Interrelation between the thermodynamic and viscometric behaviour of aqueous solutions of hydrophobically modified ethyl hydroxyethyl cellulose
Abstract Aqueous solutions of a commercial sample of hydrophobically modified ethyl hydroxyethyl cellulose (HC, Mw=100 kg/mol, nonylphenol substitution ca. 1.7 mol%) were studied with respect to their demixing behaviour and flow characteristics. Phase separation temperatures were measured turbidimetrically and by determining the first discernible macroscopic phase separation. In some cases demixing was also monitored viscometrically. Phase volume ratios yielded a critical polymer concentration of 1.87 wt.% HC (displaced considerably out of the minimum of the demixing curve towards higher polymer concentrations) and a lower critical solution temperature of 47°C. Model calculations of the spi…
Polyelectrolytes in dilute solution: viscometric access to coil dimensions and salt effects
Copolymers of acrylamide (AM) and diallyldimethylammonium chloride (DADMAC), differing in molar masses M (52.3 to 227 kDa) and degrees of charging y (0.2 to 0.6), were studied with respect to their viscometric behavior in dilute aqueous solutions containing variable amounts of NaCl. Complementary measurements were performed on a Brookhaven 90 plus particle size analyzer. M dominates the intrinsic viscosities [η]. For the viscometric interaction parameters B this is only true for large concentrations of extra salt. [η] and B as a function of solvent salinity follow Boltzmann laws. Coil dimensions, determined either via dynamic light scattering or viscometry, agree well. For low salt contents…
Shear Induced Demixing and Rheological Behavior of Aqueous Solutions of Poly(N-isopropylacrylamide)
The interrelation between the phase separation behavior and the rheological performance of aqueous solutions of high molecular weight (M w = 1 600 kg/mol) poly(N-isopropylacrylamide) was investigated. The system demixes upon heating and the cloud point temperature, T cp decreases steadily with rising polymer concentration up to 10 wt.-%. The application of shear supports phase separation and reduces T cp markedly. This observation is interpreted in terms of destruction of intersegmental clusters formed in the quiescent state owing to favorable interactions. Intrinsic viscosities and Huggins coefficients as well as the viscosities, η at higher polymer concentrations are closely connected wit…
Intrinsic Viscosity of Aqueous Solutions of Carboxymethyl Guar in the Presence and in the Absence of Salt
Intrinsic viscosities were determined for solutions of CMG in pure water and 0.9 wt.-% aqueous NaCl. To avoid the 0/0-type extrapolation typical for Huggins plots, a new procedure was used. For CMG and pure water, this requires only two adjustable parameters: the specific hydrodynamic volume of the polymer in the limit of infinite dilution and a hydrodynamic interaction parameter. The intrinsic viscosity of CMG (no salt) at room temperature is 6 050 mL · g -1 ; approximately half as large as that of Na-PSS of comparable molar mass. The ratio of the intrinsic viscosities with and without salt is ≈7 for CMG, as compared to >100 for Na-PSS. The reasons for the different behaviors of the two ty…