Solution viscosity behavior

In summary, these solution studies of sodium salts of lightly sulfonated polystyrene In tetrahydrofuran verify the presence of associating polymer behavior In lonomer solutions with nonionizing solvents. The results provide a molecular basis for the understanding of solution viscosity behavior. Individual lonomer colls are observed to retain constant dimensions while associating... 

The solution viscosity behavior of the new 3- and 4-chloro-phenyl Isocyanate derivatives are similar to that reported earlier... 

Solution Viscosity Behavior of Carboxylate and Sulfonate Ionomers. The solution behavior of sulfonated polymers has been described in some detail in a previous publication (13). It was shown in that study that... 

Effect of Temperature on the Solution Behavior of Carhoxylate and Sulfonate lonomers. Based on the results above, a substantial difference in the solution behavior of carhoxylate and sulfonate ionomers might be expected as a function of temperature. Figure 10 illustrates the effect of temperature on the solution viscosity of carboxylated and sulfonated ionomers at very low sulfonate and carhoxylate content. At low polymer concentrations it is seen that the sulfonate system manifests a higher viscosity level in 1% hexanol/xylene solution. This is consistent with the dilute solution viscosity behavior. More importantly, at high polymer concentrations it is seen from Figure 10 that the 5% S-PS curve actually goes through a maximum, while the carhoxylate system decreases mono-tonically. These results are apparently attributable to the weaker ionic association in the carhoxylate case as compared to the sulfonate system. 

Synthesis and Aqueous Solution Viscosity Behavior of Polyampholytes from Cationic-Anionic Monomer Pairs... 

The polyners eu e pr red in eiqueous emulsions at 100-120 C and 5-7 MPa pressure with a free reKiical initiator. The polymers are prepared at high monomer conversions and display normal solution viscosity behavior. Vii lidene fluoride is much more reactive than hexafluoropropylene, and, under the polymerisation conditions, no (HFP)n blocks are formed, whereas (VF2 )n sequences are present. The nudn polymer structure, therefore, is represented by the following blocks ... 

Both the intrinsic viscosity and GPC behavior of random coils are related to the radius of gyration as the appropriate size parameter. We shall see how the radius of gyration can be determined from solution viscosity data for these... 

SolubiHty parameters of 19.3, 16.2, and 16.2 (f /cm ) (7.9 (cal/cm ) ) have been determined for polyoxetane, po1y(3,3-dimethyl oxetane), and poly(3,3-diethyloxetane), respectively, by measuring solution viscosities (302). Heat capacities have been determined for POX and compared to those of other polyethers and polyethylene (303,304). The thermal decomposition behavior of poly[3,3-bis(ethoxymethyl)oxetane] has been examined (305). 

The microphase separation of an amphiphilic polyelectrolyte is clearly reflected in the viscosity behavior of its aqueous solution. As a representative example, Fig. 5 shows the reduced viscosities of ASt-x with different styrene (St) content plotted against the polymer concentration in salt-free aqueous solution [29], The AMPS homopolymer and its copolymers with low St content exhibit negative slopes, which is the typical behavior of polyelectrolytes in the concentration range shown in Fig. 5. With increasing St content, however, the slope systematically decreases and eventually turns to be slightly positive, while reduced viscosity itself markedly decreases. These data indicate that, with increasing St content, the... 

The various physical methods in use at present involve measurements, respectively, of osmotic pressure, light scattering, sedimentation equilibrium, sedimentation velocity in conjunction with diffusion, or solution viscosity. All except the last mentioned are absolute methods. Each requires extrapolation to infinite dilution for rigorous fulfillment of the requirements of theory. These various physical methods depend basically on evaluation of the thermodynamic properties of the solution (i.e., the change in free energy due to the presence of polymer molecules) or of the kinetic behavior (i.e., frictional coefficient or viscosity increment), or of a combination of the two. Polymer solutions usually exhibit deviations from their limiting infinite dilution behavior at remarkably low concentrations. Hence one is obliged not only to conduct the experiments at low concentrations but also to extrapolate to infinite dilution from measurements made at the lowest experimentally feasible concentrations. 

So far the results have been shown in which the metal alkoxide solutions are reacted in the open system. It has been shown that the metal alkoxide solutions reacted in the closed container never show the spinnability even when the starting solutions are characterized by the low acid content and low water content (4). It has been also shown from the measurements of viscosity behavior that the solution remains Newtonian in the open system, while the solution exhibits structural viscosity (shear-thinning) in the closed system. 

Viscosity Behavior. The polymeric nature of triorganotin fluorides dissolved in nonpolar solvents is outlined in the introduction. As a result of the transient polymer formation, these solutions exhibit nonlinear concentration vs. viscosity curves. 

The typical viscous behavior for many non-Newtonian fluids (e.g., polymeric fluids, flocculated suspensions, colloids, foams, gels) is illustrated by the curves labeled structural in Figs. 3-5 and 3-6. These fluids exhibit Newtonian behavior at very low and very high shear rates, with shear thinning or pseudoplastic behavior at intermediate shear rates. In some materials this can be attributed to a reversible structure or network that forms in the rest or equilibrium state. When the material is sheared, the structure breaks down, resulting in a shear-dependent (shear thinning) behavior. Some real examples of this type of behavior are shown in Fig. 3-7. These show that structural viscosity behavior is exhibited by fluids as diverse as polymer solutions, blood, latex emulsions, and mud (sediment). Equations (i.e., models) that represent this type of behavior are described below. 

The introduced THEOS did not bring about precipitation in protein solutions. This behavior differs from that observed with common silica precursors. For example, TEOS added in such small amounts caused precipitation. By using THEOS, we could prepare homogeneous mixtures. When its amount introduced into the albumin solution was less than 5 wt.%, there was no transition to a gel state (Table 3.1). A gradual increase in THEOS concentration resulted in a rise in the solution viscosity. The transition to a gel state took place as soon as a critical concentration was reached. Its value, as demonstrated in Ref. 

With the least polar solvent, 9 1 MIBK/MEOH, aggregation dominates the viscosity behavior. This solvent is of intermediate quality, between pure MeOH and the 1 1 mixture. Still, the viscosity is greatest using the 9 1 mix at all temperatures, by up to a factor of four. The effect of temperature on the aggregation in the 9 1 MIBK/MeOH solution is so large that the fmj versus 1/T curve becomes significantly nonlinear. An apparent E determined when... 

The viscosity behavior described so far is valid only for uncharged polymers. If polyelectrolytes are analyzed, a quite different viscosity behavior may be found in polar solvents (e.g., polymeric acids in water). The q p/c values at first fall off with decreasing concentration as for uncharged polymers but then climb steeply again and may drop down later again (see Fig. 2.16). Addition of salt to the solution of polyelectrolytes (e.g., 1% and 5% sodium chloride in aqueous solution) restores, step by step, the normal behavior (see Fig. 2.16, curves b and c). 

If, however, the viscosity is measured at the same concentrations in 1 N NaCI solution the behavior is identical with that for non-electrolyte polymers. It is best to proceed as follows. 30 g of NaCI are dissolved in water and made up to 100 ml in a graduated flask this solution is 5.1 normal.To prepare the solutions for measurement at the aforementioned concentrations, the required amounts of poly(methacrylic acid) are weighed into 10-ml graduated flasks, dissolved in about 5 ml of water,and 2 ml of the 5.1 N NaCI solution added.The solutions are finally made up to the mark with water to give a solution of 1 N with respect to NaCI. 

If one follows the solution viscosity in concentrated sulfuric acid with increasing polymer concentration, then one observes first a rise, afterwards, however, an abrupt decrease (about 5 to 15%, depending on the type of polymers and the experimental conditions). This transition is identical with the transformation of an optical isotropic to an optical anisotropic liquid crystalline solution with nematic behavior. Such solutions in the state of rest are weakly clouded and become opalescent when they are stirred they show birefringence, i.e., they depolarize linear polarized light. The two phases, formed at the critical concentration, can be separated by centrifugation to an isotropic and an anisotropic phase. A high amount of anisotropic phase is desirable for the fiber properties. This can be obtained by variation of the molecular weight, the solvent, the temperature, and the polymer concentration. 

The viscosity of xanthan solutions is also distinct from that of flexible polyelectrolyte solutions which generally shows a strong Cs dependence [141]. In this connection, we refer to Sho et al. [142] and Liu et al. [143], who measured the intrinsic viscosity and radius of gyration of Na salt xanthan at infinite dilution which were quite insensitive to Cs ( > 0.005 mol/1). Their finding can be attributed to the xanthan double helix which is so stiff that its conformation is hardly perturbed by the intramolecular electrostatic interactions. In fact, it has been shown that the electrostatic persistence length contributes only 10% to the total persistence length even at as low a Cs as 0.005 mol/1 [142]. Therefore, the difference in viscosity behavior between xanthan and flexible polyelectrolyte... 

The suggested rod like structure of the pendant-type FVP-Co(III) complex is supported by the viscosity behavior of the polymer-complex solution (Fig. 3)2 The PVP-Co(III) complexes have higher viscosity than PVP this suggests that the polymer complex has a linear structure and that intra-polymer chelation does not occur. The dependence of the reduced viscosity on dilution and the effect of ionic strength further show that Co(en)2(PVP)Cl] Cl2 is a poly(electrolyte). The polymer complexes with higher x values have a rodlike structure due to electrostatic repulsion or the steric bulkiness of the Co(III) chelate. On the other hand, the solubility and solution behavior of the polymer complex with a lower x value is similar to that of the polymer ligand itself. 

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