Acid dissociation of surface bound water on cellulose nanofibrils in aqueous micro nanofibrillated cellulose (MNFC) gel revealed by adsorption of calcium carbonate nanoparticles under the application of ultralow shear

Abstract

At ultralow shear rate (~0.01 s−1), acting below the yield stress of the aqueous gel, adsorption of calcium carbonate nanoparticles (<~100 nm) onto cellulose nanofibrils is induced without pigment–pigment preflocculation. Dispersant-free and polyacrylate treated dispersed carbonate particles are compared. Initially, it is seen that the polyacrylate dispersed material does not adsorb, whereas the dispersant-free carbonate adsorbs readily under the controlled ultralow shear conditions. However, repeated cycles of ultralow shear with intermittent periods in the rest state eventually induce the effect as initially seen with the dispersant-free calcium carbonate. The fibril suspension in the bulk is slightly acidic. The addition of buffer to a controlled pH in the case of the dispersant treated particles maintained a similar delay in the onset of adsorption, but adsorption occurred eventually after repeated cycles. During this cycling process, in parallel, the pH gradually drops under repeated cycles of ultralow shear, opposite to expectation, given the buffering capacity of calcium carbonate. The conductivity, in turn, progressively increases slightly at first and then significantly. The action of surface bound water on the nanofibril is considered key to the action of adsorption, and the condition of ultralow shear suggests that the residence time of the particle in contact with the nanofibril, acting under controlled strain against diffusion in the gel, is critical. It is proposed that under these specific conditions the calcium carbonate nanoparticles act as a probe of the nanofibril surface chemistry. The hydrogen bonded water, known to reside at the nanofibril surface, is thus considered the agent in the carbonate-surface interaction, effectively expressing an acid dissociation, and the calcium carbonate nanoparticles act as the probe to reveal it. An important phenomenon associated with this acid dissociation behaviour is that the adsorbed calcium carbonate particles subsequently act to flocculate the otherwise stable cellulose material, leading to release of water held in the aqueous gel matrix structure. This latter effect has major implications for the industrial ease of use of micro and nanofibrillar cellulose at increased solids content. This novel mechanism is also proposed for use to enhance the dewatering capability in general of complex cellulose-containing gel-like water-holding suspensions.