Superabsorbent polymer (SAP) hydrogels have pronounced water‐absorbing and water‐storing capacities, which are essential for numerous potential applications. It remains a challenge to better understand the network topology because of their amorphous and anisotropic structures. Synthesis parameters such as monomer concentration, degree of neutralization and crosslinking, and surface crosslinking are varied to correlate structural changes in the network with low‐field proton double‐quantum (1H DQ) NMR results. 1H DQ‐NMR data are processed by a reliable, user‐independent analysis approach to determine the fractions of network defects, of mobile sol components, and of network chains as well as the residual dipolar coupling distribution in SAPs. In addition, results obtained by applying different distributions to describe the DQ buildup curves are quantified and compared. The correlation between topological and synthesis parameters as well as the impact of temperature, swelling, and solvent of SAP on DQ signals is investigated and discussed.

Dynamics of sodium ions and water in swollen superabsorbent polymer (SAP) hydrogels are studied by 23Na‐ and 1H‐NMR, respectively. The apparent diffusion coefficients of water in swollen SAPs, probed by 1H pulsed field gradient NMR, decreases with increasing diffusion time. The degree of hindrance depends on structural and synthesis parameters. It is quantified within a tortuosity model. Based on the results, the swelling degree has the highest impact on the ion mobility, apart from synthesis parameters leading to different levels of physical and chemical crosslinks. 23Na‐NMR relaxation and diffusion reveal the 23Na+ mobility in swollen SAPs. A higher degree of neutralization leads to faster relaxation and to a smaller apparent diffusion coefficient. Surface crosslinking restricts water mobility, but has a smaller impact on the dynamics of sodium ions. The experimental results indicate an influence of SAP structure on the dynamics of ions and water molecules.

The Flory-Rehner theoretical description of the free energy in a hydrogel swelling model can be broken into two swelling components: the mixing energy and the ionic energy. Conventionally for ionized gels, the ionic energy is characterized as the main contributor to swelling and, therefore, the mixing energy is assumed negligible. However, this assumption is made at the equilibrium state and ignores the dynamics of gel swelling. Here, the influence of the mixing energy on swelling ionized gels is quantified through numerical simulations on sodium polyacrylate using a Mixed Hybrid Finite Element Method. For univalent and divalent solutions, at initial porosities greater than 0.90, the contribution of the mixing energy is negligible. However, at initial porosities less than 0.90, the total swelling pressure is significantly influenced by the mixing energy. Therefore, both ionic and mixing energies are required for the modeling of sodium polyacrylate ionized gel swelling. The numerical model results are in good agreement with the analytical solution as well as experimental swelling tests.

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