Kaolinite surfaces were modified by grinding kaolinite/quartz mixtures with mole fractions of 0.25 kaolinite and 0.75 quartz for periods of time up to 4 h. X-ray diffraction shows the loss of intensity of the d(0 0 1) spacing with mechanical treatment resulting in the delamination of the kaolinite. Thermogravimetric analyses show the kaolinite surface is significantly modified and surface hydroxyls are replaced with water molecules. Changes in the molecular structure of the surface hydroxyls of the kaolinite/quartz mixtures were followed by infrared spectroscopy. Kaolinite hydroxyls were lost after 2 h of grinding as evidenced by the decrease in intensity of the OH stretching vibrations at 3695 and 3619 cm(-1) and the deformation modes at 937 and 915 cm(-1). Changes in the surface structure of the OSiO units were reflected in the SiO stretching and OSiO bending vibrations. The decrease in intensity of the 1056 and 1034 cm(-1) bands attributed to kaolinite SiO stretching vibrations were concomitantly matched by the increase in intensity of additional bands at 1113 and 520 cm(-1) ascribed to the new mechanically synthesized kaolinite surface. Mechanochemical treatment of the kaolinite results in a new surface structure.