Mechanism of Polyacrylamide Hydrogel Instability on High-Temperature Conditions

A gel system composed of acrylamide (AM), N,N'-methylenebisAM (BIS), and ammonium persulfate ((NH₄)₂S₂O₈) was developed and applied extensively in reservoirs to reduce water cut and increase oil production in mature fields. However, this gel system suffers from thermal stability loss and syneresis at high temperatures that reduces its ability to control water flow. It has been widely accepted that the loss of gel thermal stability can be explained via three aspects: the rupture of polymer chains, the breakage of cross-linker chains, and hydrolysis of polymer. The mechanism of hydrogel syneresis through polymer hydrolysis has been investigated extensively in other publications. However, research on the other two mechanisms is quite limited. In this article, we conduct a series of experiments to demonstrate how the rupture of polymer and cross-linker chains leads to the hydrogel instability at high temperatures. Viscosity and energy-dispersive system measurements suggested that polyAM chains were disrupted by the oxidation reactions involving free radicals. The method to measure the cross-linking degree was established and in combination with X-ray photoelectron spectroscopy measurements, the results showed that cross-linker chains were broken as a result of weaker C-N bond resulting from positively charged mesomethylene carbon and hydrolysis of amide groups on the cross-linker. Because of the application of deionized water in the experiments, nuclear magnetic resonance and FTIR measurements showed that the hydrolysis degree of polymer was weak. Hence, our results verified that breakage of polymer and cross-linker chains led to the rupture of the gel network at high temperature. Besides, cross-linker chains may play a more important role in the thermal stability of the gel, which explains some work into high-temperature-resistant gels.