Hydrothermal Products Formed From Montmorillonite Clay Systems

Abstract

An investigation of the behavior of clay systems in drilling fluids was begun in 1958 to determine the cause of gelation in lime-treated muds with increased temperatures incurred during drilling operations. Mud systems were evaluated by physical property measurements, cation exchange data, X-ray diffraction analysis, and electron microscopy before and after hydrothermal treatment. Selected samples were rerun after two years' storage at laboratory temperatures.

High-temperature gelation of lime-caustic muds is caused by the synthesis of calcium silicate hydrates, hereafter referred to as CSH, in general and tobermorite (XCaO, SiO₂, H₂O) specifically. These materials are considered the principal cementing agents of Portland cement. Spheroidal poorly crystallized tobermorite was produced from interlayered illite-montmorillonite muds. Laths and needles of crystalline tobermorite (11.3–11.6 Å type) were synthesized from the pure montmorillonite systems. Zeolite minerals were synthesized concurrently and were the dominant alteration product when Ca(OH)₂ was not added to the system.

Synthesized aged (2 years) mud systems were studied after 8 weeks of dialysis with distilled water. Corundum was observed in samples where tobermorite formed, and was the dominant insoluble residue after HCl treatment. Much sharper diffraction maxima were obtained of the CSH compounds after dialysis or glycerine washing.

“Al-chlorite,” “Al-vermiculite,” and “Al-micas” were synthesized when treatments included aluminum ions. The products formed were of varying stabilities after washing with distilled water and HCl. Glycerol expanded the montmorillonite which had not reacted, but no expansion from the 10 Å or 14 Å d(001) spacing of the new product occurrred.