Diffusive processes in polyacrylic acid hydrogels
The aim of this work was to characterise the diffusive properties of superabsorbent polymer systems prepared by free radical crosslinking polymerisation of acrylic acid. The polyelectrolyte nature of these hydrogels gives rise to high swelling capacities, and their ability to absorb and retain water is highly dependent on the precise network structure. Modifying the synthesis formulation results in considerable changes to the dynamic and structural properties of these gels, providing the motive for the work presented here. The influence of two factors, namely the extent of monomer neutralisation and the level of crosslinker in the pre-gel solution, were investigated. The dynamic properties of gels were examined using Quasi-Elastic Light Scattering (QELS), from which the cooperative diffusion coefficient and degree of heterogeneity could be determined. The former was found to increase linearly with neutralisation, due to the introduction of electrostatic interactions. The diffusion coefficient initially remained constant with the addition of crosslinker, due to the dominating influence of physical entanglements, but increased above a threshold crosslinking degree, corresponding to a reduction of the network mesh size. The extent of large-scale inhomogeneity increased for higher ionisations, as both the crosslinker solubility and the efficiency of monomer-crosslinker reaction decreased. However, there was a tendency for concentration fluctuations to be minimised for higher neutralisations, making the gel more microscopically homogeneous. Kinetics of swelling experiments were used to investigate gels of varying composition. The macroscopic diffusion coefficient was found to increase rapidly with increasing neutralisation until the monomer was approximately 35% neutralised, beyond which point counterion condensation caused insignificant variation. This trend was also reflected in the equilibrium swelling ratios, and mode of diffusion. For the majority of gels, the diffusion process was characterised as case II transport. Variation of crosslinking degree caused an overall increase in the diffusion coefficient, reflecting the trend observed in the QELS studies. Nuclear Reaction Analysis (NRA) was used to probe the penetration of heavy water into dry network slabs. The concentration-depth profiles revealed a discontinuity in the diffusion coefficient, corresponding to the transition between glassy and rubbery states, for which the diffusivities differed by several orders of magnitude. The kinetics of plasticisation was assumed to be the rate determining factor in the swelling process, on the timescale of the NRA experiments. The diffusion coefficient for the swollen rubbery region, representative of the macroscopic diffusion process, was found to increase linearly with neutralisation, and decrease with crosslinking degree. The latter observation was explained as due to a reduction in the free volume available for solvent diffusion with higher levels of crosslinker.