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In this paper, the wettability properties of coatings with hierarchical surface structures and low surface energy were studied. Hierarchically structured coatings were produced by using hydrophobic fumed silica nanoparticles and polytetrafluoroethylene (PTFE) microparticles as additives in polyester (PES) and polyvinyldifluoride (PVDF). These particles created hierarchical micro–nano structures on the paint surfaces and lowered or supported the already low surface energy of the paint. Two standard application techniques for paint application were employed and the presented coatings are suitable for mass production and use in large surface areas. By regulating the particle concentrations, it was possible to modify wettability properties gradually. Highly hydrophobic surfaces were achieved with the highest contact angle of 165[Formula: see text]. Dynamic contact angle measurements were carried out for a set of selected samples and low hysteresis was obtained. Produced coatings possessed long lasting durability in the air and in underwater conditions.

While surface patterns are effective in improving tribological properties, nevertheless they alter the surface wettability, which will in turn affect the surface–lubricant interactions. When there is a shortage of lubricant on a patterned surface, the lubricant stored inside the cavities will be extracted to compensate the surface lubricant dissipation. Additionally, the lubricant retention effect provided by the cavities is competing with the release of the lubricant. With weak surface–lubricant interaction, the retention is limited. Therefore, the lubrication will have a sudden failure, giving a dramatic transition to abrasive wear. To improve the performance of polar lubricants on hydrophobic polymer surfaces, both topographical and selective surface modifications were incorporated on injection molded polypropylene surfaces. Distinctive lubrication improvement was observed when the surface structure density for the lubricant storage was high, and the release of the lubricant was controlled by the interaction with the selectively modified surfaces.

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.

We study the fabrication and optical properties of micropatterned luminescent optical epoxy samples. Five different photoluminescent materials were added to epoxy resin to form luminescent epoxies of different colors and micropatterned gratings were imprinted on the surface of the samples. The absorbance spectra of the unpatterned epoxy samples were measured with spectrometer and the luminescence intensities of all samples were measured using custom made bispectrometer. The methods used in this work offer an efficient and straightforward way to produce micro- or nanopatterned luminescent optical epoxies for various applications, such as LED coatings and solar concentrators.

Extensive studies have been performed with the aim of fabricating hierarchical surface structures inspired by nature. However, synthetic hierarchical structures have to sacrifice mechanical resistance to functionality by introducing finer scaled structures. Therefore, surfaces are less durable. Surface micro–micro hierarchy has been proven to be effective in replacing micro–nano hierarchy in the sense of superhydrophobicity. However, less attention has been paid to the combined micro–micro hierarchies with surface pillars and pits incorporated together. The fabrication of this type of hierarchy may be less straightforward, with the possibility of being a complicated multi-step process. In this study, we present a simple yet mass producible fabrication method for hierarchical structures with different combinations of surface pillars and pits. The fabrication was based on only one aluminum (Al) mold with sequential mountings. The fabricated structures exhibit high mechanical durability and structural stabilities with a normal load up to 100 kg. In addition, the theoretical estimation of the wetting state shows a promising way of stabilizing a water droplet on the surface pit structures with a more stable Cassie–Baxter state.

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.

The adhesion and contact guidance of human primary osteogenic sarcoma cells (Saos-2) were characterized on smooth, microstructured (MST) and micro- and nano-structured (MNST) polypropylene (PP) and on the same samples with a silicon-doped carbon nitride (C(3)N(4)-Si) coating. Injection molding was used to pattern the PP surfaces and the coating was obtained by using ultra-short pulsed laser deposition (USPLD). Surfaces were characterized using atomic force microscopy and surface energy components were calculated according to the Owens-Wendt model. The results showed C(3)N(4)-Si coated surfaces to be significantly more hydrophilic than uncoated ones. In addition, there were 86% more cells in the smooth C(3)N(4)-Si coated PP compared to smooth uncoated PP and 551%/476% more cells with MST/MNST C(3)N(4)-Si coated PP than could be obtained with MST/MNST uncoated PP. Thus the adhesion, spreading and contact guidance of osteoblast-like cells was effectively improved by combining surface texturing and deposition of osteocompatible C(3)N(4)-Si coating.

An effective solution mixing method starting from a synthesis solution of SiO2 nanoparticles was developed for dispersing nanoparticles into high-density polyethylene (HDPE). Spherical SiO2 nanoparticles with narrow size distribution (50–100 nm) were prepared by Stober method, and solvents of the synthesis solution (EtOH/NH4OH) were gradually replaced with toluene by evaporation under reduced pressure. The SiO2 nanodispersion, in toluene and residual ethanol, was mixed and refluxed with dissolved maleic anhydride grafted polyethylene (PEgMA) at a relatively high SiO2 content (17.8 wt %). The PEgMA-SiO2 masterbatch was filtered, dried under vacuum, and mixed with HDPE by melt compounding. SiO2 contents in the final HDPE nanocomposites were 3 and 5 wt %. SEM images of the masterbatch and final composites showed the SiO2 nanoparticles to be well dispersed in HDPE. No agglomerates were observed. FTIR results suggest that the interactions between the maleic anhydride group of PEgMA and hydroxyl groups of SiO2 surface involve ester and/or hydrogen bonding. Addition of SiO2 particles and PEgMA to HDPE slightly increased Young's modulus, tensile strength, breaking strength, and elongation at break, indicating enhanced toughness of the nanocomposites. The measured Young's moduli of HDPE-PEgMA-SiO2 composites agreed well with Young's moduli predicted by Mori-Tanaka composite theory. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

The wetting properties of polypropylene (PP) surfaces were modified by adjusting the dimensions of the surface nanostructure. The nanostructures were generated by injection molding with nanoporous anodized aluminum oxide (AAO) as the mold insert. Atomic layer deposition (ALD) of molybdenum nitride film was used to control the pore diameters of the AAO inserts. The original 50-nm pore diameter of AAO was adjusted by depositing films of thickness 5, 10, and 15 nm on AAO. Bis(tert-butylimido)-bis(dimethylamido)molybdenum and ammonia were used as precursors in deposition. The resulting pore diameters in the nitride-coated AAO inserts were 40, 30, and 20 nm, respectively. Injection molding of PP was conducted with the coated inserts, as well as with the non-coated insert. Besides the pore diameter, the injection mold temperature was varied with temperatures of 50, 70, and 90 degrees C tested. Water contact angles of PP casts were measured and compared with theoretical contact angles calculated from Wenzel and Cassie-Baxter theories. The highest contact angle, 140 degrees , was observed for PP molded with the AAO mold insert with 30-nm pore diameter. The Cassie-Baxter theory showed better fit than the Wenzel theory to the experimental values. With the optimal AAO mask, the nanofeatures in the molded PP pieces were 100 nm high. In explanation of this finding, it is suggested that some sticking and stretching of the nanofeatures occurs during the molding. Increase in the mold temperature increased the contact angle.

The surface properties of materials can be modified by tailoring the topography and chemical composition. Functional surfaces with desirable properties have been produced by precisely controlled surface structures and chemical composition at the micro-nanometer scale. Until now, the challenge has been the ability to manipulate surface morphology and chemistry at the micro-millimeter scale. This work presents a new surface modification method capable of permitting subsequent structuring and material deposition. A micro tip patterning technique is based on sharp metal tips that are used for modifying the topography and chemistry of various material surfaces at the micro-millimeter scale. The method is appropriate for characterizing different topographies by probing conductive material surfaces with a needle tip, which permits a precisely controlled surface structuring with continuous 3D profiles. The desired locations of the scanned surface can be chemically modified by delivering materials via the needle tip. The method is appropriate for the multi-object placement of numerous substances such as functional reagents and biological components in a complex microenvironment. The accurate structuring of complex 3D surface topographies and subsequent chemical deposition provides a precisely controlled functionalization of material surface properties suitable for different applications.

Mesoporous high surface area MCM-41 and SBA-15 type silica materials with fibrous morphology were synthesized and used as support materials for the ALCVD (atomic layer chemical vapor deposition) preparation of Co/MCM-41 and Co/SBA-15 catalysts. Co/MCM-41 and Co/SBA-15 catalysts were prepared by deposition of Co 2 (CO) 8 from the gas phase onto the surfaces of preheated support materials in a fluidized bed reactor. For both silica materials, two different kinds of preparation methods, direct deposition and a pulse deposition method, were used. Pure silica supports as well as supported cobalt catalysts were characterized by various spectroscopic (IR) and analytical (X-ray diffraction, Brunauer-Emmett-Teller, elemental analysis) methods. MCM-41 and SBA-15 fibers showed considerable ability to adsorb Co 2 (CO) 8 from the gas phase. For MCM-41 and SBA-15 silicas, cobalt loadings of 13.7 and 12.1 wt % were obtained using the direct deposition method. The cobalt loadings increased to 23.0 and 20.7 wt % for MCM-41 and SBA-15 silicas, respectively, when the pulse deposition method was used. The reduction behavior of silicasupported cobalt catalysts was found to depend on the catalyst preparation method and on the mesoporous structure of the support material. Almost identical reduction properties of SBA-15-supported catalysts prepared by different deposition methods are explained by the structural properties of the mesoporous support and, in particular, by the chemical structure of the inner surfaces and walls of the mesopores. Pulse O 2 /H 2 chemisorption experiments showed catalytically promising redox properties and surface stability of the prepared MCM-41- and SBA-15-supported cobalt catalysts.

Nature's functional surfaces are typically hierarchical multiscale structures. There are several techniques for producing such artificial structures on polymers but their mass production is not straightforward. We present here a simple and versatile method for manufacturing hierarchical multiscale polymer surface patterns. The microroughening technique permits the single-step production of multilevel three-dimensional surface architectures in a mechanically durable nickel mold. The molding technique is suitable for area-controlled fabrication of structures with various geometrical shapes on smooth and curved surfaces. The mold structures were transferred to polypropylene surfaces by means of injection molding. The fabricated surface structures were characterized by using a filtered power spectral density method which facilitated a quantitative study of the roughness distributions at different length scales of structure periodicities. Analysis showed that the microroughening technique is an appropriate tool for controlled production of surface roughness at a micro-nanometer scale. Roughness distribution values can be used for predicting surface structure-related properties such as wetting, and the distributions can also be simulated without an experimental preparation process. The work presents a suitable approach for mass production of hierarchical polymer surfaces at different length scales and provides a new route for designing surface structures with tunable wetting properties.

For reliable function, bioelectrodes require a stable, low-impedance contact with the target tissue. In biosignal monitoring applications, in which low ion current densities are recorded, it is important to minimize electrode contact impedances. Recently, several flexible electrode concepts have been introduced for single-patient use. These electrodes conform well on the patient skin enabling an artifact-free, low-noise recording. In this study, polydimethylsiloxane (PDMS) elastomer was used as an electrode substrate material. One half of the substrates were surface-patterned with micropillars produced by using micro-working robot-made mold inserts and a replica molding technique. The substrates were subsequently coated with thin films of titanium (Ti), copper (Cu), silver (Ag) or silver?silver chloride (Ag/AgCl). Electrical impedance spectroscopy studies revealed that the micropillar structure caused statistically significant reductions in impedance modulus and phase for each coating candidate. The relative effect was strongest for pure Ag, for which the values of the real part (Z?) and the imaginary part (Z?) decreased to less than one tenth of the original (smooth) values. However, Ag/AgCl, as expected, proved to be a superior electrode material. Coating with chloride drastically reduced the interfacial impedance compared to pure Ag. Further significant reduction was achieved by the micropillars, since the phase angle declined from 10?13? (for smooth samples, f < 50?Hz) to a value as low as 5?. Equivalent circuit modeling was used to obtain a better understanding of phenomena occurring at various electrode?electrolyte interfaces. The knowledge obtained in this study will be exploited in the further development of flexible electrodes and miniaturized biointerfaces with improved electrochemical characteristics.

The effect of bulk BaO promoter on CO oxidation activity of palladium oxide phase was studied by density functional calculations. A series of BaO(100) supported Pd(x)O(y) thin layer models were constructed, and energy profiles for CO oxidation on the films were calculated and compared with corresponding profiles for the most stable PdO bulk surfaces PdO(100) and PdO(101). The most stable of the thin films typically exhibit the same PdO(100) and PdO(101) surface planes; the PdO(100) dominates already with double layer thickness. The supporting promoter improves the CO oxidation activity of the Pd(x)O(y) phase via a direct electronic effect and introduced structural strain and corrugation. Changes in CO adsorption strength are reflected in oxidation energy barriers, and the promoting effect of even 0.3 eV can be seen locally. Easier oxygen vacancy formation may partially facilitate the reaction.

Two transparent semi-crystalline poly(4-methyl-1-pentene) copolymers (P4MP1) of different molar mass distributions were used for injection molding of high aspect ratio (height/width) diffractive gratings. High quality sub-micron and micron features with aspect ratios of 1.6:1 were obtained with low mold temperatures. According to SEM and AFM measurements, replication of the features depended on substrate thickness and polymer. The copolymer with lower Mn and Mw penetrated deeper into the feature cavities in thin substrates, but showed poorer thermal stability and replication fidelity.