Analyses of the effects of montmorillonite (clay) on the chain conformation and crystallization of syndiotactic polystyrene (s-PS) thin films are investigated using FTIR spectroscopy, X-ray diffraction, and TEM. The clay is dispersed into the s-PS matrix using a solution blending with scale in 1-2 nm or in a few tenths to 100 nm, depending on whether a surfactant is added or not. Upon adding clay, the chain conformation of s-PS tends to convert to TTTT from rTTGG after drying because the highly dispersed clay overcomes the energy barrier of chain conformation transformation. This phenomenon leads to a change in a conventional mechanism of molecular packing for s-PS in the drying stage. During melt-crystallization, clay plays a vital role in facilitating the formation of the thermodynamically favored all-trans p form crystal, particularly on the s-PS thin film. When the s-PS is melt-crystallized at a cooling rate of 1 degreesC/min from 320 degreesC, the highest absolute crystallinity of beta form up to 0.56 occurs in the clay dispersibility of few tenths to 100 nm in the s-PS matrix; then dispersibility is of 1-2 nm (0.49), and the final one is of pure s-PS (0.42). Evidently, clay significantly affects the chain conformation and crystallization of s-PS.
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