Fernando Galembeck

Catalytic Nanomotors: Self‐Propelled Sphere Dimers

Experimental and theoretical studies of the self-propelled motional dynamics of a new genre of catalytic sphere dimer, which comprises a non-catalytic silica sphere connected to a catalytic platinum sphere, are reported for the first time. Using aqueous hydrogen peroxide as the fuel to effect catalytic propulsion of the sphere dimers, both quasi-linear and quasi-circular trajectories are observed in the solution phase and analyzed for different dimensions of the platinum component. In addition, well-defined rotational motion of these sphere dimers is observed at the solution-substrate interface. The nature of the interaction between the sphere dimer and the substrate in the aqueous hydrogen peroxide phase is discussed. In computer simulations of the sphere dimer in solution and the solution-substrate interface, sphere-dimer dynamics are simulated using molecular-dynamics methods and solvent dynamics are modeled by mesoscopic multiparticle collision methods taking hydrodynamic interactions into account. The rotational and translational dynamics of the sphere dimer are found to be in good accord with the predictions of computer simulations.

Catalysts for DMFC: relation between morphology and electrochemical performance

Abstract In this work Pt–Ru/C alloys were prepared by chemical reduction using various modifications of the formic acid method with the objective of improving the performance. The supported alloys were characterized by XRD, backscattering and TEM analyses, and the active areas were determined by CO adsorption. The materials showed similar particle sizes and different morphological characteristics. The performance of the supported alloys for methanol electrooxidation was evaluated by linear sweep voltammetry experiments and curves of cell potential vs. current density in a single direct methanol fuel cell. It is shown that the difference in the morphology of the catalysts in nano- and microscale is the main effect in the different performances.

Triboelectricity: Macroscopic Charge Patterns Formed by Self-Arraying Ions on Polymer Surfaces

Tribocharged polymers display macroscopically patterned positive and negative domains, verifying the fractal geometry of electrostatic mosaics previously detected by electric probe microscopy. Excess charge on contacting polyethylene (PE) and polytetrafluoroethylene (PTFE) follows the triboelectric series but with one caveat: net charge is the arithmetic sum of patterned positive and negative charges, as opposed to the usual assumption of uniform but opposite signal charging on each surface. Extraction with n-hexane preferentially removes positive charges from PTFE, while 1,1-difluoroethane and ethanol largely remove both positive and negative charges. Using suitable analytical techniques (electron energy-loss spectral imaging, infrared microspectrophotometry and carbonization/colorimetry) and theoretical calculations, the positive species were identified as hydrocarbocations and the negative species were identified as fluorocarbanions. A comprehensive model is presented for PTFE tribocharging with PE: mechanochemical chain homolytic rupture is followed by electron transfer from hydrocarbon free radicals to the more electronegative fluorocarbon radicals. Polymer ions self-assemble according to Flory-Huggins theory, thus forming the experimentally observed macroscopic patterns. These results show that tribocharging can only be understood by considering the complex chemical events triggered by mechanical action, coupled to well-established physicochemical concepts. Patterned polymers can be cut and mounted to make macroscopic electrets and multipoles.

Electrostatic charging of hydrophilic particles due to water adsorption.

Kelvin force microscopy measurements on films of noncrystalline silica and aluminum phosphate particles reveal complex electrostatic potential patterns that change irreversibly as the relative humidity changes within an electrically shielded and grounded environment. Potential adjacent to the particle surfaces is always negative and potential gradients in excess of +/-10 MV/m are found parallel to the film surface. These results verify the following hypothesis: the atmosphere is a source and sink of electrostatic charges in dielectrics, due to the partition of OH(-) and H(+) ions associated to water adsorption. Neither contact, tribochemical or electrochemical ion or electron injection are needed to change the charge state of the noncrystalline hydrophilic solids used in this work.

Easy polymer latex self-assembly and colloidal crystal formation: the case of poly[styrene-co-(2-hydroxyethyl methacrylate)]

Abstract Poly[styrene-co-(2-hydroxyethyl methacrylate)] core and shell latex particles easily undergo self-ordering, as evidenced by the iridescence of dispersions and dry solids. Microscopic (scanning electron microscopy) observation of the dry latex and fracture surfaces reveals the coexistence of different crystallographic arrangements. Many domains are observed, in which particle positions are correlated for tens of crystallographic planes. Isotherms of latex monolayers were also obtained, showing a strong interparticle repulsion. The ease of particle self-assembly in this latex is assigned to two factors: (i) the existence of strong repulsive interparticle interactions, which allows particle ordering at long distances, while particle diffusion throughout the dispersion is still possible; (ii) the hydrophilic surface layer, which allows for strong capillary adhesion during the whole drying process, according to Nagayamas model (Nature, 361 (1993) 26).

Photoacoustic characterization of a two-layer system

In this paper the use of the so‐called open photoacoustic cell for thermal characterization of two‐layer systems of variable thickness is described. It is shown that the thermal diffusivity as well as the thermal conductivity are completely determined, based upon the effective sample model widely used in heat‐transfer problems.

Friction coefficient dependence on electrostatic tribocharging

Friction between dielectric surfaces produces patterns of fixed, stable electric charges that in turn contribute electrostatic components to surface interactions between the contacting solids. The literature presents a wealth of information on the electronic contributions to friction in metals and semiconductors but the effect of triboelectricity on friction coefficients of dielectrics is as yet poorly defined and understood. In this work, friction coefficients were measured on tribocharged polytetrafluoroethylene (PTFE), using three different techniques. As a result, friction coefficients at the macro- and nanoscales increase many-fold when PTFE surfaces are tribocharged, but this effect is eliminated by silanization of glass spheres rolling on PTFE. In conclusion, tribocharging may supersede all other contributions to macro- and nanoscale friction coefficients in PTFE and probably in other insulating polymers.

Charge Partitioning at Gas−Solid Interfaces: Humidity Causes Electricity Buildup on Metals

Isolated metals within Faraday cages spontaneously acquire charge at relative humidity above 50%: aluminum and chrome-plated brass become negative, stainless steel is rendered positive, and copper remains almost neutral. Isolated metal charging within shielded and grounded containers confirms that the atmosphere is an electric charge reservoir where OH(-) and H(+) ions transfer to gas-solid interfaces, producing net current. The electricity buildup dependence on humidity, or hygroelectricity, acts simultaneously but in opposition to the well-known charge dissipation due to the increase in surface conductance of solids under high humidity. Acknowledging this dual role of humidity improves the reproducibility of electrostatic experiments.

Surface Mechanical Properties of Thin Polymer Films Investigated by AFM in Pulsed Force Mode

Atomic force microscopy in the pulsed force mode (PFM) is applied in this work to the study of thin dewetting patterns formed by drying an aqueous solution of poly(N-isopropylacrylamide) (PNIPAM) and sodium dodecyl sulfate (SDS) on mica. This technique allows the automated acquisition of typically 4 x 10(6) force-distance curves on the sample surface together with maps showing nanodomains differentiated by their stiffness and adhesion to the tip. Topography images of dry films revealed a morphology formed by droplets distributed on the substrate. Adhesion and stiffness images with good lateral resolution show droplets containing polymer and surfactant contrasting with the substrate and also nanosized heterogeneities inside these droplets. They also revealed very small dewetted structures which could not be observed in the topography map by noncontact AFM. Adhesion interactions between the AFM tip and the polymer or the dewetted mica substrate were measured in terms of adhesion force and detachment energy, and can be used as new information to understand dewetting patterns containing silica particles, PNIPAM, and SDS. Other surface mechanical parameters such as stiffness, maximum indentation, hardness, compliance, hysteresis, and Youngs modulus were obtained by sampling many points and used to characterize the PNIPAM/SDS films formed in the dewetting process.

Friction, tribochemistry and triboelectricity: recent progress and perspectives

Production of electricity by friction is well known but poorly understood, and is the source of electrostatic discharge causing serious accidents. Recent results are in agreement with one of the conflicting views on this problem, according to which triboelectricity in polymers is triggered by mechanochemical and wear or mass transfer phenomena. These results also challenge the widely accepted paradigm of one-way charge transfer that is the basis of the triboelectric series. Experimental results from powerful analytical techniques coupled to surface charge mapping support the following hypothesis: charge-bearing species are ionic polymer fragments formed through mechanical action. Beyond this, the atmosphere participates through tribocharge build-up and dissipation due to reactive plasma formation and charge exchange at the gas–solid interface, mediated by adsorption of non-neutral water, or ion partition during water adsorption, as in hygroelectricity phenomena.