Crossover behavior in the hydrogen sensing mechanism for palladium ultrathin films.

Palladium has been extensively studied as a material for hydrogen sensors because of the simplicity of its reversible resistance change when exposed to hydrogen gas. Various palladium films and nanostructures have been used, and different responses have been observed with these diverse morphologies. In some cases, such as with nanowires, the resistance will decrease, whereas in others, such as with thick films, the resistance will increase. Each of these mechanisms has been explored for several palladium structures, but the crossover between them has not been systematically investigated. Here we report on a study aimed at deciphering the nanostructure-property relationships of ultrathin palladium films used as hydrogen gas sensors. The crossover in these films is observed at a thickness of approximately 5 nm. Ramifications for future sensor developments are discussed.

Universal dynamics of coarsening during polymer-polymer thin-film spinodal dewetting kinetics.

The dewetting dynamics of a supported bilayer polymer thin film on a solid substrate is investigated using grazing incidence x-ray photon correlation spectroscopy. We find that the top layer dewets via the spinodal mechanism. The kinetics of the dewetting is studied by monitoring the time evolution of the surface diffuse x-ray scattering intensity. We study the time evolution of fluctuations about the average surface structure by measuring the two-time x-ray intensity fluctuation correlation functions. Using these two-time correlation functions we quantify the crossover from early-time diffusive dynamics to hydrodynamics. The early diffusive regime satisfies dynamic universality. The two-time correlation functions also quantify the onset of hydrodynamic effects. The hydrodynamic regime is observed during the spinodal dewetting process as these interactions are not screened.

The role of metal nanoparticles and nanonetworks in alloy degradation.

Oxide scale, which is essential to protect structural alloys from high-temperature degradation such as oxidation, carburization and metal dusting, is usually considered to consist simply of oxide phases. Here, we report on a nanobeam X-ray and magnetic force microscopy investigation that reveals that the oxide scale actually consists of a mixture of oxide materials and metal nanoparticles. The metal nanoparticles self-assemble into nanonetworks, forming continuous channels for carbon transport through the oxide scales. To avoid the formation of these metallic particles in the oxide scale, alloys must develop a scale without spinel phase. We have designed a novel alloy that has been tested in a high-carbon-activity environment. Our results show that the incubation time for carbon transport through the oxide scale of the new alloy is more than an order of magnitude longer compared with commercial alloys with similar chromium content.

Hierarchical assembly and compliance of aligned nanoscale polymer cylinders in confinement.

We report a combined top-down/bottom-up hierarchical approach to fabricate massively parallel arrays of aligned nanoscale domains by means of the self-assembly of asymmetric polystyrene-block-poly(ethylene-alt-propylene) diblock copolymers. Silicon nitride grating substrates of various depths and periodicities are used to template the alignment of the high-aspect-ratio cylindrical polymer domains. Alignment is nucleated by polystyrene preferentially wetting the trough sidewalls and is thermally extended throughout the polymer film by defect annihilation. Topics discussed include a detailed analysis of the capacity of this system to accommodate lithographic defects and observations of alignment beyond the confined channel volumes. This graphoepitaxial methodology can be exploited in hybrid hard/soft condensed matter systems for a variety of applications.

Surface vibrations in alkanethiol self-assembled monolayers of varying chain length.

The effect of chain length on the low-energy vibrations of alkanethiol striped phase self-assembled monolayers on Au(111) was studied. We have examined the low-energy vibrational structure of well-ordered, low-density 1-decanethiol (C10), 1-octanethiol (C8), and 1-hexanethiol (C6) to further understand the interaction between adsorbate and substrate. Dispersionless Einstein mode phonons, polarized perpendicularly to the surface, were observed for the striped phases of C10, C8, and C6 at 8.0, 7.3, and 7.3 meV, respectively. An overtone at 12.3 meV was also observed for C6/Au(111). These results, in concert with molecular dynamics simulations, indicate that the forces between the adsorbate and substrate can be described using simple van der Waals forces between the hydrocarbon chains and the Au substrate with the sulfur chemisorbed in the threefold hollow site.