Rheological properties of guar and its methyl, hydroxypropyl and hydroxypropyl-methyl derivatives in semidilute and concentrated aqueous solutions

We report on a comparative study of the rheological properties of guar GG], methyl guar MG], hydroxypropyl guar HPG] and hydroxypropyl-methyl guar MHPG] polymers aqueous solutions in semidilute (both unentangled and entangled) and concentrated regimes, using oscillatory and steady-shear techniques. In the dilute regime, molecular weights and radii of gyration have been investigated by means of light scattering measurements.Data obtained from steady-shear rheology were satisfactorily analyzed according to Cross model and the effects of polymer concentration and temperature on the rheological behaviour of guar and guar derivatives have been investigated and discussed in terms of rheological parameters, such as the zero-shear viscosity η₀, the characteristic time τ and critical coil-overlap concentration C^∗.The storage and loss moduli of guar and guar derivatives aqueous solutions have been measured using angular frequencies in the range between 10⁻³ and 10 rad/s. The data have been analyzed using the “blob” model for semidilute solutions and the scaling approach proposed by Rubinstein, Dobrynin and Colby for concentrated solutions. These rheological parameters obey a time-concentration superposition principle, so that master curves can be constructed over a wide frequency range. Moreover, we show that, at lower temperatures, these systems behave as thermo-rheological simple systems, in that the oscillatory shear response at different temperatures can be superimposed according to the empirical time-temperature superposition principle. Although these systems can be conveniently described within a unifying scaling model, the behaviour of guar derivatives are somewhat different. At higher temperatures, relatively small deviations from the scaling behaviour of the storage modulus of MG and MHPG polymers were observed. These findings can be justified by a structural re-organization of the macromolecular network, due to the hydrophobic interactions.