The flotation behavior of kaolinite was investigated using a series of tertiary amines (DRN, DEN, DPN and DBN). Maximum recoveries of kaolinite were 93%, 88% and 84% for DEN, DPN and DRN, respectively. The recovery for DBN was very low. On the basis of the Zeta potential and FT-IR spectra, the ionization of surface hydroxyl and the isomorphic exchange of surface ions accounts for the charging mechanisms of the kaolinite surface. The adsorption mechanism of tertiary amines onto the kaolinite surface was mainly electrostatic. We determined that the IEP of kaolinite increased from 3.4 to higher values after the interaction of kaolinite with the four tertiary amines. FT-IR spectra of kaolinite changed to include sharp peaks of tertiary amines. Inductive electronic effects and space-steric effects of -CH(3), -C(2)H(5), -C(3)H(7) and -C(7)H(7) bound to the N atom result in different collecting powers for the four tertiary amines. (C) 2009 Published by Elsevier Ltd.