Placement and performance of pH-triggered polyacrylic acid in cement fractures

A primary concern in the geologic storage of anthropogenic carbon dioxide is the leakage of buoyant CO₂ plumes into shallower formations, aquifers, or the surface. Man-made wells drilled through these formations present a potential leakage pathway for this CO₂ as the cement binding the well to the earth develops fractures or debonded microannuli form over time. Typically, wells with poor cementing or suspected leaks are subject to a cement-squeeze, in which new cement is injected to eliminate the leakage pathway. However, small fractures or leakage pathways are often difficult for oilfield cement to repair, as the cement dispersion is potentially screened out from dispersing fluid and cannot enter the fracture. Therefore a low-viscosity sealant is desired that can enter these leakage pathways easily and provide a robust seal. A class of poly(acrylic acid) polymers known commercially as Carbopol® are pH-sensitive microgels and swell/thicken upon neutralization with alkali cement components. These polymer dispersions are tested for ease of placement into cement fractures and subsequent development of resistance to displacement. Laboratory experiments involved injecting various unswollen polymer microgel dispersion into constructed cement fractures while measuring injection pressure and the pH of the polymer effluent to quantify the chemical reactions taking place and the induced viscosity changes. Fractures were constructed in order to allow for visual inspection of the polymer microgel swelling during and after injection, qualitatively useful in determining the polymer’s efficiency at blocking cement fractures. It was determined that polymer microgels undergo syneresis in the presence of calcium cations that are dissolved from minerals present in cement. The syneresis causes the polymer to collapse onto the cement fracture face and expelled water is left to fill the rest of the fracture, providing little to no resistance to subsequent flow. However, the syneresed polymer does show some potential in blocking or partially blocking small aperture fractures and is not entirely detrimental to fracture blockage in small amounts. An acid pre-flush prior to polymer injection has been seen to favorably reduce the amount of calcium and therefore extent of syneresis, allowing swollen polymer microgels to remain intact and block fluid flow.