Rheological dilute solution viscosity

Solutions of HEC are pseudoplastic. Newtonian rheology is approached by very dilute solutions as well as by lower molecular-weight products. Viscosities change Httie between pH 2 and 12, but are affected by acid hydrolysis or alkaline oxidation under pH and temperature extremes. Viscosities of HEC solutions change reversibly with temperature, increasing when cooled and decreasing when warmed. 

The ionic strength dependence of intrinsic viscosity is function of molecular structure and protein folding, ft is well known that the conformational and rheological properties of charged biopolymer solutions are dependent not only upon electrostatic interactions between macromolecules but also upon interactions between biopolymer chains and mobile ions. Due electrostatic interactions the specific viscosity of extremely dilute solutions seems to increase infinitely with decreasing ionic concentration. Variations of the intrinsic viscosity of a charged polyampholite with ionic strength have problems of characterization. 

Taking into account the relevance of the range of semi-dilute solutions (in which intermolecular interactions and entanglements are of increasing importance) for industrial applications, a more detailed picture of the interrelationships between the solution structure and the rheological properties of these solutions was needed. The nature of entanglements at concentrations above the critical value c leads to the viscoelastic properties observable in shear flow experiments. The viscous part of the flow behaviour of a polymer in solution is usually represented by the zero-shear viscosity, rj0, which depends on the con-... 

A rheological instrument such as a viscometer can be used to evaluate t and 7 and hence obtain a value for the shear viscosity, 17. Examples of Newtonian fluids are pure gases, mixtures of gases, pure liquids of low molecular weight, dilute solutions, and dilute emulsions. In some instances, a fluid may be Newtonian at a certain shear-rate range but deviate from Newton s law of viscosity under either very low or very high shear rates (2). 

Rheology is a powerful method for the characterization of HA properties. In particular, rotational rheometers are particularly suitable in studying the rheological properties of HA. In such rheometers, different geometries (cone/plate, plate/plate, and concentric cylinders) are applied to concentrated, semi-diluted, and diluted solutions. A typical rheometric test performed on a HA solution is the so-called "flow curve". In such a test, the dynamic viscosity (q) is measured as a function of the shear rate (7) at constant strain (shear rate or stress sweep). From the flow curve, the Newtonian dynamic viscosity (qo), first plateau, and the critical shear rate ( 7 c), onset of non-Newtonian flow, could be determined. 

We can see that Eqs. (2 101) (2-104) are sufficient to calculate the continuum-level stress a given the strain-rate and vorticity tensors E and SI. As such, this is a complete constitutive model for the dilute solution/suspension. The rheological properties predicted for steady and time-dependent linear flows of the type (2-99), with T = I t), have been studied quite thoroughly (see, e g., Larson34). Of course, we should note that the contribution of the particles/macromolecules to the stress is actually quite small. Because the solution/suspension is assumed to be dilute, the volume fraction is very small, (p 1. Nevertheless, the qualitative nature of the particle contribution to the stress is found to be quite similar to that measured (at larger concentrations) for many polymeric liquids and other complex fluids. For example, the apparent viscosity in a simple shear flow is found to shear thin (i.e., to decrease with increase of shear rate). These qualitative similarities are indicative of the generic nature of viscoelasticity in a variety of complex fluids. So far as we are aware, however, the full model has not been used for flow predictions in a fluid mechanics context. This is because the model is too complex, even for this simplest of viscoelastic fluids. The primary problem is that calculation of the stress requires solution of the full two-dimensional (2D) convection-diffusion equation, (2-102), at each point in the flow domain where we want to know the stress. 

Dilute Solution Properties. The rheology of dilute polymer solutions has been used extensively to gain insight into the structure and conformation of polymers in solution (11). The intrinsic viscosity provides a measure of the molecular weight of a polymer through a relationship such as the Mark-Houwink-Sakurada equation. Earlier studies of polyacrylamide (PAM) systems and details of the complexity of the characterization of high-molecular-weight water-soluble systems can be found in references 9, 13, and 14. 

Hydrophobic associations can dominate polymer conformation in solution and solution rheological properties. Intrinsic viscosity and Huggins interaction coefficients provided information on the conformation and intramolecular aggregation behavior of these polymers in dilute solution. The presence of hydrophobic associations caused a decrease in the intrinsic viscosity and an increase in the Huggins constant. These effects could be counterbalanced by increasing the ionic charge on the polymer through hydrolysis or by copolymerization with sodium acrylate. 

Simha, R., Effect of shape and interaction on the viscosity of dilute solutions. Proceedings of the International Congress on Rheology, Holland (1948), Interscience Publishers, New York (1949). 

The addition of solute(s) further complicates rheology beeause in sueh mixtures solvents may not only interact among themselves but also with the solute(s). There are also interactions between solutes and the effect of ionized species with and without solvent participation. Only very dilute solutions of low molecular weight substances exhibit Newtonian viscosity. In these solutions, viscosity is a constant, proportionality factor of shear rate and shear stress. The viscosity of these solutions is usually well described by the classical, Einstein s equation ... 

The zero shear viscosity scales with Nf" to contrast Af dependence for isotropic polymers [20] So far, we have examined the dynamics of rod-Uke macromolecules in isotropic semi-dilute solution. For anisotropic LCP solutions in which the rods are oriented in a certain direction, the diffusion constant increases, and the viscosity decreases, but their scaling behavior with the molecular weight is expected to be unchanged [2,17], Little experimental work has been reported on this subject. The dynamics of thermotropic liquid crystalline polymer melts may be considered as a special case of the concentrated solution with no solvent. Many experimental results [16-18] showed the strong molecular weight dependence of the melt viscosity as predicted by the Doi-Edwards theory. However, the complex rheological behaviors of TLCPs have not been well theorized. 

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