Delayed Crosslinking and Plugging Performance of Polyacrylamide Gel Using CaCl₂-Tolerant Delayed-Release Crosslinker...

Lost circulation is a major technical bottleneck restricting safe and efficient while-drilling plugging operations. Polyacrylamide gel has become a widely used plugging material in drilling engineering. Unlike rigid, cement-like plugging materials, the gel system formed in this study does not develop a hardened, consolidated structure capable of anchoring or binding the drill bit during subsequent drilling operations, thereby eliminating the risk of bit-sticking. Nevertheless, the gel possesses sufficient elastic (viscoelastic) structural strength-reflected in its storage modulus (G')-to effectively resist deformation and displacement under differential pressure, thereby providing reliable fracture-sealing performance, which effectively prevents pipe-sticking risks. However, high-concentration PAM molecular chains easily stretch and entangle in aqueous solution, triggering an abnormal increase in initial viscosity and poor pumpability. Although Ca²⁺ can inhibit the premature water absorption and thickening of PAM to maintain system fluidity, an excessively high Ca²⁺ concentration will suppress the hydrolysis of Al³⁺ and hinder the formation of hydroxyaluminum-the key crosslinking component of the gel system. To solve the above contradiction, a CaCl₂-tolerant delayed-release crosslinker was synthesized. ZnO was selected as a carrier to adsorb and immobilize polynuclear hydroxyaluminum complexes hydrolyzed from an inorganic aluminum crosslinker at 70 °C, realizing the controlled delayed release of the crosslinker. The microstructures and chemical bonding were characterized by SEM elemental mapping, FT-IR and ²⁷Al MAS NMR. The results confirm that abundant aluminum species are uniformly loaded on the ZnO surface to form stable Zn-O-Al covalent bonds, and the loaded aluminum exists mainly in the form of hydroxyaluminum. With increasing temperature, the Zn-O-Al bonds gradually break and slowly release hydroxyaluminum species. A novel delayed crosslinking gel system was ultimately optimized, composed of 6% CaCl₂, 10.4% PAM and 3% ZnO loaded with polynuclear hydroxyaluminum. The system exhibits excellent delayed gelation behavior, with a fluidity loss time longer than 120 min and a gelation time over 200 min. It maintains favorable fluidity within 30-90 °C, and the formed gel shows a stable elastic modulus (G') and viscous modulus (G″). Moreover, the system achieves a plugging rate of more than 90% and a breakthrough pressure above 5 MPa, demonstrating superior comprehensive plugging performance for while-drilling plugging applications.