Viscosity polymer solutions, 576 review

The heat of dissociation in hexane solution of lithium polyisoprene, erroneously assumed to be dimeric, was reported in a 1984 review 71) to be 154.7 KJ/mole. This value, taken from the paperl05> published in 1964 by one of its authors, was based on a viscometric study. The reported viscometric data were shown i06) to yield greatly divergent AH values, depending on what value of a, the exponent relating the viscosity p of a concentrated polymer solution to DPW of the polymer (q DP ), is used in calculation. As shown by a recent compilation 1071 the experimental a values vary from 3.3 to 3.5, and another recent paper 108) reports its variation from 3.14 to 4. Even a minute variation of oe results in an enormous change of the computed AH, namely from 104.5 KJ/mole for oe = 3.38 to 209 KJ/mole for oe = 3.42. Hence, the AH = 154.7 KJ/mole, computed for a = 3.40, is meaningless. For the same reasons the value of 99.5 KJ/mole for the dissociation of the dimeric lithium polystyrene reported in the same review and obtained by the viscometric procedure is without foundation. 

In this review we have briefly discussed the theoretical and experimental aspects of both Newtonian and non-Newtonian viscosities of polymer solutions. To protein chemists one of the interesting developments is no doubt the re-examination of the (Newtonian) viscosity treatments of protein solutions. There are many assumptions involved in the effective use of intrinsic viscosity measurements for evaluating the asymmetry of the protein molecules, however attractive the conventional treatment may have appeared for the past two decades. Carefully interpreted, the intrinsic viscosity (at zero gradient) can still provide a reasonable estimate of the axial ratios of the protein molecules. The concept of equivalent hydrodynamic volume, sound in principle, has put the viscometry of protein solutions in a proper perspective, although the quantitative aspects of this new approach still... 

Viscosity Maxima. The low-shear-rate viscosities of both commercial and model associative thickeners below their c /, values will increase with the addition of conventional low molecular weight surfactants or coalescing aid (22). With HEUR polymers, solution viscosities are observed to increase, achieve a maximum value, and then decrease with continued increase in surfactant concentration (23). This type of behavior is illustrated (Figure 5) for four commercial HEURs with a nonionic surfactant (typical of that used in coating formulations). A similar behavior has been observed (24) with a classical anionic surfactant and hydrophobically modified (hydroxy-ethyl)cellulose (HMHEC) and is reviewed in Chapter 18. Intermicellar networks, formed by the participation of one or more hydrophobes from different polymers in the micelles of conventional surfactants, were again recently suggested (25) to affect viscous solutions. 

Drag reduction can be achieved by direct injection of microbubbles through slots or porous skin (193-196) or the generation of hydrogen by electrolysis at the wall (197). The primary parameters, independent of gas type and Reynolds number, appear to be the actual gas flow rate referenced to injector conditions of temperature and pressure (198-200) and the location of the bubbles in the turbulent boundary layer (198,199,201-203). Merkle and Deutsch (196) have provided a comprehensive review on skin friction reduction by microbubble injection. Mahadevan and co-workers (204) postulated that microbubbles like polymer solution destroy turbulence production by selectively increasing the viscosity near the buffer region. They increase the local dynamic viscosity. Pal and co-workers (205) demonstrated that microbubble and polymer solution shear stress statistics as measured by flush moimted hot film sensors are similar at equivalent value of drag reduction. 

This chapter has made a systematic review of the published literature on the viscosity of nondilute polymer solutions. The primary conclusion here is that t](c, M) has a uniform behavior, namely that r] c, M) follows a stretched exponential in c and M, in all systems for r]/r]Q less than a few hundred, and in many systems up to extremely large q/r Q. In a considerable number of other systems, there is a transition viscosity rjt, above which r (c, M) follows a power law c. The location of the solutionlike-meltlike transition, when it occurs at all, has a characteristic viscosity rit is typically several hundred in dimensionless units. The transition is not identified by a characteristic concentration c+. In natural units, c [t]] for... 

In order to understand how shear flow affects the phase behaviom of polymer blends, it is useful to consider first how homogeneous polymeric systems respond to an imposed shear flow. This is a subject that has received considerable attention, and many of the details are imnecessary for this review however, a basic understanding of polymer rheology [15] is essential, and so we present a brief overview of the most relevant ideas. When a polymer solution or blend (or indeed any viscoelastic medium) is subjected to a steady shear, its response can be characterised by the viscosity. 

These normal stresses are more pronounced for polymers with a very broad molecular weight distribution. Viscosities and viscoelastic behavior decrease with increasing temperature. In some cases a marked viscosity decrease with time is observed in solutions stored at constant temperature and 2ero shear. The decrease may be due to changes in polymer conformation. The rheological behavior of pure polyacrylamides over wide concentration ranges has been reviewed (5). 

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