Intrinsic viscosity experimental results

Reference 24. The temperature of the experimental was not reported. Values obtained from intrinsic viscosity measurements. Results corresponding to the molecular weight larger than... 

Fox and Floryf used experimental molecular weights, intrinsic viscosities, and rms end-to-end distances from light scattering to evaluate the constant in Eq. (9.55). For polystyrene in the solvents and at the temperatures noted, the following results were assembled ... 

In order to do this, experimental determinations of the intrinsic viscosities of both the standards and the fractions from the unknown polymer are required. It is possible to obtain commercial gel permeation chromatographs that will do this routinely, and hence to exploit the concept of universal cali-hration. Care must he taken, though, to ensure that the separation of the polymer molecules occurs purely as a result of size exclusion. If there are any other specific interactions, e.g. hydrogen bonding, between the polymer and the column packing, such as may occur with water-soluhle polymers, Benoit s approach does not work and the universal cafihrafion plot is not valid. 

For poly electrolyte solutions with added salt, prior experimental studies found that the intrinsic viscosity decreases with increasing salt concentration. This can be explained by the tertiary electroviscous effect. As more salts are added, the intrachain electrostatic repulsion is weakened by the stronger screening effect of small ions. As a result, the polyelectrolytes are more compact and flexible, leading to a smaller resistance to fluid flow and thus a lower viscosity. For a wormlike-chain model by incorporating the tertiary effect on the chain... 

TREATMENT OF EXPERIMENTAL RESULTS INTRINSIC VISCOSITIES OF NONIONIC POLYMERS ... 

An appropriate formalism for Mark-Houwink-Sakurada (M-H-S) equations for copolymers and higher multispecies polymers has been developed, with specific equations for copolymers and terpolymers created by addition across single double bonds in the respective monomers. These relate intrinsic viscosity to both polymer MW and composition. Experimentally determined intrinsic viscosities were obtained for poly(styrene-acrylonitrile) in three solvents, DMF, THF, and MEK, and for poly(styrene-maleic anhydride-methyl methacrylate) in MEK as a function of MW and composition, where SEC/LALLS was used for MW characterization. Results demonstrate both the validity of the generalized equations for these systems and the limitations of the specific (numerical) expressions in particular solvents. 

The model parameters q and ML can be estimated from experimental data for radius of gyration, intrinsic viscosity, sedimentation coefficient, diffusion coefficient and so on in dilute solutions. The typical methods are expounded in several recent articles and books [20-22], Here we refer only to the results of the application to representative liquid-crystalline polymers (See Table 1). 

Another interesting contribution to the study of viscosity behavior in the helix-coil Jransition region is the one due to Hayashi et al. (22) on a PBLA sample (Mw = 23.2 x 104) in m-cresol and a mixture of chloroform and DCA (5.7 voL-% DCA). As mentioned in Chapter B, PBLA undergoes an inverse transition in the chloroform-DCA mixture, while it undergoes a normal transition in m-cresol. Furthermore, its cooperativity parameter is distinctly smaller in the former solvent than in the latter. Thus we may expect that, when compared at the same helical fraction and chain length, the PBLA molecule in the chloroform-DCA mixture assumes a more extended shape and hence a larger intrinsic viscosity than in m-cresol, provided these two solvents have comparable solvent powers for the polymer. The experimental results shown in Fig. 32 are taken to substantiate this prediction, because the approximate agreement of the data points atfN=0 indicates that the two solvents have nearly equal solvent powers for the solute. 

Figure 4.12a shows plots of the intrinsic viscosity —in volume fraction units —as a function of axial ratio according to the Simha equation. Figure 4.12b shows some experimental results obtained for tobacco mosaic virus particles. These particles —an electron micrograph of which is shown in Figure 1.12a—can be approximated as prolate ellipsoids. Intrinsic viscosities are given by the slopes of Figure 4.12b, and the parameters on the curves are axial ratios determined by the Simha equation. Thus we see that particle asymmetry can also be quantified from intrinsic viscosity measurements for unsolvated particles. 

Evaluate the intrinsic viscosity for each size of spherical particle and comment on the results in terms of the Einstein prediction that [17] should be independent of particle size. Is the fact that benzyl alcohol is only a moderately good solvent for linear polystyrene consistent with the observed deviation between the experimental and theoretical values for [17] Explain. 

In an earlier procedure applying universal calibration, viscosities of the four most concentrated fractions eluting about the peak were measured, and the intrinsic viscosities were plotted against count. The intrinsic viscosities of all the fractions were obtained by extrapolation of the plot for use in the calculations to obtain degree of polymerization (DP). In the present method the DP of each fraction is obtained from the relationship MW = (cod size/K)1/1+ derived from Benoit s concept and the Mark-Houwink equation. Results from the new procedure are in excellent agreement with those obtained independently on cotton by others. Anomalies in results obtained previously on some samples disappear while marked improvement is noted for others. The determination is speeded up greatly by computer processing of data, and experimental error is reduced. 

Experimental evidence on whether L or other molecular parameters (Stokes radius, viscosity radius, radius of gyration, the product of intrinsic viscosity and molecular weight, etc.) govern partitioning in SEC supports has been summarized by Dubin [29]. He concludes that none of these parameters perfectly correlates with SEC partitioning when a wide variety of macromolecules, of both rigid and flexible structure, are used as test probes. This may result from the complex uncharacterized nature of the pore space occupying the porous supports commonly utilized. 

According to the statistical-mechanical theory of rubber elasticity, it is possible to obtain the temperature coefficient of the unperturbed dimensions, d InsjdT, from measurements of elastic moduli as a function of temperature for lightly cross-linked amorphous networks [Volken-stein and Ptitsyn (258 ) Flory, Hoeve and Ciferri (103a)]. This possibility, which rests on the reasonable assumption that the chains in undiluted amorphous polymer have essentially their unperturbed mean dimensions [see Flory (5)j, has been realized experimentally for polyethylene, polyisobutylene, natural rubber and poly(dimethylsiloxane) [Ciferri, Hoeve and Flory (66") and Ciferri (66 )] and the results have been confirmed by observations of intrinsic viscosities in athermal (but not theta ) solvents for polyethylene and poly(dimethylsiloxane). In all these cases, the derivative d In sjdT is no greater than about 10-3 per degree, and is actually positive for natural rubber and for the siloxane polymer. 

In summarizing the intrinsic viscosity relations presented in this section, it must be admitted that they represent nothing more than rather small semi-empirical refinements of the Flory excluded volume theory and the Flory-Fox viscosity theory. For a large fraction of the existing body of experimental data, they offer merely a slight improvement in curve-fitting. But for polymers in good solvents it is believed that a more transcendental result has been achieved. The new equations permit more reliable assessment of unperturbed chain dimensions in such cases, and in some instances (e. g., certain cellulose derivatives see Section III B) they offer possible explanations of heretofore paradoxical solution behavior. 

The hydrodynamic properties of solutions of native double-stranded DNA have thus far eluded complete quantitative interpretation, in spite of very extensive investigation. A synthesis of experimental data has recently been furnished by Doty [84 ) some of the earlier experimental results may be found in the papers of Doty, Bunce-McGiix, and Rice (86) Doty, Makmur, Eignek, and Schildkraut (55) and Kawade and Watanabe (135 ). It is easy to see that the double helices are not perfectly inflexible, for the observed intrinsic viscosities are far lower than those of rigid rods or ellipsoids with the Watson-Crick dimensions, p = Af/4600. On the other hand, the customary flexible-coil treatments also do not apply to these data. For example, if the correlation plot of against g (a) M l [) ], / is attempted, it is found that... 

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