The fine structure in the solid state and phase transition behavior of newly synthesized comb copolymers having fluorocarbon and hydrocarbon side-chains were investigated by temperature controlled wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). From the WAXD profiles, two kinds of short spacing peaks based on the formation of the subcell for fluorinated and hydrogenated sidechains were confirmed at 5.0 and 4.1 Å , respectively. Furthermore, two kinds of endothermic peaks, which corresponded to melting peaks of both side-chain crystals, appeared in heating process of the DSC thermograms. From these experimental findings, the phase separation structure having the independently packed immiscible sidechain crystalline was formed in the whole polymer crystal. In addition, it was found that these comb polymers formed highly ordered (double) layer structure estimated using WAXD and small angle X-ray scattering (SAXS). These fluorinated comb copolymers form a monolayer on the water surface and their transferred film with phase-separated structure at nanometer size on solid. There were hydrogenated domains at 10-20 nm diameter scales in these phase separated surface structure of monolayers. From these experimental results, these copolymer monolayers are expected to be used as a new molecular device such as nanolithography based on the surface patterning of polymer nanomaterials. V V C 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: [416][417][418][419][420][421][422][423][424][425] 2006

Surface morphology of monolayers related to solid‐state structure for methacrylate comb copolymers having fluorocarbon and hydrocarbon side‐chains was investigated by X‐ray diffraction (XRD), differential scanning calorimetry, and atomic force microscopy (AFM). From the XRD profiles, two kinds of short spacing peaks were confirmed at 5.0 and 4.2 Å, which assigned the sub‐cells for both side‐chains. Furthermore, two kinds of endothermic peaks, which corresponded to melting peaks of the both side‐chain crystals, appeared in the thermograms. From the AFM observation, it was found that there were hydrogenated domains at a few hundred nanometer diameter in their monolayers, whereas corresponding acrylate copolymer monolayers form the phase‐separated structure at 10–30 nm order scales. POLYM. ENG. SCI., 47:354–364, 2007. © 2007 Society of Plastics Engineers.

The molecular orientation in monolayer and multilayer films of fluorinated comb copolymers with various monomer ratios can be characterized by in‐plane and out‐of plane X‐ray diffraction (XRD), near‐edge X‐ray absorption fine structures (NEXAFS) spectroscopy at the C K‐edges, and atomic force microscopic observation. And further, the fine structure in the solid state and phase transition behavior of newly synthesized comb copolymers having fluorocarbon and hydrocarbon side‐chains were investigated by temperature controlled wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC). From the WAXD profiles, two kinds of short spacing peaks based on the formation of the sub‐cell for fluorinated and hydrogenated side‐chains were confirmed at 5.0 and 4.1 Å, respectively. Furthermore, two kinds of endothermic peaks, which corresponded to melting peaks of both side‐chain crystals, appeared in the heating process of the DSC thermograms. From these experimental findings, the phase separation structure having the independently packed immiscible side‐chain crystalline formed in the whole polymer crystal. In addition, it was found that these comb polymers formed highly ordered (double) layer structures estimated using WAXD and small‐angle X‐ray scattering (SAXS). These fluorinated comb copolymers form the monolayer on the water surface and their transferred film with phase separated structure at nanometer size on the solid. There were hydrogenated domains at 10–20 nm diameter scales in these phase separated surface structures of the monolayers. From these experimental results, these copolymer monolayers are expected to be used as in new molecular devices such as nano‐lithography based on the surface patterning of polymer nano‐materials. Copyright © 2006 John Wiley & Sons, Ltd.

We investigated the molecular orientation of organized molecular films with regard to solid-state structures for newly synthesized comb copolymers with N-vinylcarbazole (NVCz) by in-plane and out-of plane X-ray diffraction (XRD), differential scanning calorimetry (DSC), and atomic force microscopy (AFM). In the bulk state, hydrogenated and fluorinated comb copolymers form sidechain crystals for a two-dimensional lattice spacing of 4.2 and 5.0 Å , respectively. The findings suggest that the carbazole rings in the main-chain are arranged in opposition to each other. From the results of the DSC measurement, sharp-shaped melting peaks appear on the relatively lower temperature side of the thermograms. This result supports the formation of side-chain crystals in the synthesized comb copolymers. These monolayers of the copolymers on the water surface were extremely condensed, except for the fluorocarbon:NVCz ¼ 1:1 copolymer. From the in-plane XRD measurement of multilayers on solids, the changes in the two-dimensional lattice structure of fluorinated comb copolymer films containing NVCz units, as opposed to their bulk state, were confirmed. It seems that these structural changes are caused by the stronger p-p interaction between the carbazole rings rather than the van der Waals interaction between fluorocarbons.

Summary: Surface morphology of monolayers related to solid-state structure for methacrylate comb copolymers having fluorocarbon and hydrocarbon side-chains was investigated by X-ray diffraction (XRD), differential scanning calorimetry (DSC), and atomic force microscopy (AFM). From the XRD profiles, two kinds of short spacing peaks were confirmed at 5.0 and 4.2 Å, which assigned the sub-cells for both side-chains. Furthermore, two kinds of endothermic peaks, which corresponded to melting peaks of the both side-chain crystals, appeared in the thermograms. From the AFM observation, it was found that there were hydrogenated domains at a few hundred nm diameter in their monolayers, whereas corresponding acrylate copolymer monolayers form the phase-separated structure at 10-30 nm order scales.