A coercivity model with competing anisotropies

In standard coercivity theory, formulae derived for homogeneous material are applied to inhomogeneous situations. The model considered here contains inherent inhomogeneity in the form of competing volume and surface anisotropies. Its coercivity never exceeds half the Stoner-Wohlfarth value, decreases with particle size, and vanishes at a finite critical size.     

On fiber-preserving isotopies of surface homeomorphisms

We show that there are homeomorphisms of closed oriented genus surfaces which are fiber-preserving with respect to an irregular branched covering and isotopic to the identity, but which are not fiber-isotopic to the identity.

     

Investigation of the rh-catalyzed asymmetric reductive aldol reaction. Expanded scope based on reaction analysis

[reaction: see text] A series of experiments are described that suggest that the Rh-catalyzed reductive aldol reaction proceeds by addition of a Rh(I) hydride, generated in situ, to the reacting acrylate followed by a stereochemistry-controlling aldol addition reaction. On the basis of this hypothesis, reaction conditions are engineered that allow for increased substrate scope.     

Rheological behavior of precursor PPV monolayers

The rheological behavior of different precursor poly(p-phenylene vinylene) (prec-PPV) monolayers at the air-water interface was investigated using an interfacial stress rheometer (ISR). This device nicely reveals a transition of the precursor poly(2,5-dimethoxy-1,4 phenylene vinylene) (prec-DMePPV) monolayer from Newtonian to elastic behavior with increasing surface pressure. The transition is accompanied by an increase in the modulus. This behavior coincides with the coagulation of different 2D condensed domains as revealed by Brewster angle microscopy (BAM). However, partly converted prec-DMePPV monolayers show elastic behavior even at low surface pressures, although a sudden increase of the moduli does occur. This phenomenon is attributed to enhanced hydrophobic interactions between the conjugated moieties in the partly converted polymers. The latter also explains the stretching behavior of the partly converted prec-DMePPV upon transfer in Langmuir-Blodgett-type vertical dipping. The increase of the moduli which is observed is much more gradual in the precursor poly(2,5-dibutoxy-1,4-phenylene vinylene), prec-DBuPPV, a monolayer which is in agreement with the expected expanded state of the latter monolayer.     

Toward a total synthesis of the stemofoline alkaloids: Advancement of a 1,3-dipolar cycloaddition strategy

Novel, intramolecular 1,3-dipolar cycloadditions of azomethine ylides have been applied to the synthesis of functionalized core structures of the stemofoline alkaloids. In an effort to maximize the efficiency of this key transformation in the context of an eventual total synthesis of these complex natural products, a number of strategic modifications to the cycloaddition substrate were investigated. The collective efforts have provided useful insights into the operative, regiochemical control elements for 1,3-dipolar cycloadditions leading to stemofoline alkaloids. A potential intermediate in the synthesis of these alkaloids was prepared.     

Relaxation dynamics of selected polymer chain segments and comparison with theoretical models

Simultaneous measurement of infrared dichroism and birefringence is used to study selected polymer segment dynamics in isotopically labeled block copolymers. Two different polymers were studied: polybutadiene and poly (ethylene propylene). The first type consisted of a triblock with a short middle block labeled and a diblock with a short end block labeled, while the second type consisted of a triblock with three equal blocks and the end blocks labeled. Results of step strain experiments at –10°C for polybutadiene and at room temperature for poly(ethylene propylene) indicated that segments located at chain ends relax faster than segments located at chain centers. These experimental data were compared to the predictions of two molecular models: the bead-spring model of Rouse and the tube model of Doi and Edwards, and it was found that both models correctly predict the qualitative features of segmental relaxation. However, the tube-model predictions were closer to the experimental results. In addition, when the effects of orientational coupling interactions between segments in the melt were incorporated into this model, its predictions quantitatively agreed with the experimental results. The orientational coupling coefficient for poly(ethylene propylene) was 0.45 as measured from previous work, and for polybutadiene it was found to be 0.4.Delivered as a Keynote Lecture at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.Dedicated to Prof. R.S. Stein, University of Massachussets at Amherst, USA, on the occasion of his 65th birthday.     

Development characteristics of drag-reducing surfactant solution flow in a duct

Development characteristics of dilute cationic surfactant solution flow have been studied through the measurements of the time characteristics of surfactant solution by birefringence experiments and of the streamwise mean velocity profiles of surfactant solution duct flow by a laser Doppler velocimetry system. For both experiments, the concentration of cationic surfactant (oleylbishydroxymethylethylammonium chloride: Ethoquad O/12) was kept constant at 1000 ppm and the molar ratio of the counter ion of sodium salicylate to the surfactants was at 1.5. From the birefringence experiments, dilute surfactant solution shows very long retardation time corresponding to micellar shear induced structure formation. This causes very slow flow development of surfactant solution in a duct. Even at the end of the test section with the distance of 112 times of hydraulic diameter form the inlet, the flow is not fully developed but still has the developing boundary layer characteristics on the duct wall. From the time characteristics and the boundary layer development, it is concluded that the entry length of 1000 to 2000 times hydraulic diameter is required for fully developed surfactant solution flow.List of abbreviations and symbols A₁, A₂ Coefficients for time constant fitting [-] - B Breadth of the test duct [m] - C₁, C₂ Coefficients for time constant fitting [-] - D Pipe diameter [m] - D_H Hydraulic diameter [m] - g Impulse response function [Pa] - H Width of the test duct [m] - n Index of Bird-Carreau model [-] - Re Reynolds number (=U_mD_H/) - Re_D Pipe Reynolds number (=U_mD/) - Re_x Streamwise distance Reynolds number (=U₀x/) - T Absolute temperature [K] - t Time [s] - t_a Retardation time [s] - t_b Build-up time [s] - t_x Relaxation time [s] - t_x1, t_x2 Relaxation time for double time constant fitting [s] - t Time constant in Bird-Carreau model [s] - U Time mean velocity [m/s] - U_m Bulk mean velocity [m/s] - U_max Maximum velocity in a pipe [m/s] - U₀ Main flow velocity [m/s] - u Friction velocity [m/s] - x, y Coordinates [m] - Shear rate [s^–1] - Mean shear rate [s^–1] - n Birefringence [-] - 99% boundary layer thickness [m] - Solution viscosity [Pa·s] - _P, _S Surfactant and solvent viscosity [Pa·s] - ₀, Zero and infinite viscosity of Bird-Carreau model [Pa·s] - Characteristic time in Maxwell model [s] - Water kinematic viscosity [m²/s] - Density [kg/m³] - Solution shear stress [Pa] - _P, _S Surfactant and solvent shear stress [Pa] - Time in convolution [s]     

Dynamics of rigid and flexible polymer chains in confined geometries. part I: steady simple shear flow

This paper describes exact solutions to the response of both the elastic and rigid dumbbell models to a steady simple shear flow in a channel having a length scale comparable to the dumbbells themselves. Results are given for rheological properties over the entire range of the ratio of the channel width to the length of the dumbbell. It is found that both models lead to a decrease in viscosity as the channel is reduced in size with the elastic dumbbell predicting a stronger dependence on that parameter compared with the rigid dumbbell. The elastic dumbbell predicts shear independent rheological properties whereas the rigid dumbell predicts shear thinning as in the case of unbounded flows. The rate of shear thinning, however, decreases with decreasing channel width.