Morphology mapping of phase-separated polymer films using nanothermal analysis

Abstract

Polymers films are attractive, in part, because their physical properties can be tuned by blending polymer with complementary characteristics. However, blending is typically challenging because most polymers will undergo phase separation, resulting in unpredictable behavior. Here, we introduce band excitation nanothermal analysis (BE-NanoTA) as a nondestructive AFM-based technique for mapping the near surface, thermal properties of polymeric coatings. BE-NanoTA was used to investigate phase separation and domain growth in poly(styrene-ran-acrylonitrile):poly(methyl methacrylate) SAN:PMMA films. The size and shape of PMMA-rich domains are consistent with prior measurements on the same system using a destructive method, namely UV-ozone etching of PMMA followed by topography mapping using standard AFM. Moreover, new insights into the mechanism of phase separation were uncovered including the observation of SAN-and PMMA-rich channels near the surface at early times as well as small SAN-rich domains trapped within large PMMA domains during intermediate times. Because it is nondestructive, BE-NanoTA can be used to explore in situ phase evolution in soft matter systems (e.g., polymer nanocomposites) which do not lend themselves to the UV-ozone etching method. © 2010 American Chemical Society.