Superhydrophobic polyolefin surfaces were prepared by simultaneous micro- and nanostructuring. Electropolished aluminum foil was microstructured with a micro working robot and then anodized in polyprotic acid. The surface microstructure can be tailored by adjusting the settings of the micro working robot and the nanostructure by adjusting the parameters of the anodization procedure. Surface structuring was done by injection molding where a microstructured anodized aluminum oxide mold insert was used to pattern the surfaces. Structuring had a marked effect on the contact angle between the injection-molded polyolefins and water. When the optimized microstructure was covered with nanostructure, the static contact angle between polypropylene and water obtained a value of about 165 degrees and the sliding angle decreased to about 2.5 degrees. The superhydrophobic state was achieved.

Superhydrophobic polymer surfaces are typically fabricated by combining hierarchical micro-nanostructures. The surfaces have a great technological potential because of their special water-repellent and self-cleaning properties. However, the poor mechanical robustness of such surfaces has severely limited their use in practical applications. This study presents a simple and swift mass production method for manufacturing hierarchically structured polymer surfaces at micrometer scale. Polypropylene surface structuring was done using injection molding, where the microstructured molds were made with a microworking robot. The effect of the micro-microstructuring on the polymer surface wettability and mechanical robustness was studied and compared to the corresponding properties of micro-nanostructured surfaces. The static contact angles of the micro-microstructured surfaces were greater than 150° and the contact angle hysteresis was low, showing that the effect of hierarchy on the surface wetting properties works equally well at micrometer scale. Hierarchically micro-microstructured polymer surfaces exhibited the same superhydrophobic wetting properties as did the hierarchically micro-nanostructured surfaces. Micro-microstructures had superior mechanical robustness in wear tests as compared to the micro-nanostructured surfaces. The new microstructuring technique offers a precisely controlled way to produce superhydrophobic wetting properties to injection moldable polymers with sufficiently high intrinsic hydrophobicity.

Density functional calculations were performed in order to investigate CO oxidation on two of the most stable bulk PdO surfaces. The most stable PdO(100) surface, with oxygen excess, is inert against CO adsorption, whereas strong adsorption on the stoichiometric PdO(101) surface leads to favorable oxidation via the Langmuir-Hinshelwood mechanism. The reaction with a surface oxygen atom has an activation energy of 0.66 eV, which is comparable to the lowest activation energies observed on metallic surfaces. However, the reaction rate may be limited by the coverage of molecular oxygen. Actually, the reaction with the site blocking molecular oxygen is slightly more favorable, enabling also possible formation of carbonate surface species at low temperatures. The extreme activity of strongly bonded surface oxygen atoms is more greatly emphasized on the PdO(100)-O surface. The direct reaction without adsorption, following the Eley-Rideal mechanism and taking advantage of the reaction tunnel provided by the adjacent palladium atom, has an activation energy of only 0.24 eV. The reaction mechanism and activation energy for the palladium activated CO oxidation on the most stable PdO(100)-O surface are in good agreement with experimental observations.

Dissociation of the first C–H bond of methane was investigated at the interface of partial PdO(101) monolayer and supporting Pd(100) surface with density functional calculations. Activation pathways of CH4 on the bulk PdO(100), PdO(101), Pd(100), and Pd(100) supported PdO(101) monolayer surfaces were also examined. The PdO(101)@Pd(100) boundary enables several new routes for methane dissociation compared to the bulk surfaces, the lowest activation energy barrier being 0.8 eV. The barrier on the most stable and dominant bulk PdO(100) surface is as high as 1.2 eV, whereas on the lower proportion bulk PdO(101) surface it is only 0.5 eV. However, the corresponding barrier increases to 1.2 eV in the case of supported PdO(101) monolayer. A low activation energy of 0.7 eV is observed also on the Pd(100) surface, however, the reaction enthalpy on the metal surface is not as favored as on oxide surfaces or at the phase boundary. Hydrogen diffusion from metal to oxide phase can improve the reaction enthalpy, but it causes increase in the total activation energy. Overall, the results indicate that the presence of phase boundary between PdO and Pd enhances the activity in methane combustion, rationalizing experimental findings.

Considerable attention is currently being devoted less to the question of whether it is possible to produce superhydrophobic polymer surfaces than to just how robust they can be made. The present study demonstrates a new route for improving the mechanical durability of water-repellent structured surfaces. The key idea is the protection of fragile fine-scale surface topographies against wear by larger scale sacrificial micropillars. A variety of surface patterns was manufactured on polypropylene using a microstructuring technique and injection molding. The surfaces subjected to mechanical pressure and abrasive wear were characterized by water contact and sliding angle measurements as well as by scanning electron microscopy and roughness analysis based on optical profilometry. The superhydrophobic polypropylene surfaces with protective structures were found to maintain their wetting properties in mechanical compression up to 20 MPa and in abrasive wear tests up to 120 kPa. For durable properties, the optimal surface density of the protective pillars was found to be about 15%. The present approach to the production of water-repellent polymer surfaces provides the advantages of mass production and mechanical robustness with practical applications of structurally functionalized surfaces.