Calorimetric evidence for a mobile surface layer in ultrathin polymeric films: poly(2-vinyl pyridine).

Specific heat spectroscopy was used to study the dynamic glass transition of ultrathin poly(2-vinyl pyridine) films (thicknesses: 405-10 nm). The amplitude and the phase angle of the differential voltage were obtained as a measure of the complex heat capacity. In a traditional data analysis, the dynamic glass transition temperature Tg is estimated from the phase angle. These data showed no thickness dependency on Tg down to 22 nm (error of the measurement of ±3 K). A derivative-based method was established, evidencing a decrease in Tg with decreasing thickness up to 7 K, which can be explained by a surface layer. For ultrathin films, data showed broadening at the lower temperature side of the spectra, supporting the existence of a surface layer. Finally, temperature dependence of the heat capacity in the glassy and liquid states changes with film thickness, which can be considered as a confinement effect.

Multiscaling Approach for Non-Destructive Adhesion Studies of Metal/Polymer Composites.

The adhesion of polyamide 6 (PA6) and polyethylene (PE) toward an aluminum alloy (Al-A) and a dual phase steel (DPS) is studied by contact angle (CA) measurements and atomic force microscopy (AFM). With the combination of the two methods the adhesion properties on a macro- and (sub)microscopic scale can be determined in a nondestructive way. The work of adhesion per area (Wad) of the studied metal/polymer hybrids qualitatively scales the same on both length scales, that is, Al-A/PA6 > DPS/PA6 > Al-A/PE, DPS/PE. The polymer dominates the adhesion. The lower adhesion for PE toward the metal surfaces is explained by dominating van der Waals attraction forces, whereas adhesion for PA6 can also be attributed to attractive polar forces such as hydrogen bonding. For metal/PA6, Wad on a macro- and microscopic length scale is similar. For metal/PE, a discrepancy is measured with lower adhesion values on the microscopic scale than on the macroscopic scale.

Dynamics of linear poly(N-isopropylacrylamide) in water around the phase transition investigated by dielectric relaxation spectroscopy.

The molecular dynamics of linear poly(N-isopropylacrylamide) (pNIPAM) in aqueous media at temperatures below and above the lower critical solution temperature (LCST) are investigated using broadband dielectric relaxation spectroscopy in a frequency range from 10(-1) to 10(11) Hz. Below the LCST, two relaxation processes are observed in the megahertz and gigahertz region assigned to the reorientation of dipoles of the solvated polymer segments (p-process) and water molecules (w-process), respectively. Both relaxation processes are analyzed using the Havriliak-Negami (HN) function, taking special attention to the w-process. Above the LCST, the dielectric spectra of the pNIPAM solutions resemble that of pure water, showing only the high frequency relaxation process of the water molecules with a more or less Debye-type behavior. The non-Debye behavior of the w-process below the LCST is mainly induced by the interactions between water and pNIPAM chains via hydrogen bonding. The relaxation time and strength of the w-process is studied with dependence on the concentration, temperature, and the polymer chain length (molecular weight). The information obtained is useful for a deeper understanding of the dehydration behavior at the phase transition. The suggestion of dehydration of the pNIPAM chains at the LCST is confirmed by calculating a dehydration number.