Phase Separation in Poly(tert-butyl acrylate)/Polyhedral Oligomeric Silsesquioxane (POSS) Thin Film Blends

Abstract

Phase separation in thin film blends of poly(tert-butyl acrylate) (PtBA) and a polyhedral oligomeric silsesquioxane (POSS), trisilanolphenyl-POSS (TPP), is studied as functions of annealing temperature and time, using reflected light optical microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. The results demonstrate that the PtBA/TPP blend system confined to thin films ( approximately 90 nm) exhibits lower critical solution temperature (LCST) behavior with a critical temperature of approximately 70 degrees C and a critical composition of 60 wt % PtBA with insignificant dewetting at the phase boundary. Off-critical spinodal behavior is observed for 58 and 62 wt % PtBA blend films. Phase separation by nucleation and growth is observed for all compositions outside the window between 58 and 62 wt % PtBA. The temporal evolution of spinodal decomposition in 60 wt % PtBA blend films is explored at annealing temperatures of 75, 85, 95, and 105 degrees C. The morphological evolution in 60 wt % PtBA blend films is similar for all experimental temperatures (75, 85, 95, and 105 degrees C) with the expected shorter time scales for phase evolution at higher annealing temperatures. Fast Fourier transforms of optical micrographs reveal that these blend films immediately undergo phase separation by spinodal decomposition during temperature jump experiments. Power law scaling for the characteristic wavevector with time (q approximately t(n) with n approximately -1/4 to -1/3) for domain growth during the early stages of phase separation yields to domain pinning at the later stages for 60 wt % PtBA blend films annealed at 75, 85, and 95 degrees C. In contrast, domain growth is pinned over the entire experimental time scale for 60 wt % PtBA blend films annealed at 105 degrees C.