Sphere intrinsic viscosity

If the molecules of the solute in a solution behave as hard spheres, intrinsic viscosity is independent of the molecular weight of the solute. The value of a, the exponent in the Mark-Houwiiik equation (7.7), then becomes equal to zero, i.c., [ q = KaP = K. Examples ... 

This concludes our discussion of the viscosity of polymer solutions per se, although various aspects of the viscous resistance to particle motion continue to appear in the remainder of the chapter. We began this chapter by discussing the intrinsic viscosity and the friction factor for rigid spheres. Now that we have developed the intrinsic viscosity well beyond that first introduction, we shall do the same (more or less) for the friction factor. We turn to this in the next section, considering the relationship between the friction factor and diffusion. 

All that can be concluded from the data given in the preceding example is that the particle is not an unsolvated sphere. However, when an appropriate display of contours is examined for f/fo (e.g.. Ref. 2), the latter is found to be consistent with an unsolvated particle of axial ratio about 4 1 or with a spherical particle hydrated to the extent of about 0.48 g water (g polymer). Of course, there are a number of combinations of these variables which are also possible, and some additional experimental data—such as the intrinsic viscosity—are needed to select that combination which is consistent with all experimental observations. 

The simplest indicator of conformation comes not from but the sedimentation concentration dependence coefficient, ks. Wales and Van Holde [106] were the first to show that the ratio of fcs to the intrinsic viscosity, [/ ] was a measure of particle conformation. It was shown empirically by Creeth and Knight [107] that this has a value of 1.6 for compact spheres and non-draining coils, and adopted lower values for more extended structures. Rowe [36,37] subsequently provided a derivation for rigid particles, a derivation later supported by Lavrenko and coworkers [10]. The Rowe theory assumed there were no free-draining effects and also that the solvent had suf-... 

Theory presented earlier in this chapter led to the expectation that the frictional coefficient /o for a polymer molecule at infinite dilution should be proportional to its linear dimension. This result, embodied in Eq. (18) where P is regarded as a universal parameter which is the analog of of the viscosity treatment, is reminiscent of Stokes law for spheres. Recasting this equation by analogy with the formulation of Eqs. (26) and (27) for the intrinsic viscosity, we obtain ... 

The specific viscosity )jsp of a dilute solution of spheres is directly related to their hydrodynamic volume VV Nl denotes Avogadro s number. Typically the intrinsic viscosity [tj] follows a scaling law, the so-called Mark-Houwink-Sakurada equation ... 

The intrinsic viscosity of microgels described in [9] decreased with increasing fractions of the crosslinking monomer to about 8 ml/g which was still above the theoretical value for hard spheres of about 2.36 ml/g according to the Einstein equation and assuming a density of 1.1 g/ml. Obviously, due to the relatively low fraction of the crosslinking monomer, these microgels did not behave like hard spheres and were still swellable to some extent. 

The solution properties of dendrigraft polybutadienes are, as in the previous cases discussed, consistent with a hard sphere morphology. The intrinsic viscosity of arborescent-poly(butadienes) levels off for the G1 and G2 polymers. Additionally, the ratio of the radius of gyration in solution (Rg) to the hydrodynamic radius (Rb) of the molecules decreases from RJRb = 1.4 to 0.8 from G1 to G2. For linear polymer chains with a coiled conformation in solution, a ratio RJRb = 1.48-1.50 is expected. For rigid spheres, in comparison, a limiting value RJRb = 0.775 is predicted. 

The next step consists of the determination of the size of the macromolecules in space. Two equivalent sphere radii can be measured directly by means of static and dynamic LS. Another one can be determined from a combination of the molar mass and the second virial coefficient A2. Similarly, an equivalent sphere radius is obtained from a combination of the molar mass with the intrinsic viscosity. This is outlined in the following sections. 

Similar to what was done with the intrinsic viscosity we may compare Eq. (24) with the corresponding equation for hard spheres which is given by [3,74,75]... 

Staudinger showed that the intrinsic viscosity or LVN of a solution ([tj]) is related to the molecular weight of the polymer. The present form of this relationship was developed by Mark-Houwink (and is known as the Mark Houwink equation), in which the proportionality constant K is characteristic of the polymer and solvent, and the exponential a is a function of the shape of the polymer in a solution. For theta solvents, the value of a is 0.5. This value, which is actually a measure of the interaction of the solvent and polymer, increases as the coil expands, and the value is between 1.8 and 2.0 for rigid polymer chains extended to their full contour length and zero for spheres. When a is 1.0, the Mark Houwink equation (3.26) becomes the Staudinger viscosity equation. 

The hydrodynamic shape factor and axial ratio are related (see Eigure 4.18), but are not generally used interchangeably in the literature. The axial ratio is used almost exclusively to characterize the shape of biological particles, so this is what we will utilize here. As the ellipsoidal particle becomes less and less spherical, the viscosity deviates further and further from the Einstein equation (see Eigure 4.19). Note that in the limit of a = b, both the prolate and oblate ellipsoid give an intrinsic viscosity of 2.5, as predicted for spheres by the Einstein equation. 

The Einstein theory is based on a model of dilute, unsolvated spheres. In this section we examine the consequences on intrinsic viscosity of deviations from the Einstein model in each of the following areas ... 

Equation (48) has been derived under the assumption that the volume fraction can reach unity as more and more particles are added to the dispersion. This is clearly physically impossible, and in practice one has an upper limit for , which we denote by max. This limit is approximately 0.64 for random close packing and roughly 0.71 for the closest possible arrangement of spheres (face-centered cubic packing or hexagonal close packing). In this case, d in Equation (46) is replaced by d(j>/[ 1 — (/m[Pg.169]

EXAMPLE 13.5 Determination of the Thickness of Adsorbed Polymer Layer from the Intrinsic Viscosity of the Dispersion. An adsorbed layer of thickness 8RS on the surface of spherical particles of radius R increases the volume fraction occupied by the spheres and therefore makes the intrinsic viscosity of the dispersion greater than predicted by the Einstein theory. Derive an expression that allows the thickness of the adsorbed layer to be calculated from experimental values of intrinsic viscosity. 

Several theoretical tentatives have been proposed to explain the empirical equations between [r ] and M. The effects of hydrodynamic interactions between the elements of a Gaussian chain were taken into account by Kirkwood and Riseman [46] in their theory of intrinsic viscosity describing the permeability of the polymer coil. Later, it was found that the Kirdwood - Riseman treatment contained errors which led to overestimate of hydrodynamic radii Rv Flory [47] has pointed out that most polymer chains with an appreciable molecular weight approximate the behavior of impermeable coils, and this leads to a great simplification in the interpretation of intrinsic viscosity. Substituting for the polymer coil a hydrodynamically equivalent sphere with a molar volume Ve, it was possible to obtain... 

The physical properties of these polymeric dendrimers have been studied to some extent. Intrinsic viscosity measurements combined with MW afford values of according to Eq. (5). Alternatively, the translational diffusion coefficient leads to Rh according to Eq. (6). These equations may well be applicable, since it is observed that Rn and Rh scale with the 1/3 power of MW in support of the equal density hard-sphere assumption [88]. 

Fig. 37. The ratio of the equivalent hard sphere volume fraction based on the measured intrinsic viscosity as a function of for polyfmethyl methacrylate) spheres with grafted poly( 12-hydroxy stearic add) layers such that a/L = 4.7 (Mewis et ai, 1989). Open and closed circles correspond to the low and high shear limits of suspension viscosity.

Being able to determine [r ] as a function of elution volume, one can now compare the hydrodynamic volumes Vh for different polymers. The hydrodynamic volume is, through Einstein s viscosity law, related to intrinsic viscosity and molar mass by Vh=[r ]M/2.5. Einstein s law is, strictly speaking, valid only for impenetrable spheres at infinitely low volume fractions of the solute (equivalent to concentration at very low values). However, it can be extended to particles of other shapes, defining the particle radius then as the radius of a hydrody-namically equivalent sphere. In this case Vjj is defined as the molar volume of impenetrable spheres which would have the same frictional properties or enhance viscosity to the same degree as the actual polymer in solution. 

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