Solution Viscometry

Before we are in a position to discuss the viscosity of polymer melts, we must first give a quantitative definition of what is meant by viscosity and then say something about how this property is measured. This will not be our only exposure to experimental viscosity in this volume—other methods for determining bulk viscosity will be taken up in the next chapter and the viscosity of solutions will be discussed in Chap. 9—so the discussion of viscometry will only be introductory. Throughout we shall be concerned with constant temperature experiments conducted under nonturbulent flow conditions. 

Analysis for Poly(Ethylene Oxide). Another special analytical method takes advantage of the fact that poly(ethylene oxide) forms a water-insoluble association compound with poly(acryhc acid). This reaction can be used in the analysis of the concentration of poly(ethylene oxide) in a dilute aqueous solution. Ereshly prepared poly(acryhc acid) is added to a solution of unknown poly(ethylene oxide) concentration. A precipitate forms, and its concentration can be measured turbidimetricaHy. Using appropriate caUbration standards, the precipitate concentration can then be converted to concentration of poly(ethylene oxide). The optimum resin concentration in the unknown sample is 0.2—0.4 ppm. Therefore, it is necessary to dilute more concentrated solutions to this range before analysis (97). Low concentrations of poly(ethylene oxide) in water may also be determined by viscometry (98) or by complexation with KI and then titration with Na2S202 (99). 

The presence of a critical St content in ASt-x can also be seen in fluorescence spectra [29], This copolymer in aqueous solution shows an excimer emission peaking at 325 nra. As shown in Fig. 8, the intensity of the excimer emission increases, while the monomer emission decreases, with increasing St content. Eventually the excimer dominates the monomer emission at an St content of 72 mol%. The excimer emission becomes apparent at an St content of about 50 mol%, which agrees with the critical St content estimated by viscometry and NMR spectroscopy. The existence of the critical St content suggests the hydro-phobic self-aggregation to be a cooperative process. 

Hie hydrolytic depolymerization of nylon-6 was followed by gel permeation chromatography (GPC), viscometry, and gravimetry. GPC determinations were performed on a Waters 150C chromatography system using benzyl alcohol as die eluant, two Plgel 10-p.m crosslinked polystyrene columns, and a differential refractometer detector. The flow rate was 1 mL/min. The concentration of the polymer solutions was 0.5 wt% and dissolution was accomplished at 130°C. 

Monkos, Karol 2004. On the hydrodynamics and temperature dependence of the solution conformation of human serum albumin from viscometry approach. Biochimica et Biophysica Acta 1700, 27-34. 

Few sets of K,a parameters were given in references 17 and 22 K and a are parameters which may depends on the fine structure i.e. rhamnose content, DE... when they play on the stiffness of the chain. Nevertheless, it seems that the viscometry must be used in carefully defined conditions to avoid aggregation which often surestimates the viscosity in that conditions, [ti] is related to the physical properties of the solution (tickening properties) but not directly to My. 

In order to understand polymer solution behaviour, the samples have to be characterised with respect to their molecular configuration, their molar mass and polydispersity, the polymer concentration and the shear rate. Classical techniques of polymer characterisation (light scattering, viscometry, ultracentrifugation, etc.) yield information on the solution structure and conformation of single macromolecules, as well as on the thermodynamic interactions with the solvent. In technical concentrations the behaviour of the dissolved polymer is more complicated because additional intramolecular and intermolecular interactions between polymer segments appear. 

Dilute Solution Viscometry - The hydrogenated and hydroformyl ated (10%) PBD were completely soluble in toluene. Intrinsic viscosity measurements were carried out in toluene at 30°C using a Cannon-Ubbelohde viscometer. 

Chain Length Properties of the Modified Polymers. A number of partially hydrogenated and hydroxymethyl ated polybutadienes were analyzed using vapour pressure osmometry, dilute solution viscometry and gel permeation chromatography. The parent polybutadiene had Mn in the range of 9,000 to 50,000. In the case of vapour pressure osmometry, the data were reproducible for polymers with Mn less than 20,000. All the polymers obtained (hydrogenated and... 

The viscosities of products in solution (0.5 Weight %/volume) were measured by dilute solution viscometry using a Cannon Ubellohde viscometer at 35 °C. 

Sections of several packages were tested by dilute solution viscometry in decahydronaphthalene at 135°C to determine if the failures are consistent with UV degradation. The top surface of each package was partially covered by a paper label. This label should have shielded the underlying film from UV exposure, and there should be a difference in the solution viscosity of material taken from the shielded center of the package and material taken from the UV-exposed edge. Sections from the center and edge of three samples were... 

Table 16 Summary of dilute solution viscometry results ...

Shrinking of the polymer chains as a function of temperature was observed by capillary viscometry. The reduced viscosity, r]Sp/c, of polymer solutions approaches zero when the polymers are in their fully collapsed compact state and flow freely through the capillary. Above the cloud point, rjSp/c increases, which is indicative of aggregate formation. At low temperatures the... 

In addition, data on the size, shape and solvation of the polymer particles in aqueous solutions at temperatures below and above the transition phenomena registered by HS-DSC have been obtained [42]. Table 2 shows the results of capillary viscometry and light scattering experiments for the fractions p and s of poly(NVCl-co-NVIAz) synthesized at 65 °C from the feed with the initial molar comonomer ratio equal to 85 15. Since fraction p precipitates from the aqueous solution at temperatures > 34 °C, its intrinsic viscosity can be determined only at 20 °C, whereas for the fraction s such measurements were possible above and below the temperatures of the HS-DSC-registered conformational transition. 

Microgels are distinguished from linear and branched macromolecules by their fixed shape which limits the number of conformations of their network chains like in crosslinked polymers of macroscopic dimensions. The feature of microgels common with linear and branched macromolecules is their ability to form colloidal solutions. This property opens up a number of methods to analyze microgels such as viscometry and determination of molar mass which are not applicable to the characterization of other crosslinked polymers. 

For Molecular weight determination by viscometry we do not need absolute h value, viscosity measurements may be carried out in simple Ostwald Viscometer. Because of (the non-Newtonian behaviour of most macromolecular solutions at high velocity gradients in the capillary, the viscometer dimensions are chosen in such a manner that the viscosity gradient is the smallest possible. 

Values calculated from dilute solution viscometry (DSV) data for PAMAMs obtained in the same solution as in a for PPIs from ref. 19 for PBzEs from ref. 15. 

Polypropyleneimines have been examined by dilute solution viscometry by several groups of investigators [17-19, 22], For example, Scherrenberg and... 

Compared to dilute solution viscometry and to some extent to bulk rheology, the flow properties of dendrimers in concentrated solutions have been the least investigated area of dendrimer rheology. In fact, with the notable exception of some recent data on generation 4 PPI in water [22] the only [32] reported... 

It should be noted that discrepancies amidst available data may result from different methods of determination. For example, selected hydrodynamic radii of PAMAM dendrimers of Table 14.1 were obtained by two different experimental methods for generations 1 through 4 by dilute solution viscometry, while for generations 5 through 10 by size exclusion chromatography. 

---