Diffusion shear viscosity

A united-atom model for [C4mim][PF6] and [C4mim][N03] was developed in the framework of the GROMOS96 force field [71]. The equilibrium properties in the 298-363 K temperature range were validated against known experimental properties, namely, density, self-diffusion, shear viscosity, and isothermal compressibility [71]. The properties obtained from the MD simulations agreed with experimental data and showed the same temperature dependence. 

Bhargava and Balasubramanian used equilibrium MD to compute the self-diffusivity, shear viscosity, and electrical conductivity for [Cimim][Cl] at... 

In the following, the Green-Kubo formulas for self-diffusion, shear viscosity and thermal conductivity coefficients are compiled. A complete list of all the thermal transport coefficients of one- and two-component systems was given by Hoheisel Vogelsang (1988). 

Modern kinetic theory is able to predict the transport coefficients of the Lennard-Jones liquid (1-center Lennard-Jones interaction between particles) to a fairly good approximation (Karkheck 1986 Hoheisel 1993). The results of these theories have been compared in detail with the exact MD computation results (Borgelt et al. 1990). Comparisons for self-diffusion, shear viscosity and thermal conductivity are presented in Figures 9.2-9.4. 

The general form of Green-Kubo formulas has already been given in Section 9.1.1. However, for molecular liquids the microscopic formulation of the currents for self-diffusion, shear viscosity and thermal conductivity must be modified (Marechal Ryckaert 1983 Hoheisel 1993). 

The shear viscosity is a tensor quantity, with components T] y, t],cz, T)yx> Vyz> Vzx> Vzy If property of the whole sample rather than of individual atoms and so cannot be calculat< with the same accuracy as the self-diffusion coefficient. For a homogeneous fluid the cor ponents of the shear viscosity should all be equal and so the statistical error can be reducf by averaging over the six components. An estimate of the precision of the calculation c then be determined by evaluating the standard deviation of these components from tl average. Unfortunately, Equation (7.89) cannot be directly used in periodic systems, evi if the positions have been unfolded, because the unfolded distance between two particl may not correspond to the distance of the minimum image that is used to calculate the fore For this reason alternative approaches are required. 

While electrical conductivity, diffusion coefficients, and shear viscosity are determined by weak perturbations of the fundamental diffu-sional motions, thermal conductivity is dominated by the vibrational motions of ions. Heat can be transmitted through material substances without any bulk flow or long-range diffusion occurring, simply by the exchange of momentum via collisions of particles. It is for this reason that in liquids in which the rate constants for viscous flow and electrical conductivity are highly temperature dependent, the thermal conductivity remains essentially the same at lower as at much higher temperatures and more fluid conditions. 

Hydrodynamic properties, such as the translational diffusion coefficient, or the shear viscosity, are very useful in the conformational study of chain molecules, and are routinely employed to characterize different types of polymers [15,20, 21]. One can consider the translational friction coefficient, fi, related to a transport property, the translational diffusion coefficient, D, through the Einstein equation, applicable for infinitely dilute solutions ... 

This article reviews the following solution properties of liquid-crystalline stiff-chain polymers (1) osmotic pressure and osmotic compressibility, (2) phase behavior involving liquid crystal phasefs), (3) orientational order parameter, (4) translational and rotational diffusion coefficients, (5) zero-shear viscosity, and (6) rheological behavior in the liquid crystal state. Among the related theories, the scaled particle theory is chosen to compare with experimental results for properties (1H3), the fuzzy cylinder model theory for properties (4) and (5), and Doi s theory for property (6). In most cases the agreement between experiment and theory is satisfactory, enabling one to predict solution properties from basic molecular parameters. Procedures for data analysis are described in detail. 

In the second half of this article, we discuss dynamic properties of stiff-chain liquid-crystalline polymers in solution. If the position and orientation of a stiff or semiflexible chain in a solution is specified by its center of mass and end-to-end vector, respectively, the translational and rotational motions of the whole chain can be described in terms of the time-dependent single-particle distribution function f(r, a t), where r and a are the position vector of the center of mass and the unit vector parallel to the end-to-end vector of the chain, respectively, and t is time, (a should be distinguished from the unit tangent vector to the chain contour appearing in the previous sections, except for rodlike polymers.) Since this distribution function cannot describe internal motions of the chain, our discussion below is restricted to such global chain dynamics as translational and rotational diffusion and zero-shear viscosity. 

In Sect. 6.3, we have neglected the intermolecular hydrodynamic interaction in formulating the diffusion coefficients of stiff-chain polymers. Here we use the same approximation by neglecting the concentration dependence of qoV), and apply Eq. (73) even at finite concentrations. Then, the total zero-shear viscosity t 0 is represented by [19]... 

As for the properties themselves, there are many chemically useful autocorrelation functions. For instance, particle position or velocity autocorrelation functions can be used to determine diffusion coefficients (Ernst, Hauge, and van Leeuwen 1971), stress autocorrelation functions can be used to determine shear viscosities (Haile 1992), and dipole autocorrelation functions are related to vibrational (infrared) spectra as their reverse Fourier transforms (Berens and Wilson 1981). There are also many useful correlation functions between two different variables (Zwanzig 1965). A more detailed discussion, however, is beyond the scope of this text. 

Figure 2. A pictorial representation of the mode coupling theory scheme for the calculation of the time-dependent friction (f) on a tagged molecule at time t. The rest of the notation is as follows Fs(q,t), self-scattering function F(q,t), intermediate scattering function D, self-diffusion coefficient t]s(t), time-dependnet shear viscosity Cu(q,t), longitudinal current correlation function C q,t), longitudinal current correlation functioa...

Figure 24. A comparison of the data obtained from a range of surface rheological measurements of samples of /3-lg as a function of Tween 20 concentration. ( ), The surface diffusion coefficient of FITC-jS-lg (0.2 mg/ml) at the interfaces of a/w thin films (X), the surface shear viscosity of /3-lg (0.01 mg/ml) at the o/w interface after 5 hours adsorption ( ), the surface dilational elasticity and (o) the dilational loss modulus of /3-lg (0.2 mg/ml).

G. Murrucci and N. Grizzuti, The effect of polydispersity on rotational diffusivity and shear viscosity of rodlike polymer in concentrated solutions, J. Polym. Sci., Polym. Lett. Ed., 21, 83 (1983). 

Sewell and co workers [145-148] have performed molecular dynamics simulations using the HMX model developed by Smith and Bharadwaj [142] to predict thermophysical and mechanical properties of HMX for use in mesoscale simulations of HMX-containing plastic-bonded explosives. Since much of the information needed for the mesoscale models cannot readily be obtained through experimental measurement, Menikoff and Sewell [145] demonstrate how information on HMX generated through molecular dynamics simulation supplement the available experimental information to provide the necessary data for the mesoscale models. The information generated from molecular dynamics simulations of HMX using the Smith and Bharadwaj model [142] includes shear viscosity, self-diffusion [146] and thermal conductivity [147] of liquid HMX. Sewell et al. have also assessed the validity of the HMX flexible model proposed by Smith and Bharadwaj in molecular dynamics studies of HMX crystalline polymorphs. 

Generally, one may establish that in some cases greatly enhanced concentration fluctuations occur under flow, in others, however, the size of concentration fluctuations is reduced and, obviously, flow promotes mutual miscibility of the polymers. Concentration fluctuations are accompanied by inhomogeneities of transport quantities as shear viscosity and diffusity. In a flow field the molecules are transferred into a non-equilibrium situation of extension. Two polymer molecules in a state of excess extension feel an additional repulsion due to the enhanced normal stress difference. Thus, the rate of dissipation by diffusion is low compared with the shear rate and the concentration fluctuations tend to grow. The opposite is true for a state of lower extension. In that case the dissipation of the concentration fluctuations is enhanced owing to an additional attraction between the chain molecules. 

In all expressions the Einstein repeated index summation convention is used. Xi, x2 and x3 will be taken to be synonymous with x, y and z so that o-n = axx etc. The parameter B will be temperature-dependent through an activation energy expression and can be related to microstructural parameters such as grain size, diffusion coefficients, etc., on a case-by-case basis depending on the mechanism of creep involved.1 In addition, the index will depend on the mechanism which is active. In the linear case, n = 1 and B is equal to 1/3t/ where 17 is the linear shear viscosity of the material. Stresses, strains, and material parameters for the fibers will be denoted with a subscript or superscript/, and those for the matrix with a subscript or superscript m. 

The theoretical analysis indicated that asymmetric drainage was caused by the hydrodynamic instability being a result of surface tension driven flow. A criterion giving the conditions of the onset of instability that causes asymmetric drainage in foam films was proposed. This analysis showed as well that surface-tension-driven flow was stabilised by surface dilational viscosity, surface diffusivity and especially surface shear viscosity. 

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