Influence of poly(acrylic acid) xerogel structure on swelling kinetics in distilled water

The basic structural properties of xerogels of crosslinked poly(acrylic acid) were defined and determined: xerogel density (rho(xg)), xerogel volume fraction in the equilibrium-swollen state (v(2)), the number average molar mass between network crosslinks ((M) over bar (c)), the crosslink density (rho(c)) and the distance between macromolecular chains (d). A crosslinking ratio (X) increase leads to a linear increase in the values for rho(xg) and rho(c), while the values (M) over bar (c) and d decrease. The isothermal swelling kinetic curves of four samples of structurally different poly(acrylic acid) xerogels in bidistilled water at different temperatures ranging from 25 to 45 degrees C were determined. It is shown that isothermal kinetic swelling curves could not be described with the model of first-order reaction kinetics in entire. It was found that these curves could be described by the Johanson-Mampel-Avrami (JMA) equation. For all of the investigated xerogel samples, the initial swelling rate (v(in)), effective reaction rate constant (k) and equilibrium swelling degree increased with swelling temperature increase. Based on the determined values of the vin and k, the activation energy (E-a) and pre-exponential factor (lnA) were determined. It was concluded that the activation energy linearly increased with increasing distance between macromolecular chains (d) and molar mass between the network crosslinks ((M) over bar (c)). The relationship between the activation energy changes with pre-exponential factor (compensation effect) caused by xerogel structural properties was established. Isothermal swelling kinetics could be completely described by the kinetics of phase transition of the xerogel transformation from glassy to rubbery state, i.e. with the JMA kinetic equation.