Rate viscosity dependence

With dynamic testing, the processed plastic s elastic modulus (relating to energy storage) and loss modulus (relative measure of a damping ability) are determined. Steady testing provides information about creep and recovery, viscosity, rate dependence, etc. 

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. 

From stochastic molecnlar dynamics calcnlations on the same system, in the viscosity regime covered by the experiment, it appears that intra- and intennolecnlar energy flow occur on comparable time scales, which leads to the conclnsion that cyclohexane isomerization in liquid CS2 is an activated process [99]. Classical molecnlar dynamics calcnlations [104] also reprodnce the observed non-monotonic viscosity dependence of ic. Furthennore, they also yield a solvent contribntion to the free energy of activation for tlie isomerization reaction which in liquid CS, increases by abont 0.4 kJ moC when the solvent density is increased from 1.3 to 1.5 g cm T Tims the molecnlar dynamics calcnlations support the conclnsion that the high-pressure limit of this unimolecular reaction is not attained in liquid solntion at ambient pressure. It has to be remembered, though, that the analysis of the measnred isomerization rates depends critically on the estimated valne of... 

With several springs, which function as torque gauges, and a number of spindles, viscosities can be measured up to 10 mPa-s with the Brookfield viscometer. The shear rates depend on the model and the sensor system they are ca 0.1 100 for the disk spindles, <132 for concentric cylinders, and <1500 for the cone—plate forlow viscosity samples. Viscosities at very low (ca 10 — 1 )) shear rates can be measured with the concentric... 

Viscosity. Sedimentation rate increases with decreased viscosity, )J., and viscosity is dependent on temperature. Often mineral oils, which are highly viscous at room temperature, have a viscosity that is reduced by a factor of 10 at 70—80°C. Tar, soHd at room temperature, is a low viscosity Hquid at 150—200°C and can be clarified of inorganic soHds at high flow rates. Even the viscosity of water changes significantly when the temperature changes between 10 and 35°C (10). 

In a fluid under stress, the ratio of the shear stress, r. to the rate of strain, y, is called the shear viscosity, rj, and is analogous to the modulus of a solid. In an ideal (Newtonian) fluid the viscosity is a material constant. However, for plastics the viscosity varies depending on the stress, strain rate, temperature etc. A typical relationship between shear stress and shear rate for a plastic is shown in Fig. 5.1. 

Assume laminar flow of filtrate of liquid through the filter cake. Rate of filtration is usually measured as the rate at which liquid filtrate is collected. The filtration rate depends on the area of the filter cloth, the viscosity of the liquid, the pressure drop across the filter and filter cake resistance. At any instant during filtration, the rate of filtration is given by the equation ... 

From the weak dependence of ef on the surrounding medium viscosity, it was proposed that the activation energy for bond scission proceeds from the intramolecular friction between polymer segments rather than from the polymer-solvent interactions. Instead of the bulk viscosity, the rate of chain scission is now related to the internal viscosity of the molecular coil which is strain rate dependent and could reach a much higher value than r s during a fast transient deformation (Eqs. 17 and 18). This representation is similar to the large loops internal viscosity model proposed by de Gennes [38]. It fails, however, to predict the independence of the scission yield on solvent quality (if this proves to be correct). 

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 ... 

Shear rate dependence of apparent viscosity for Newtonian and non-Newtonian fluids plotted on linear co-ordinates... 

A kinetic study for the polymerization of styrene, initiated with n BuLi, was designed to explore the Trommsdorff effect on rate constants of initiation and propagation and polystyryl anion association. Initiator association, initiation rate and propagation rates are essentially independent of solution viscosity, Polystyryl anion association is dependent on media viscosity. Temperature dependency correlates as an Arrhenius relationship. Observations were restricted to viscosities less than 200 centipoise. Population density distribution analysis indicates that rate constants are also independent of degree of polymerization, which is consistent with Flory s principle of equal reactivity. 

In the present chapter we shall be concerned with quantitative treatment of the swelling action of the solvent on the polymer molecule in infinitely dilute solution, and in particular with the factor a by which the linear dimensions of the molecule are altered as a consequence thereof. The frictional characteristics of polymer molecules in dilute solution, as manifested in solution viscosities, sedimentation velocities, and diffusion rates, depend directly on the size of the molecular domain. Hence these properties are intimately related to the molecular configuration, including the factor a. It is for this reason that treatment of intramolecular thermodynamic interaction has been reserved for the present chapter, where it may be presented in conjunction with the discussion of intrinsic viscosity and related subjects. 

For polymer melts or solutions, Graessley [40-42] has shown that for a random coil molecule with a Gaussian segment distribution and a uniform number of segments per unit volume, a shear rate dependent viscosity arises. This effect is attributed to shear-induced entanglement scission. 

Polymers in solution or as melts exhibit a shear rate dependent viscosity above a critical shear rate, ycrit. The region in which the viscosity is a decreasing function of shear rate is called the non-Newtonian or power-law region. As the concentration increases, for constant molar mass, the value of ycrit is shifted to lower shear rates. Below ycrit the solution viscosity is independent of shear rate and is called the zero-shear viscosity, q0. Flow curves (plots of log q vs. log y) for a very high molar mass polystyrene in toluene at various concentrations are presented in Fig. 9. The transition from the shear-rate independent to the shear-rate dependent viscosity occurs over a relatively small region due to the narrow molar mass distribution of the PS sample. 

For a precise analysis of the shear rate dependent viscosity it is necessary to know at which critical rate of deformation shear-induced disturbance can no longer be leveled out by the recoil of the polymers. 

It is possible to approximate the shear rate dependent viscosity at any rate of deformation (y> ycrit), to such an extent that degradation may be neglected. 

The coordinates (x, y, z) define the (velocity, gradient, vorticity) axes, respectively. For non-Newtonian viscoelastic liquids, such flow results not only in shear stress, but in anisotropic normal stresses, describable by the first and second normal stress differences (oxx-Oyy) and (o - ozz). The shear-rate dependent viscosity and normal stress coefficients are then [1]... 

The measurement of viscosity is important for many food products as the flow properties of the material relate directly to how the product will perform or be perceived by the consumer. Measurements of fluid viscosity were based on a correlation between relaxation times and fluid viscosity. The dependence of relaxation times on fluid viscosity was predicted and demonstrated in the late 1940 s [29]. This type of correlation has been found to hold for a large number of simple fluid foods including molten hard candies, concentrated coffee and concentrated milk. Shown in Figure 4.7.6 are the relaxation times measured at 10 MHz for solutions of rehydrated instant coffee compared with measured Newtonian viscosities of the solution. The correlations and the measurement provide an accurate estimate of viscosity at a specific shear rate. 

Therefore, the final equation is relatively simple despite the fact that the derivation is complex. Equation (145) shows that the intrinsic dissolution rate depends on the diffusion coefficient and solubility of the drug, disk rotational speed, and the viscosity of the dissolution medium. The amount of drug dissolving per unit area is the same everywhere on the disk s surface. This makes the disk a powerful experimental tool in drug discovery and development. 

Chain-growth polymerizations are diffusion controlled in bulk polymerizations. This is expected to occur rapidly, even prior to network development in step-growth mechanisms. Traditionally, rate constants are expressed in terms of viscosity. In dilute solutions, viscosity is proportional to molecular weight to a power that lies between 0.6 and 0.8 (22). Melt viscosity is more complex (23) Below a critical value for the number of atoms per chain, viscosity correlates to the 1.75 power. Above this critical value, the power is nearly 3 4 for a number of thermoplastics at low shear rates. In thermosets, as the extent of conversion reaches gellation, the viscosity asymptotically increases. However, if network formation is restricted to tightly crosslinked, localized regions, viscosity may not be appreciably affected. In the current study, an exponential function of degree of polymerization was selected as a first estimate of the rate dependency on viscosity. 

The usual approach for non-Newtonian fluids is to start with known results for Newtonian fluids and modify them to account for the non-Newtonian properties. For example, the definition of the Reynolds number for a power law fluid can be obtained by replacing the viscosity in the Newtonian definition by an appropriate shear rate dependent viscosity function. If the characteristic shear rate for flow over a sphere is taken to be V/d, for example, then the power law viscosity function becomes... 

Fig. 9.12 (A) Time variation of elongational viscosity for PLA-based nanocomposite (MMT = 4wt%) melt at 170°C (B) Strain rate dependence of up-rising Hencky strain. Reprinted from [47], 2003 Wiley-VCH Verlag GmbH Co.

A similar variety of samples was tested for thermal stability by capillary rheometry and TGA. Figure 6.3 shows the viscosity-shear rate dependence for PCTFE homopolymers and one copolymer (Alcon 3000). All materials, save one, showed virtually identical viscosity relationships despite large changes in inherent viscosity. Only the polymers from runs initiated by fluorochemical peroxides (FCP) showed a dependence of molecular weight (as measured by inherent viscosity) upon melt viscosity. 

Fluids of different viscosities flow through the capillary tube at different rates depending on then viscosities. 

There is a relationship that is used to cross between time and shear rate dependence regimes and that is the Cox-Merz rule.5 The dynamic viscosity when plotted as a function of frequency, has a similar... 

Another interesting consequence arises from the fact that diffusion and viscosity both depend on temperature. As the viscosity decreases, the diffusivity increases. As a consequence of this, the column performance as measured by the plate count is exclusively determined by the column backpressure. While this is not 100% accurate, it is at least a good rule of thumb. To get about the same column performance, you should increase the flow rate when you increase the temperature such that the column... 

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