The contribution of internal degrees of freedom to the non-Newtonian rheology of model polymer fluids

We report non-equilibrium molecular dynamics simulations of rigid and non-rigid dumbbell fluids to determine the contribution of internal degrees of freedom to strain-rate-dependent shear viscosity. The model adopted for non-rigid molecules is a modification of the finitely extensible nonlinear elastic (FENE) dumbbell commonly used in kinetic theories of polymer solutions. We consider model polymer melts — that is, fluids composed of rigid dumbbells and of FENE dumbbells. We report the steady-state stress tensor and the transient stress response to an applied Couerte strain field for several strain rates. We find that the rheological properties of the rigid and FENE dumbbells are qualitatively and quantitatively similar. (The only exception to this is the zero strain rate shear viscosity.) Except at high strain rates, the average conformation of the FENE dumbbells in a Couette strain field is found to be very similar to that of FENE dumbbells in the absence of strain. The theological properties of the two dumbbell fluids are compared to those of a corresponding fluid of spheres which is shown to be the most non-Newtonian of the three fluids considered.Symbol Definition b dimensionless time constant relating vibration to other forms of motion - F force on center of mass of dumbbell - F _i force on bead i of dumbbell - F force between center of masses of dumbbells and - F _ij force between beads i and j - h vector connecting bead to center of mass of dumbbell - H dimensionless spring constant for dumbbells, in units of / ² - I moment of inertia of dumbbell - J general current induced by applied field - k _B Boltzmann's constant - L angular momentum - m mass of bead, (= m/2) - M mass of dumbbell, g - N number of dumbbells in simulation cell - P translational momentum of center of mass of dumbbell - P pressure tensor - P _xy xy component of pressure tensor - Q separation of beads in dumbbell - Q _eq equilibrium extension of FENE dumbbell and fixed extension of rigid dumbbell - Q ₀ maximum extension of dumbbell - r _ij vector connecting beads i and j - r position vector of center of mass dumbbell - R vector connecting centers of mass of two dumbbells - t time - t ^* dimensionless time, in units of m/ - T ^* dimensionless temperature, in units of /k - u potential energy - u velocity vector of flow field - u _x x component of velocity vector - V volume of simulation cell - X general applied field - strain rate, s^–1 - ^* dimensionless shear rate, in units of /m ² - general transport property - Lennard-Jones potential well depth - friction factor for Gaussian thermostat - shear viscosity, g/cms - ^* dimensionless shear viscosity, in units of m/ ² - ^* dimensionless number density, in units of ^–3 - Lennard-Jones separation of minimum energy - relaxation time of a fluid - angular velocity of dumbbell - orientation angle of dumbbell      

Aqua ions-graphene interfacial and confinement behavior: insights from isobaric-isothermal molecular dynamics

We carry out a systematic microstructural characterization of the solid-fluid interface (SFI) of water and simple metal chloride aqueous solutions in contact with a free-standing plate or with two such plates separated by an interplate distance 0 ≤ h (?) ≤ 30 at ambient conditions via isothermal-isobaric molecular dynamics. With this characterization, we target the interrogation of the system in search for answers to fundamental questions regarding the structure of the "external" and "internal" (confined) SFIs, the effect of the differential hydration behavior among species, and its link to species expulsion from confinement. For water at ambient conditions, we found that the structure of the "external" SFIs is independent of the interplate distance h in the range 0 ≤ h (?) ≤ 30, that is, the absence of wall-mediated correlation effects between "external" and "internal" SFIs, and that for h < 9 ? the slit-pores dewet. Moreover, we observed a selective expulsion of ions caused by the differential hydration between the anion and the cations with a consequent charging of the slit-pore. All these observations were interpreted in terms of the axial profiles for precisely defined order parameters, including tetrahedral configuration, hydrogen bonding, and species coordination numbers.     

Resummed thermodynamic perturbation theory for central force associating potential. Multi-patch models

A resummed thermodynamic perturbation theory for associating fluids with multiply bondable central force associating potential is extended for the fluid with multiple number of multiply bondable associating sites. We consider a multi-patch hard-sphere model for associating fluids. The model is represented by the hard-sphere fluid system with several spherical attractive patches on the surface of each hard sphere. Resummation is carried out to account for blocking effects, i.e., when the bonding of a particle restricts (blocks) its ability to bond with other particles. Closed form analytical expressions for thermodynamical properties (Helmholtz free energy, pressure, internal energy, and chemical potential) of the models with arbitrary number of doubly bondable patches at all degrees of the blockage are presented. In the limiting case of total blockage, when the patches become only singly bondable, our theory reduces to Wertheim's thermodynamic perturbation theory (TPT) for polymerizing fluids. To validate the accuracy of the theory we compare to exact values, for the thermodynamical properties of the system, as determined by Monte Carlo computer simulations. In addition we compare the fraction of multiply bonded particles at different values of the density and temperature. In general, predictions of the present theory are in good agreement with values for the model calculated using Monte Carlo simulations, i.e., the accuracy of our theory in the case of the models with multiply bondable sites is similar to that of Wertheim's TPT in the case of the models with singly bondable sites.     

H2F2 chain reaction rate investigation

Experimental performance of chemical lasers pumped by the H₂ + F₂ chain reaction has consistently fallen below expectations, although the “hot”, H+F₂→HF(ν)+F, pumping reaction produces greater vibrational excitation than the “cold”, F+H₂→HF(ν)+H, reaction used in most HF cw chemical lasers. The reasons for this discrepancy are examined by measuring spatially-resolved HF(ν) number density and the temperature profiles in a laminar, parallel flow, hydrogen-fluorine mixing layer and comparing the results with theoretical computations. By dissociating either the hydrogen or fluorine molecules with arc heaters, kinetics of the hot and cold reaction systems are separately investigated. From a comparison of the experimental vibrational populations and the theoretical predictions, it is concluded that: (1) previously-used pumping and deactivation rates associated with the cold reaction are approximately correct, (2) the deactivation of high vibrational levels populated by the hot reaction is much faster than previously stated in Ref. (1), and (3) the inclusion of multiquantum HF(ν) V-T (or V-R) deactivation reactions, which sharply decreases the number density of the upper vibrational levels, greatly improves the agreement between theory and experiment.     

A short gamma-ray burst apparently associated with an elliptical galaxy at redshift z = 0.225

Gamma-ray bursts (GRBs) come in two classes: long (> 2 s), soft-spectrum bursts and short, hard events. Most progress has been made on understanding the long GRBs, which are typically observed at high redshift (z approximately 1) and found in subluminous star-forming host galaxies. They are likely to be produced in core-collapse explosions of massive stars. In contrast, no short GRB had been accurately (< 10') and rapidly (minutes) located. Here we report the detection of the X-ray afterglow from--and the localization of--the short burst GRB 050509B. Its position on the sky is near a luminous, non-star-forming elliptical galaxy at a redshift of 0.225, which is the location one would expect if the origin of this GRB is through the merger of neutron-star or black-hole binaries. The X-ray afterglow was weak and faded below the detection limit within a few hours; no optical afterglow was detected to stringent limits, explaining the past difficulty in localizing short GRBs.     

The strength of the deuterium bond

The fall in frequency on deuteration, by some 4 cm^?1, of the intermolecular stretching mode v_σ of hydrogen bonded complexes, is larger than can be accounted for by any reasonable harmonic force field. It is shown that this does not imply a different potential function for the deuterium bond; it may be quantitatively accounted for by anharmonicity in the v_σ mode, together with anharmonic interaction with the AH stretching mode v_s.     

Proposal for measurement of helium-II condensate

A method is proposed for an experimental determination of the equilibrium condensate fraction in He⁴II which relies only on measurement of the liquid structure factor as a function of temperature. Existing data at 0.79°K and 1.4°K indicate the value to be about 10%.