초록
Dehydroxylation and mullitization of primary and secondary kaolins were investigated in order to compare and understand the differences in thermal behaviours by DTA and TG up to $1,100^{\circ}C$. Chemical analyses and EPMA of the samples revealed nearly ideal unit-cell formulae of kaolins. The weight losses of dickite and halloysite are 14% and 12.5% on the average, respectively. The activation energies of dehydroxylation of kaolin minerals were calculated according to Kissinger's approach which uses various heating rates in DTA to estimate the activation energy of thermal reactions. The activation energies of dehydroxylation of halloysites from Daemoung and Buksam mines are about $163kJmor^{-1}$ (white), $168kJmor^{-1}$ (pink), and $176kJmor^{-1}$ respectively. The activation energies of dickites collected from Sungsan and Ogmae mines are about $166kJmor^{-1}$ and $387kJmor^{-1}$. The asymmetric shape of endothermic peak in DTA, the relative intensities of OH-stretching bands in FTIR spectroscopy and the existence of residual XRD peaks of the samples which were heated at $550^{\circ}C$ for 2 hours indicate that Sungsan dickite may be more disordered than Ogmae dickite. The new phase formed in thermally treated samples in the range of $900^{\circ}C$ to $1,100^{\circ}C$ was identified as mullite by XRD on the basis of disappearing of the characteristic peaks of kaolins and increasing of amorphous background upon heat treatment. On further heating, loss of more water from dehydroxylate resulted in the formation of mullite and the characteristic X-ray diffraction patterns of mullite began to appear at about $900{\sim}1,000^{\circ}C$ in kaolins.