Thermally Triggered Self-Reinforcing Double-Network Nanocomposite Hydrogels for Fracture Sealing Under Cyclic Steam Exposure.

Abstract

Hydrogels used for fracture sealing during heavy-oil thermal recovery are repeatedly exposed to high-temperature steam, dehydration, pressure disturbance, and cooling, conditions that often lead to progressive network deterioration and loss of sealing efficiency. To address this limitation, a thermally triggered self-reinforcing covalent-physical double-network nanocomposite hydrogel was developed by combining a sparse MBAA-crosslinked P(NaAMPS-co-NVP-co-AM) covalent scaffold with a reversible Laponite-mediated physical network. The material response was systematically evaluated through cyclic hydrothermal treatment at 180 °C, while fracture-sealing and resealing performance was examined separately under steam-exposure conditions. Artifact-controlled experiments were further introduced to distinguish genuine cycle-induced reinforcement from dehydration, continued post-curing, and conventional thermal aging. The results show that the NaAMPS/NVP/AM molar ratio of 40/20/40 with 1.00 wt% Laponite provided a suitable balance between precursor processability, hydrothermal stability, and mature network stiffness. After five thermal cycles at 180 °C, the storage modulus of the Lap-DN hydrogel increased from 74.4 to 89.1 kPa, while the compressive stress at 50% strain increased from 0.641 to 0.842 MPa, corresponding to reinforcement ratios of 1.198 and 1.314, respectively. Meanwhile, the mean equivalent pore diameter decreased from 6.2 to 4.8 μm, indicating progressive refinement of the load-bearing network. The hydrogel retained 76.3% of its initial water and 81.6% of its initial volume after five cycles in the reference brine and preserved a cycle-5 modulus retention of 101.3% even at 150,000 mg/L salinity. In fracture-sealing tests, Lap-DN sustained a breakthrough pressure of 3.47 MPa and reduced fracture conductivity by 92.4% in a 1.60 mm fracture. More importantly, the same sealing body maintained a breakthrough pressure of 4.55 MPa after five steam impact-recovery cycles in a 1.20 mm fracture, corresponding to 106.1% of the first-cycle value, while 95.0% of the pre-breakthrough pressure resistance was restored within 30 min of cooling. These results are consistent with a cycle-induced reorganization of the Laponite-mediated physical constraints within the permanent covalent scaffold, although the transient dissociation and reassociation of individual polymer-Laponite junctions were not directly observed. Within this evidence-based interpretation, cyclic thermal perturbation is associated with mechanical reinforcement and repeated fracture resealing rather than acting solely as a damaging factor. This work provides a materials-design strategy for hydrogel sealing systems operating under cyclic steam and high-salinity conditions.