutual good solvent, there is no evidence that interactions between unlike monomers lead to additional expansion of the entire molecule, as measured by R_h, nor expansion of the individual blocks as probed by light scattering with one block optically masked. However, at low but finite concentration there is evidence (the coefficients of the binary interaction terms in the viscosity and the mutual diffusion coefficient, and the second and third virial coefficients) that a weak ordering effect may exist in block copolymer solutions, far from the conditions where microphase separation occurs. Finally, measurements of ternary polymer-polymer-solvent solutions show no dependence on monomer composition or monomer distribution for the tracer diffusion of probe PS-PMMA copolymers in a PMMA/toluene matrix. This indicate that the frictional interaction is largely unaffected by interactions between unlike monomers. However, there is evidence that the thermodynamic interaction is more unfavorable between a random copolymer and the homopolymer matrix than between a diblock and the matrix. © 1994 John Wiley & Sons, Inc.     

Reduction of tympanic membrane displacement during vocalization of the arboreal frog, Eleutherodactylus coqui.

Tympanic membrane (TM) velocities of vocalizing male frogs, Eleutherodactylus coqui, were measured in the field using laser vibrometry. The animal's call produced levels of 114-120 dB SPL measured at distances of 12-20 mm from the eardrum and mean TM displacements in response to the two notes of the male's own advertisement call were 1.84 and 2.08 nm, respectively. These values are close to the TM displacements obtained in response to playback of the two-note call at much lower sound levels. Thus TM vibrations are attenuated during phonation in the frog, and several candidate mechanisms for auditory sensitivity reduction are discussed.