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Melting behavior in thin films of linear low-density polyethylene (LLDPE) and high-density polyethylene (HDPE) was studied by local thermal analysis (µTA). Even in the films thinner than 100 nm, the melting temperature ( Tm) was successfully observed by µTA. For LLDPE, Tm decreased as the thickness became thinner than 150 nm. For HDPE, Tm increased with decreasing thickness. Polarized infrared spectroscopy revealed that an edge-on lamellar structure formed in both cases, meaning that the crystallite orientation may not be a reason why the thickness dependence of Tm was not the same for both resins. A possible explanation is that for LLDPE the segmental mobility in the amorphous region predominates with decreasing thickness, and for HDPE the chain orientation in the region predominates with decreasing thickness.

Crystal structure in thin films of melt-crystallized and annealed polyethylene (PE) was examined by grazing incidence X-ray diffraction measurements. Choosing appropriate incident angles of X-rays to the films, surface and bulk molecular aggregation states were successfully extracted. Consequently, it was found that chain packing structure in the surface region was different from that in the bulk one. Based on paracrystalline analysis for the (110) reflection and its higher-order ones of PE orthorhombic crystal, it was clarified that the ordering for the crystalline lattice was lower in the surface region. Also, apparent crystallinity in the surface was lower than the bulk one. These results indicate that disordered crystallites were preferentially formed in the surface region.

The molecular aggregation state of octadecylsiloxane monolayers on Si-wafer substrate surfaces prepared from octadecyltrimethoxysilane (OTMS) or octadecyltrichlorosilane (OTS) was investigated on the basis of grazing incidence X-ray diffraction (GIXD), Fourier transform infrared spectroscopy (FT-IR), contact angle measurement, field emission scanning electron microscopy (FE-SEM), and scanning force microscopy (SFM). The OTMS monolayer was prepared by using the chemical vapor adsorption (CVA) method, and the OTS monolayers, which were used as reference samples, were prepared either by chemisorption (OTS-S) or by the water-cast method (OTS-W). The GIXD, FT-IR, lateral force microscopic (LFM) measurements, and FE-SEM observation revealed that the alkyl chains in the OTMS monolayers prepared using the CVA method are in an amorphous state at room temperature. According to the LFM measurement, the transition temperature from the hexagonal crystalline phase to the amorphous phase was found to be ca. 333 K for the OTS-S monolayer prepared by the chemisorption method. However, the phase transition was not observed in the OTMS monolayer prepared by the CVA method. Also, the atomic force microscopic (AFM) observation and the contact angle measurement showed that the OTMS monolayer prepared by the CVA method has a uniform surface when compared to the OTS monolayers. These results indicated that organosilane compounds in the monolayer prepared by the CVA method were immobilized on the Si-wafer substrate surface in an amorphous state, which was quite different from the hexagonal crystalline state obtained by the chemisorption and water-cast methods.

Molecular aggregation structure of poly(fluoroalkyl acrylate) [PFA-Cy, where y is the fluoromethylene number of the fluoroalkyl (Rf) groups] thin films was characterized by grazing-incidence X-ray ...