Stability of organically modified montmorillonites and their polystyrene nanocomposites after prolonged thermal treatment

Melt intercalation of montmorillonite (MMT) into polymeric matrices to improve the mechanical properties of polymers has evolved into a subject of tremendous fundamental and technological interest. The thermal treatment experienced during processing or end use can substantially affect the clay and diminish the target properties of polymer/clay nanocomposites (NCs) because of deintercalation or degradation of surface modifiers. In this work, changes in morphology, chemistry, and thermal stability of organically modified (OM) MMT after annealing in O-2-rich and N-2 environments are investigated. Degradation of the alkyl ammonium cation occurs at temperatures as low as 105 degrees C upon prolonged exposure in an O-2-rich environment. X-ray diffractometry (XRD) performed in situ establishes the response of two OM-MMTs to elevated temperatures at short times, whereas ex situ XRD provides insight into high-temperature exposure at long times. Active sites on the silicate surfaces are found to induce scission of, as well as chemical interaction with, the chains comprising a polystyrene (PS) matrix. Size-exclusion chromatography indicates that PS chain scission occurs primarily after relatively short annealing times, whereas branching and cross-linking are more prevalent after long exposure times in an O-2-rich environment.