Effect of dynamical asymmetry on the viscosity of a random copolymer melt

The variation of the viscosity as a function of the sequence distribution in an A-B random copolymer melt is determined. The parameters that characterize the random copolymer are the fraction of A monomers f, the parameter lambda which determines the correlation in the monomer identities along a chain and the Flory chi parameter chi(F) which determines the strength of the enthalpic repulsion between monomers of type A and B. For lambda>0, there is a greater probability of finding like monomers at adjacent positions along the chain, and for lambda<0 unlike monomers are more likely to be adjacent to each other. The traditional Markov model for the random copolymer melt is altered to remove ultraviolet divergences in the equations for the renormalized viscosity, and the phase diagram for the modified model has a binary fluid type transition for lambda>0 and does not exhibit a phase transition for lambda<0. A mode coupling analysis is used to determine the renormalization of the viscosity due to the dependence of the bare viscosity on the local concentration field. Due to the dissipative nature of the coupling. there are nonlinearities both in the transport equation and in the noise correlation. The concentration dependence of the transport coefficient presents additional difficulties in the formulation due to the Ito-Stratonovich dilemma, and there is some ambiguity about the choice of the concentration to be used while calculating the noise correlation. In the Appendix, it is shown using a diagrammatic perturbation analysis that the Ito prescription for the calculation of the transport coefficient, when coupled with a causal discretization scheme, provides a consistent formulation that satisfies stationarity and the fluctuation dissipation theorem. This functional integral formalism is used in the present analysis, and consistency is verified for the present problem as well. The upper critical dimension for this type of renormaliaation is 2, and so there is no divergence in the viscosity in the vicinity of a critical point. The results indicate that there is a systematic dependence of the viscosity on lambda and chi(F). The fluctuations tend to increase the viscosity for lambda<0, and decrease the viscosity for lambda>0, and an increase in chi(F) tends to decrease the viscosity. (C) 1996 American Institute of Physics.

Critical earthquake input power spectral density function models for engineering structures

The problem of determining optimal power spectral density models for earthquake excitation which satisfy constraints on total average power, zero crossing rate and which produce the highest response variance in a given linear system is considered. The solution to this problem is obtained using linear programming methods. The resulting solutions are shown to display a highly deterministic structure and, therefore, fail to capture the stochastic nature of the input. A modification to the definition of critical excitation is proposed which takes into account the entropy rate as a measure of uncertainty in the earthquake loads. The resulting problem is solved using calculus of variations and also within linear programming framework. Illustrative examples on specifying seismic inputs for a nuclear power plant and a tall earth dam are considered and the resulting solutions are shown to be realistic.

The concentration dependent cooperative friction coefficient of dilute polymer solutions at the theta point

We combine multiple scattering and renormalization group methods to calculate the leading order dimensionless virial coefficient k(s) for the friction coefficient of dilute polymer solutions under conditions where the osmotic second virial coefficient vanishes (i.e., at the theta point T-theta). Our calculations are formulated in terms of coupled kinetic equations for the polymer and solvent, in which the polymers are modeled as continuous chains whose configurations evolve under the action of random forces in, the velocity field of the solvent. To lowest order in epsilon=4-d, we find that k(s) = 1.06. This result compares satisfactorily with existing experimental estimates of k(s), which are in the range 0.7-0.8. It is also in good agreement with other theoretical results on chains and suspensions at T-theta. Our calculated k(s) is also found to be identical to the leading order virial coefficient of the tracer friction coefficient at the theta point. We discuss possible reasons for the difficulties encountered when attempting to evaluate k(s) by extrapolating prior renormalization group calculations from semidilute concentrations to the infinitely dilute limit. (C) 1996 American Institute of Physics.

Application of selective F-1 decoupled H-1 NMR for enantiomer resolution and accurate measurement of enantiomeric excess at low chiral substrate/auxiliary concentration

The higher substrate and chiral auxiliary concentration is a pre-requisite to obtain efficient separation of H-1 NMR signals of enantiomers. The higher concentration of chiral lanthanide shift reagents provides broadened spectral lines resulting in a severe loss of resolution between the enantiomer resonances. In order to circumvent such difficulties, herein we present the application and the usefulness of a selective F-1 decoupled correlation (COSY) experiment which yields proton decoupled proton spectra in the indirect dimension. The potentiality of the experiment is demonstrated on several chiral compounds possessing different functional groups, employing either a lanthanide shift reagent or a solvating reagent as chiral auxiliaries. (C) 2011 Elsevier B.V. All rights reserved.

Low-temperature magnetoresistance of ?-phase FexNi80-xCr20 alloys near the critical composition for ferromagnetism

We present a comprehensive study of magnetoresistance (MR) of the crystalline pseudobinary ?-phase Fe alloy series FexNi80-xCr20 (50?x?66). This alloy series shows exotic magnetic phases as the composition (x) is varied. It has a critical composition for ferromagnetism at x=xc?59�60. MR was measured in the temperature range 1.7�110 K and up to a field of 7 T. The observed MR was small and the change was ?1%. The temperature dependence of MR was found to contain a positive and a negative contribution. The positive term was found to be ?H2 and it dominates at high field and high temperatures. We explain this as a manifestation of Kohler�s rule. The negative MR was found to have a quadratic dependence on magnetization M. The magnitude of the negative MR reaches a maximum as x?xc.

Critical buckling temperature of single-walled carbon nanotubes embedded in a one-parameter elastic medium based on nonlocal continuum mechanics

In this paper, the critical budding temperature of single-walled carbon nanotubes (SWCNTs), which are embedded in one-parameter elastic medium (Winkler foundation) is estimated under the umbrella of continuum mechanics theory. Nonlocal continuum theory is incorporated into Timoshenko beam model and the governing differential equations of motion are derived. An explicit expression for the non-dimensional critical buckling temperature is also derived in this work. The effect of the nonlocal small scale coefficient, the Winkler foundation parameter and the ratio of the length to the diameter on the critical buckling temperature is investigated in detail. It can be observed that the effects of nonlocal small scale parameter and the Winkler foundation parameter are significant and should be considered for thermal analysis of SWCNTs. The results presented in this paper can provide useful guidance for the study and design of the next generation of nanodevices that make use of the thermal buckling properties of embedded single-walled carbon nanotubes. (C) 2011 Elsevier B.V. All rights reserved.

Levitation effect and its dependence on sorbate concentration

Earlier work has reported the existence of a diffusion anomaly in porous solids at dilute sorbate concentrations. In this work we have carried out molecular dynamics simulations at higher sorbate concetrations. Results indicate the persistence of a diffusion anomaly even at significantly higher sorbate concentrations, which means that this anomaly can be used for separation of mixtures under conditions prevailing in industries.

Nonequilibrium phase transition in the kinetic Ising model: Critical slowing down and the specific-heat singularity

The nonequilibrium dynamic phase transition, in the kinetic Ising model in the presence of an oscillating magnetic field has been studied both by Monte Carlo simulation and by solving numerically the mean-field dynamic equation of motion for the average magnetization. In both cases, the Debye ''relaxation'' behavior of the dynamic order parameter has been observed and the ''relaxation time'' is found to diverge near the dynamic transition point. The Debye relaxation of the dynamic order parameter and the power law divergence of the relaxation time have been obtained from a very approximate solution of the mean-field dynamic equation. The temperature variation of appropriately defined ''specific heat'' is studied by the Monte Carlo simulation near the transition point. The specific heat has been observed to diverge near the dynamic transition point.

On the water-induced critical double point in a polymer solution: the role of isotopic substitution

This paper examines the effect of substitution of water by heavy water in a polymer solution of polystyrene (molecular weight = 13000) and acetone. A critical double point (CDP), at which the upper and the lower partially-miscible regions merge, occurs at nearly the same coordinates as for the system [polystyrene + acetone + water]. The shape of the critical line for [polystyrene + acetone + heavy water] is highly asymmetric. An explanation for the occurrence of the water-induced CDP in [polystyrene + acetone] is advanced in terms of the interplay between contact energy dissimilarity and free-volume disparity of the polymer and the solvent. The question of the possible existence of a one-phase hole in an hourglass phase diagram is addressed in [polystyrene + acetone + water]. Our data exclude such a possibility.

Passive pressure coefficients, critical failure surface and its kinematic admissibility

Using a combination of a logarithmic spiral and a straight line as a failure surface, comprehensive charts have been developed to determine the passive earth pressure coefficients and the positions of the critical failure surface for positive as well as negative wall friction angles. Translational movement of the wall has been examined in detail, considering the soil as either an associated flow dilatant material or a non-dilatant material, to determine the kinematic admissibility of the limit equilibrium solutions.

The Tevatron Higgs exclusion limits and theoretical uncertainties: A critical appraisal

We examine the exclusion limits set by the CDF and D0 experiments on the Standard Model Higgs boson mass from their searches at the Tevatron in the light of large theoretical uncertainties on the signal and background cross sections. We show that when these uncertainties are consistently taken into account, the sensitivity of the experiments becomes significantly lower and the currently excluded mass range M-H = 158-175 GeV could be entirely reopened. The necessary luminosity required to recover the current sensitivity is found to be a factor of two higher than the present one. (C) 2011 Elsevier B.V. All rights reserved.

Anomalous Behavior of Linear Hydrocarbon Chains in Water-DMSO Binary Mixture at Low DMSO Concentration

We find that at a mole fraction 0.05 of DMSO (x(DMSO) = 0.05) in aqueous solution, a linear hydrocarbon chain of intermediate length (n = 30-40) adopts the most stable collapsed conformation. In pure water, the same chain exhibits an intermittent oscillation between the collapsed and the extended coiled conformations. Even when the mole fraction of DMSO in the bulk is 0.05, the concentration of the same in the first hydration layer around the hydrocarbon of chain length 30 (n = 30) is as large as 17%. Formation of such hydrophobic environment around the hydrocarbon chain may be viewed as the reason for the collapsed conformation gaining additional stability. We find a second anomalous behavior to emerge near x(DMSO) = 0.15, due to a chain-like aggregation of the methyl groups of DMSO in water that lowers the relative concentration of the DMSO molecules in the hydration layer. We further find that as the concentration of DMSO is gradually increased, it progressively attains the extended coiled structure as the stable conformation. Although Flory-Huggins theory (for binary mixture solvent) fails to predict the anomaly at x(DMSO) = 0.05, it seems to capture the essence of the anomaly at 0.15.

Subquadratic quantum number dependence and other anomalies of vibrational dephasing in liquid nitrogen: Molecular dynamics simulation study from the triple point to the critical point and beyond

Vibrational phase relaxation near gas-liquid and liquid-solid phase coexistence has been studied by molecular dynamics simulations of N-N stretch in N-2. Experimentally observed pronounced insensitivity of phase relaxation from the triple point to beyond the boiling point is found to originate from a competition between density relaxation and resonant-energy transfer terms. The sharp rise in relaxation rate near the critical point (CP) can be attributed at least partly to the sharp, rise in vibration-rotation coupling contribution. Substantial subquadratic quantum number dependence of overtone dephasing rate is found near the CP and in supercritical fluids. [S0031-9007 (99)09318-7].