Viscosification in polymer-surfactant mixtures at low temperatures.

Interactions between the anionic surfactant sodium dodecyl sulfate (SDS) and hydroxyethylcellulose (HEC) or its hydrophobically modified analogue (HM-HEC) have been studied over an extended temperature region with the aid of turbidimetry, small-angle neutron scattering (SANS), and shear viscosimetry. Anomalous viscosity enhancements were observed for semidilute HEC/SDS and HM-HEC/SDS solutions at high SDS concentrations at temperatures far below the Krafft point for aqueous solutions of SDS. From the Arrhenius-Frenkel-Eyring (AFE) plots of the temperature dependence of the zero-shear viscosity, the activation energy of chain disengagement (DeltaE(vis)) was found to be on the order of 40 kJ mol(-1) for the HEC/SDS mixtures, whereas for the HM-HEC/SDS system, much higher values of DeltaE(vis) (up to 141 kJ mol(-1)) were reported, and the activation energy increased with an increasing level of SDS addition. Break points in the AFE plots were observed for both the HEC/SDS and HM-HEC/SDS systems at low temperatures and high SDS concentrations. Time evolutions of both the turbidity and the shear viscosity were monitored after quenching of the temperature from 25 to 1 degrees C. The turbidity results revealed in general a less pronounced transition for the HEC/SDS and HM-HEC/SDS systems than for the corresponding polymer-free SDS/water solutions. In the course of time, a significant viscosity enhancement was found for the HEC/SDS system at high levels of SDS addition, and a much stronger viscosification was observed for the HM-HEC/SDS system at the highest surfactant concentration. The overall results suggest that hydrated SDS aggregates act as cross-linkers of the network and generate the substantial viscosification of the systems at low temperature and high levels of SDS addition. For the HM-HEC/SDS system, further strengthening of the network occurs because of the contribution from hydrophobic interactions. The SANS data on HEC/SDS mixtures reveal that some structural reorganization takes place at low temperatures in the presence of high SDS concentrations, and this is ascribed to enhanced polymer-SDS interactions and the formation of clusters that strengthened the cross-links of the network.

Characterization of polyelectrolyte features in polysaccharide systems and mucin.

This review elucidates several aspects on the behavior of charged polysaccharides and mucin. Viscosification of dilute aqueous solutions of hyaluronan (HA) occurs in the course of time at low shear flow, whereas shear thinning as time evolves is found at moderate shear rates. Hydrogen bonds and electrostatic interaction play an important role for the emergence of these features. No time effect of the viscosity is observed for semidilute HA solutions. A degradation of HA is observed at low and high pH and this effect continues over long times, and it is only in the approximate interval 5>2 the negative charges suppress the tendency of forming associations. At pH<2, the mucin chains are compressed and they are decorated by some positive charges. In the semidilute regime, a fragmented network is developed. The intense association in semidilute solutions of mucin at pH=2 is further supported by the results from rheo-small angle light scattering measurements. Effects of ionic strength on the radius of gyration (R(g)) for dilute solutions of HA (pH=7) and positively charged hydroxyethylcellulose (HEC(+)) are studied with the aid of Monte Carlo simulations, and essential features of the polyelectrolyte effect on R(g) are captured in the computer simulation. Strong interactions are observed in aqueous mixtures of an anionic polysaccharide (HEC(-)) and an oppositely charged surfactant (cetyltrimethylammonium bromide; CTAB); this gives rise to extensive associations and macroscopic phase separation is approached. The massive association complexes are disclosed in the SANS experiments by a pronounced upturn in the scattered intensity at low values of the wave vector.

Characterization of thermally sensitive interactions in aqueous mixtures of hydrophobically modified hydroxyethylcellulose and cyclodextrins.

Effects of beta-cyclodextrin (beta-CD) or hydroxypropyl-beta-cyclodextrin (HP-beta-CD) addition and temperature on thermodynamic, rheological, and structural features of semidilute solutions of hydroxyethylcellulose (HEC) and its hydrophobically modified analogue (HM-HEC) are reported. Differential scanning calorimetric (DSC) measurements revealed a thermally induced crystal melting transition of beta-CD at high concentrations in solutions of HEC and HM-HEC. No transition with HP-beta-CD was observed in aqueous solution. Viscosity results indicated that at a cosolute concentration of 2 mm, the beta-CD units are threaded onto hydrophobic tails of HM-HEC (C16 groups) to form columnar structures. This arrangement is more effective in the encapsulation of the hydrophobic chains than the monomer hydrophobic deactivation accomplished by the HP-beta-CD units. At cosolute concentrations above 8 mm, no further decoupling of the hydrophobic interactions occurs for any of the cosolutes. Small-angle neutron scattering (SANS) experiments on HM-HEC/beta-CD mixtures suggest that the large-scale association structures in HM-HEC/D(2)O solutions are reduced upon addition of beta-CD, and an interesting temperature effect is observed at 2 mm beta-CD addition. At high beta-CD concentrations and low temperatures, the formation of large beta-CD clusters or crystallites generates cross-links in the HEC and HM-HEC networks, resulting in a viscosity enhancement of several orders of magnitude. This strong temperature effect is not reflected in the structural features probed by SANS.

Characterization of interactions in aqueous solutions of hydroxyethylcellulose and its hydrophobically modified analogue in the presence of a cyclodextrin derivative.

The formation of associative networks in semidilute aqueous solutions of hydrophobically modified hydroxyethylcellulose (HM-HEC) is dependent on intermolecular hydrophobic interactions. Addition of hydroxypropyl-beta-cyclodextrin (HP-beta-CD) monomers to the system provides decoupling of these associations via inclusion complex formation with the polymer hydrophobic tails. Results from viscosity, polymer NMR self-diffusion, and dynamic light scattering (DLS) measurements show that the hydrophobic interactions in HM-HEC solutions are effectively suppressed when the level of HP-beta-CD addition increases. Small-angle neutron scattering (SANS) results reveal that the large-scale association complexes in HM-HEC solutions are strongly diminished when the concentration of HP-beta-CD rises. The time correlation data obtained from the DLS experiments unveiled the existence of two relaxation modes: one single exponential at short times followed by a stretched exponential at longer times. The fast mode is always diffusive, whereas the slow mode exhibits progressively stronger wavevector dependence as the intensity of the hydrophobic interactions increases. This feature, as well as the accompanying drop of the stretched exponential beta as the HP-beta-CD concentration decreases, is attributed to enhanced hydrophobic interactions and can be well rationalized in the framework of the coupling model of Ngai.