In Situ RheoNMR Correlation of Polymer Segmental Mobility with Mechanical Properties during Hydrogel Synthesis

Understanding polymer gelation over multiple length‐scales is crucial to develop advanced materials. An experimental setup is developed that combines rheological measurements with simultaneous time‐domain (1)H NMR relaxometry (TD‐NMR) techniques, which are used to study molecular motion (<10 nm) in soft matter. This so‐called low‐field RheoNMR setup is used to study the impact of varying degrees of crosslinking (DC) on the gelation kinetics of acrylic acid (AAc) and N,N′‐methylene bisacrylamide (MBA) free radical crosslinking copolymerization. A stretched exponential function describes the T (2) relaxation curves throughout the gelation process. The stretching exponent β decreases from 0.90 to 0.67 as a function of increasing DC, suggesting an increase in network heterogeneity with a broad T (2) distribution at higher DC. The inverse correlation of the elastic modulus G′ with T (2) relaxation times reveals a pronounced molecular rigidity for higher DC at early gelation times, indicating the formation of inelastic, rigid domains such as crosslinking clusters. The authors further correlate G′ with the polymer concentration during gelation using a T (1) filter for solvent suppression. A characteristic scaling exponent of 2.3 is found, which is in agreement with theoretical predictions of G′ based on the confining tube model in semi‐dilute entangled polymer solutions.