Impact of CaCl2 concentration and in situ rheometric setup configuration on fast alginate–Ca2+ reaction

Abstract

Recording kinetics during a reaction is a challenging effort that provides significant insight into gelation. We recently published our work based on a novel custom-made rheometric setup for in situ cross-linking reaction [Besiri et al., Carbohydr. Polym., 2020, 246, 116615]. It facilitates the instant injection of CaCl2 solution into alginate via micro-holes of the lower plate configuration to initiate the process. Considering that the time evolution of the viscoelastic parameters is related to the developed structure, we can obtain the reaction kinetics. This study aims to improve the setup by increasing the number of micro-holes from 2 to 4, investigating the mass ratio effects, and considering the proposed design as a batch reactor. As the volume and concentration of the reactants can be controlled during the initiation of the process, we investigate the molarity effect on the gelation. The long-term behavior of rheological oscillatory shear experiments indicates that the reaction is based on the mass of cations. The stoichiometry of reactants affects the diffusion of ions to alginate since, at high concentration and low volume of CaCl2, the mechanical properties are increased compared to lower concentration and higher volume of the cationic solution. Systematic time sweep experiments prove that at low angular frequencies, ω, the driving force of the reaction is the distribution of ions to the polymer. For higher values of ω, the force acting on the oscillating geometry of the rheometer is possibly the factor causing an enhanced mixing of the reactants, with a corresponding increase in moduli.