Time-dependent viscosity

Figure 6. Viscosity-Time Dependence of Bisulfite-Reduced Crosslinking Solutions.

I. Y. Belyaev, S. Eriksson, J. Nygren, J. Torudd and M. Harms-Ringdahl, Effects of ethidium bromide on DNA loop organisation in human lymphocytes measured by anomalous viscosity time dependence and single cell gel electrophoresis, Biochim. Biophys. Acta, 1999, 1428, 348-356. 

Theoretical models of the film viscosity lead to values about 10 times smaller than those often observed [113, 114]. It may be that the experimental phenomenology is not that supposed in derivations such as those of Eqs. rV-20 and IV-22. Alternatively, it may be that virtually all of the measured surface viscosity is developed in the substrate through its interactions with the film (note Fig. IV-3). Recent hydrodynamic calculations of shape transitions in lipid domains by Stone and McConnell indicate that the transition rate depends only on the subphase viscosity [115]. Brownian motion of lipid monolayer domains also follow a fluid mechanical model wherein the mobility is independent of film viscosity but depends on the viscosity of the subphase [116]. This contrasts with the supposition that there is little coupling between the monolayer and the subphase [117] complete explanation of the film viscosity remains unresolved. 

Monte Carlo simulations require less computer time to execute each iteration than a molecular dynamics simulation on the same system. However, Monte Carlo simulations are more limited in that they cannot yield time-dependent information, such as diffusion coefficients or viscosity. As with molecular dynamics, constant NVT simulations are most common, but constant NPT simulations are possible using a coordinate scaling step. Calculations that are not constant N can be constructed by including probabilities for particle creation and annihilation. These calculations present technical difficulties due to having very low probabilities for creation and annihilation, thus requiring very large collections of molecules and long simulation times. 

Molecular dynamics calculations are more time-consuming than Monte Carlo calculations. This is because energy derivatives must be computed and used to solve the equations of motion. Molecular dynamics simulations are capable of yielding all the same properties as are obtained from Monte Carlo calculations. The advantage of molecular dynamics is that it is capable of modeling time-dependent properties, which can not be computed with Monte Carlo simulations. This is how diffusion coefficients must be computed. It is also possible to use shearing boundaries in order to obtain a viscosity. Molec-... 

Viscous Hquids are classified based on their rheological behavior characterized by the relationship of shear stress with shear rate. Eor Newtonian Hquids, the viscosity represented by the ratio of shear stress to shear rate is independent of shear rate, whereas non-Newtonian Hquid viscosity changes with shear rate. Non-Newtonian Hquids are further divided into three categories time-independent, time-dependent, and viscoelastic. A detailed discussion of these rheologically complex Hquids is given elsewhere (see Rheological measurements). 

The other models can be appHed to non-Newtonian materials where time-dependent effects are absent. This situation encompasses many technically important materials from polymer solutions to latices, pigment slurries, and polymer melts. At high shear rates most of these materials tend to a Newtonian viscosity limit. At low shear rates they tend either to a yield point or to a low shear Newtonian limiting viscosity. At intermediate shear rates, the power law or the Casson model is a useful approximation. 

Thixotropy and Other Time Effects. In addition to the nonideal behavior described, many fluids exhibit time-dependent effects. Some fluids increase in viscosity (rheopexy) or decrease in viscosity (thixotropy) with time when sheared at a constant shear rate. These effects can occur in fluids with or without yield values. Rheopexy is a rare phenomenon, but thixotropic fluids are common. Examples of thixotropic materials are starch pastes, gelatin, mayoimaise, drilling muds, and latex paints. The thixotropic effect is shown in Figure 5, where the curves are for a specimen exposed first to increasing and then to decreasing shear rates. Because of the decrease in viscosity with time as weU as shear rate, the up-and-down flow curves do not superimpose. Instead, they form a hysteresis loop, often called a thixotropic loop. Because flow curves for thixotropic or rheopectic Hquids depend on the shear history of the sample, different curves for the same material can be obtained, depending on the experimental procedure. 

A rotational viscometer connected to a recorder is used. After the sample is loaded and allowed to come to mechanical and thermal equiUbtium, the viscometer is turned on and the rotational speed is increased in steps, starting from the lowest speed. The resultant shear stress is recorded with time. On each speed change the shear stress reaches a maximum value and then decreases exponentially toward an equiUbrium level. The peak shear stress, which is obtained by extrapolating the curve to zero time, and the equiUbrium shear stress are indicative of the viscosity—shear behavior of unsheared and sheared material, respectively. The stress-decay curves are indicative of the time-dependent behavior. A rate constant for the relaxation process can be deterrnined at each shear rate. In addition, zero-time and equiUbrium shear stress values can be used to constmct a hysteresis loop that is similar to that shown in Figure 5, but unlike that plot, is independent of acceleration and time of shear. 

The basic design is that of the Ostwald viscometer a U-tube with two reservoir bulbs separated by a capillary, as shown in Figure 24a. The Hquid is added to the viscometer, pulled into the upper reservoir by suction, and then allowed to drain by gravity back into the lower reservoir. The time that it takes for the Hquid to pass between two etched marks, one above and one below the upper reservoir, is a measure of the viscosity. In U-tube viscometers, the effective pressure head and therefore the flow time depend on the volume of Hquid in the instmment. Hence, the conditions must be the same for each measurement. 

Sihcate solutions of equivalent composition may exhibit different physical properties and chemical reactivities because of differences in the distributions of polymer sihcate species. This effect is keenly observed in commercial alkah sihcate solutions with compositions that he in the metastable region near the solubihty limit of amorphous sihca. Experimental studies have shown that the precipitation boundaries of sodium sihcate solutions expand as a function of time, depending on the concentration of metal salts (29,58). Apparently, the high viscosity of concentrated alkah sihcate solutions contributes to the slow approach to equihbrium. 

Here v is the space- and time-dependent velocity field, p is the density of the fluid, p is the local pressure, v is the kinematic viscosity, and / is some arbitrary body-force acting on each small element of the fluid (gravitation, for example). 

Non-Newtonian fluids vary significantly in their properties that control flow and pressure loss during flow from the properties of Newtonian fluids. The key factors influencing non-Newtonian fluids are their shear thinning or thickening characteristics and time dependency of viscosity on the stress in the fluid. 

Many fluids, including some that are encountered very widely both industrially and domestically, exhibit non-Newtonian behaviour and their apparent viscosities may depend on the rate at which they are sheared and on their previous shear history. At any position and time in the fluid, the apparent viscosity pa which is defined as the ratio of the shear stress to the shear rate at that point is given by ... 

When the apparent viscosity is a function of the shear rate, the behaviour is said to he shear-dependenf, when it is a function of the duration of shearing at a particular rate, it is referred to as time-dependent. Any shear-dependent fluid must to some extent be time-dependent because, if the shear rate is suddenly changed, the apparent viscosity does not alter instantaneously, but gradually moves towards its new value. In many eases, however, the time-scale for the flow process may be sufficiently long for the effects of time-dependence to be negligible. 

Figure 3.34. Effect of sudden change of shear rate on apparent viscosity of time-dependent fluid...

Molecular Rotational Diffusion. Rotational diffusion is the dominant intrinsic cause of depolarization under conditions of low solution viscosity and low fluorophore concentration. Polarization measurements are accurate indicators of molecular size. Two types of measurements are used steady-state depolarization and time-dependent (dynamic) depolarization. 

For the calculation of shear stress, the time-dependent impeller power, particle diameter dp and viscosity v according to v = K/9 with the representative shear gradient y = for the non Newtonian broth (see equation (17) [28]) were used. 

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