Elastic wave propagation in smooth and wrinkled stratified polymer films.

Periodic materials with sub-micrometer characteristic length scale can provide means for control of propagation of hypersonic phonons. In addition to propagation stopbands for the acoustic phonons, distinct dispersive modes can reveal specific thermal and mechanical behavior under confinement. Here, we employ both experimental and theoretical methods to characterize the phonon dispersion relation (frequency versus wave vector). We employed Brillouin light scattering (BLS) spectroscopy to record the phonon dispersion in stratified multilayer polymer films. These films consist of 4-128 alternate polycarbonate (PC) and poly (methyl methacrylate) (PMMA) layers along and normal to the periodicity direction. The distinct direction-dependent phonon propagation was theoretically accounted for, by considering the polarization, frequency and intensity of the observed modes in the BLS spectra. Layer-guiding was also supported by the glass transition temperatures of the PC and PMMA layers. The number of phonon dispersion branches increased with the number of layers but only a few branches were observable by BLS. Introduction of an additional in-plane periodicity, through a permanent wrinkling of the smooth PC/PMMA films, had only subtle consequences in the phonon propagation. Using the frequencies of the periodicity induced modes and momentum conservation equation we were able to precisely back calculate the wrinkle periodicity. However, a wrinkling-induced acoustic stopband utilizing flexible layered materials is still a challenge.

One-dimensional hypersonic phononic crystals.

We report experimental observation of a normal incidence phononic band gap in one-dimensional periodic (SiO(2)/poly(methyl methacrylate)) multilayer film at gigahertz frequencies using Brillouin spectroscopy. The band gap to midgap ratio of 0.30 occurs for elastic wave propagation along the periodicity direction, whereas for inplane propagation the system displays an effective medium behavior. The phononic properties are well captured by numerical simulations. The porosity in the silica layers presents a structural scaffold for the introduction of secondary active media for potential coupling between phonons and other excitations, such as photons and electrons.

Does Brillouin light scattering probe the primary glass transition process at temperatures well above glass transition?

The primary alpha-relaxation time (tau(alpha)) for molecular and polymeric glass formers probed by dielectric spectroscopy and two light scattering techniques (depolarized light scattering and photon correlation spectroscopy) relates to the decay of the torsional autocorrelation function computed by molecular dynamics simulation. It is well known that Brillouin light scattering spectroscopy (BLS) operating in gigahertz frequencies probes a fast (10-100 ps) relaxation of the longitudinal modulus M*. The characteristic relaxation time, irrespective of the fitting procedure, is faster than the alpha-relaxation which obeys the non-Arrhenius Vogel-Fulcher-Tammann equation. Albeit, this has been noticed, it remains a puzzling finding in glass forming systems. The available knowledge is based only on temperature dependent BLS experiments performed, however, at a single wave vector (frequency). Using a new BLS spectrometer, we studied the phonon dispersion at gigahertz frequencies in molecular [o-terphenyl (OTP)] and polymeric [polyisoprene (PI) and polypropylene (PP)] glass formers. We found that the hypersonic dispersion does relate to the glass transition dynamics but the disparity between the BLS-relaxation times and tau(alpha) is system dependent. In PI and PP, the former is more than one order of magnitude faster than tau(alpha), whereas the two relaxation times become comparable in the case of OTP. The difference between the two relaxation times appears to relate to the "breadth" of the relaxation time distribution function. In OTP the alpha-relaxation process assumes a virtually single exponential decay at high temperatures well above the glass transition temperature, in clear contrast with the case of the amorphous bulk polymers.

Phonon dispersion and nanomechanical properties of periodic 1D multilayer polymer films.

We report on the first systematic study of phonon propagation in nanostructured composite polymer multilayer films as a function of periodicity and composition using Brillouin light scattering and numerical simulations. The high sensitivity of phonon dispersion to structure and composition allows the probing of the mechanical properties down to the single-layer level. We observe a strikingly different dependence of the longitudinal and shear moduli on confinement effects in the polymer nanolayers. In addition, temperature dependent measurements of sound velocities reveal the presence of distinct glass transition temperatures, indicative of phonon localization in films with large layer thicknesses in agreement with theoretical predictions.