RESUMO
We investigate carboxymethyl hydroxypropyl guar gum (CMHPG) solution properties in water and NaCl, KCl, and CaCl2 aqueous solutions. The Huggins, Kraemer, and Rao models were applied by fitting specific and relative viscosity of CMHPG/water and CMHPG/salt/water to determine the intrinsic viscosity [η]. The Rao models yielded better results (R2 = 0.779-0.999) than Huggins and Kraemer equations. [η] decreased up to 84% in salt solution over the range 0.9-100 mM compared to water. Salt effects screened the CMHPG charged side groups chains leading to a compacted structure. In 0.9 mM NaCl(aq), the hydrodynamic coil radius (Rcoil) was 28% smaller and 45% smaller in 100 mM NaCl solution relative to water. Similar decreases were seen in KCl and CaCl2 solutions. KCl and CaCl2 were more effective than NaCl. CMHPG is salt-tolerant and shows comparatively less viscosity change than native guar gum, with modest reduced viscosity increases with CMHPG dilution at all salt concentrations. The electrostatic interactions were effective up to 100 mM salt. The activation energy of viscous flow for CMHPG solutions was computed and compared to measured xanthan gum and several literature values. These data show that the barrier to CMHPG flow is higher than for xanthan gum.
Assuntos
Gomas Vegetais , Polissacarídeos , Cloreto de Sódio , Cloreto de Cálcio , Gomas Vegetais/química , Galactanos/química , Mananas/química , Água/química , ViscosidadeRESUMO
Aiming at the fundamental understanding of solvent effects in amphiphilic polymer systems, we considered poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers in water mixed with an ionic liquid-ethylammonium nitrate (EAN), 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6), or 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4)-and we investigated the hexagonal lyotropic liquid crystal structures by means of small-angle X-ray scattering (SAXS). At 50% polymer, the hexagonal structure (cylinders of self-assembled block copolymer) was maintained across the solvent mixing ratio. The effects of the ionic liquids were reflected in the characteristic length scales of the hexagonal structure and were interpreted in terms of the location of the ionic liquid in the self-assembled block copolymer domains. The protic ionic liquid EAN was evenly distributed within the aqueous domains and showed no affinity for the interface, whereas BMIMPF6 preferred to swell PEO and was located at the interface so as to reduce contact with water. BMIMBF4 was also interfacially active, but to a lesser extent.
RESUMO
Xanthan gum (XG) is a carbohydrate polymer with anionic properties that is widely used as a rheology modifier in various applications, including foods and petroleum extraction. The aim was to investigate the effect of Na+, K+, and Ca2+ on the physicochemical properties of XG in an aqueous solution as a function of temperature. Huggins, Kraemer, and Rao models were applied to determine intrinsic viscosity, [η], by fitting the relative viscosity (ηrel) or specific viscosity (ηsp) of XG/water and XG/salt/water solutions. With increasing temperature in water, Rao 1 gave [η] the closest to the Huggins and Kraemer values. In water, [η] was more sensitive to temperature increase (~30% increase in [η], 20-50 °C) compared to salt solutions (~15-25% increase). At a constant temperature, salt counterions screened the XG side-chain-charged groups and decreased [η] by up to 60% over 0.05-100 mM salt. Overall, Ca2+ was much more effective than the monovalent cations in screening charge. As the salt valency and concentration increased, the XG coil radius decreased, making evident the effect of shielding the intramolecular and intermolecular XG anionic charge. The reduction in repulsive forces caused XG structural contraction. Further, higher temperatures led to chain expansion that facilitated increased intermolecular interactions, which worked against the salt effect.