Resonance Cassie-Wenzel wetting transition for horizontally vibrated drops deposited on a rough surface

The transition between the Cassie and Wenzel wetting regimes has been observed under horizontal vibrations of a water drop placed on the rough micrometrically scaled polymer pattern. The observed transition has a distinct resonance character. The resonance frequencies as established experimentally coincide with the calculated eigenfrequencies of capillary-gravity standing waves on the drop surface. The resonance Cassie-Wenzel transition is related to the displacement of the triple line caused by both the inertia force and the increase in the Laplace pressure. This strengthens the idea that the Cassie-Wenzel wetting transition is most likely a 1D affair stipulated by the triple-line behavior. The study of the vibrated drop deposited on the rough surface supplied valuable information concerning the Cassie-Wenzel wetting transition.     

Electron microscopy methods for studying polymer blends—comparison of scanning electron microscopy and transmission electron microscopy

The possibility of using a scanning electron microscope (SEM) for studying the morphology of mechanical polymer blends was investigated. Compounds of SBS/EPDM, and both filled and unfilled NBR/EPDM were tested. OsO₄-stained thin-sections were also examined in a transmission electron microscope (TEM) and the results were compared.It seemed to be quite possible to use atomic number contrast detection in combination with OsO₄ staining for visualizing the morphology of the blends in SEM. Domains as small as 0·1 μm were clearly seen. This was done by means of a Robinson backscattered electron detector. Sample preparation was easy, 2 mm thick rubber plates were cut on dry ice to obtain a smooth surface. After staining, the samples were coated with a thin conductive carbon layer.The inner structures of SBS and the carbon black particles were not resolved in SEM but were easily seen in TEM.     

X-ray absorption fine structure and scanning transmission electron microscopic analysis of polymer electrolyte fuel cells

We introduce nano-X-ray absorption fine structure and scanning transmission electron microscope-energy dispersive X-ray spectroscopy, which are identical location measurement methods that can provide complementary information on the various constituents of polymer electrolyte fuel cells. In these methods, the membrane electrode assembly samples were measured ex situ in conditions as close as possible to those in fuel cells under humid N₂. The sample preparation and measurement optimization are important. Herein, we mainly reported on these identical location measurement methods, that is, the nano-X-ray absorption fine structure and scanning transmission electron microscope-energy dispersive X-ray spectroscopy and then discuss the results that could be obtained.     

Recent progress in scanning electron microscopy for the characterization of fine structural details of nano materials

Research concerning nano-materials (metal-organic frameworks (MOFs), zeolites, mesoporous silicas, etc.) and the nano-scale, including potential barriers for the particulates to diffusion to/from is of increasing importance to the understanding of the catalytic utility of porous materials when combined with any potential super structures (such as hierarchically porous materials). However, it is difficult to characterize the structure of for example MOFs via X-ray powder diffraction because of the serious overlapping of reflections caused by their large unit cells, and it is also difficult to directly observe the opening of surface pores using ordinary methods. Electron-microscopic methods including high-resolution scanning electron microscopy (HRSEM) have therefore become imperative for the above challenges. Here, we present the theory and practical application of recent advances such as through-the-lens detection systems, which permit a reduced landing energy and the selection of high-resolution, topographically specific emitted electrons, even from electrically insulating nano-materials.     

Application of scanning electrochemical microscopy and scanning electron microscopy for the characterization of carbon-spray modified electrodes

Different gold surfaces modified by carbon-spray have been investigated by scanning electron microscopy (SEM) and scanning electrochemical microscopy (SECM). A transformation of the SECM image to a distance-location profile is proposed which assists the correlation of both images. The structures found in the transformed SECM images of carbon-spray layers on gold substrates can be explained by the topographic features visible in the SEM pictures. Tempering the carbon spray results in an increased density of electrochemically reactive carbon particles which could be confirmed by cyclic voltammetric investigations. Gold minigrids modified with carbon spray expose some areas of especially large currents which could not be predicted from their SEM images. This effect may result from particles located at the edge of a wire intersection having relatively large active surfaces per particle. They contribute significantly to the total current of the minigrid.     

Composite structure of liquid crystal/polymer nanotubes revealed by high-angle annular dark-field scanning transmission electron microscopy.

We have applied high-angle annular dark-field microscopy to the characterization of the structure of template-grown nanotubes composed of a polymer and a discotic liquid crystalline material. Selective staining of the liquid crystal phase with ruthenium tetroxide was used to develop adequate Z-contrast that allows us to distinguish between the two phases. At appropriate staining conditions, we could clearly visualize, in the annular dark-field mode, a 5-15-nm thin liquid crystalline layer precipitated on the inner surface of the polymer tubes. Cryo-electron diffraction has shown high alignment of the discotic columns within the layer parallel to the tube axis. However, although the polymer/liquid crystal phase separation is almost complete, the wetting behavior of the polymer in relation to the template appears to be sensitively influenced by kinetic factors.     

Characterization of mo deposited on a TiO2(110) surface by scanning tunneling microscopy and Auger electron spectroscopy

The properties of Mo ultrathin films deposited on a TiO2(110) surface were investigated by scanning tunneling microscopy (STM) and spectroscopy (STS), as well as by Auger electron spectroscopy (AES). The substrate exhibited mainly large (1 x 1) terraces decorated by additional [001] rows (missing or added 1D structures) of reduced TiO(x) phases. Only a few percent of the surface exhibited a cross-linked (1 x 2) arrangement. The deposition of Mo layers at room temperature with a rate of approximately 0.4 monolayer/ min resulted in nanoclusters of 1-2 nm with a low-profile shape (2D-like). Preferential decoration of the atomic steps was not found; at the same time, the 1D defect sites of missing or added rows on the (110) terraces were characteristically decorated by larger Mo nanocrystallites. This behavior indicates that the mobility of Mo atoms is higher on the more reduced regions of the substrate. The high dispersion of the Mo adlayer changed only slightly on annealing up to 700 K; in the range of 900-1050 K, however, a significant increase of the particle size accompanied by splitting of the TiO2(110) terraces was observed. This behavior may be explained by the partial oxidation of the supported Mo (accompanied by the reduction of the substrate) into tetragonal crystallites oriented and slightly elongated in the [001] or [110] direction of the TiO2(110) support. STS measurements indicated that the crystallites or the support/crystallite interface formed above 900 K possesses a wide band gap. The annealing above 1050 K resulted in the disappearance of Mo from the TiO2(110) surface, which may be explained by the formation and sublimation of MoO3 species at the perimeter of the nanoparticles. The change of AES signal intensities for O(KLL) and Mo(MNN) as a function of the annealing temperature also supports this mechanism.     

Applications of triple resonance NMR techniques to the study of polymer structure and reactivity

The utility of isotopic labeling combined with triple resonance nuclear magnetic resonance (NMR) techniques for polymer structure and reactivity investigations will be demonstrated. One dimensional (1D) and two dimensional (2D) ¹H/¹⁹F/¹³C triple resonance NMR experiments have been used to study the structure of fluoropolymers; and ¹H/²H/¹³C triple resonance techniques have been used to study the reactivity of poly[(styrene-alt-(methyl methacrylate)] and the structure of deuterated polybutadiene. These methods provide a unique ability to selectively detect resonances of structural features that are present in minute amounts in polymers, without interference from the much larger signals of the rest of the polymer.     

Assessing the accuracy of contact angle measurements for sessile drops on liquid-repellent surfaces

Gravity-induced sagging can amplify variations in goniometric measurements of the contact angles of sessile drops on super-liquid-repellent surfaces. The very large value of the effective contact angle leads to increased optical noise in the drop profile near the solid-liquid free surface and the progressive failure of simple geometric approximations. We demonstrate a systematic approach to determining the effective contact angle of drops on super-repellent surfaces. We use a perturbation solution of the Bashforth-Adams equation to estimate the contact angles of sessile drops of water, ethylene glycol, and diiodomethane on an omniphobic surface using direct measurements of the maximum drop width and height. The results and analysis can be represented in terms of a dimensionless Bond number that depends on the maximum drop width and the capillary length of the liquid to quantify the extent of gravity-induced sagging. Finally, we illustrate the inherent sensitivity of goniometric contact angle measurement techniques to drop dimensions as the apparent contact angle approaches 180°.     

A scanning electron microscopy study on hollow silica microspheres: defects and influences of the synthesis composition

Defects on hollow silica spheres synthesized in a tetraethylorthosilicate-octylamine-HCl-H₂O system were recorded by scanning microscope. Based on the results, influences of synthesis composition on the formation of these defects are discussed. It is evidenced that products prepared with different octylamine-to-tetraethylorthosilicate ratios may have surface depressions, cracks and non-hollow microspheres. However, by changing water and acid additions, these defects could be reduced or eliminated. Generally, samples synthesized with a large octylamine addition commonly exhibit surface depressions. A small octylamine or a large water addition benefits the formation of solid silica microspheres among the product. Acid, although is not indispensable for the formation of hollow spheres, helps to eliminate or reduce depressions on the hollow shells. It is explained that the added acid gives rise to a relative localized fast hydrolysis versus condensation, facilitating an easy mobility of hydrolyzed silica species, and consequently the shell surface is smoothened.     

X-ray diffraction and scanning electron microscopy of galvannealed coatings on steel

The formation of Fe–Zn intermetallic compounds, as relevant in the commercial product galvannealed steel sheet, was investigated by scanning electron microscopy and different methods of X-ray diffraction. A scanning electron microscope with high resolution was applied to investigate the layers of the galvannealed coating and its topography. Grazing incidence X-ray diffraction (GID) was preferred over conventional Bragg–Brentano geometry for analysing thin crystalline layers because of its lower incidence angle α and its lower depth of information. Furthermore, in situ experiments at an environmental scanning electron microscope (ESEM) with an internal heating plate and at an X-ray diffractometer equipped with a high-temperature chamber were carried out. Thus, it was possible to investigate the phase evolution during heat treatment by X-ray diffraction and to display the growth of the ζ crystals in the ESEM.     

A scanning tunneling microscopy study of self-assembled nickel(II) octaethylporphyrin deposited from solutions on HOPG

The adsorption of nickel(II) octaethylporphyrin (NiOEP) from benzene and chloroform solutions on highly ordered pyrolytic graphite (HOPG) was investigated with a scanning tunneling microscope (STM) operated in ambient conditions. STM images show that NiOEP self-assembles on the graphite surface and that the molecules lie flat and form 2D lattices with spacings of 1.58 +/- 0.03 nm by 1.46 +/- 0.06 nm with a lattice angle of 69 degrees +/- 4 degrees averaged over both solvents. We were unable to eliminate the possibility that one unit cell distance is twice the above-reported distance. The corresponding molecular packing density, 4.5 +/- 0.3 x 10(13) molecules/cm(2), was essentially the same for benzene and chloroform solution deposition. These results differ somewhat from the structure revealed by high-resolution STM images of NiOEP on Au (111). The lack of apparent height (image intensity) in the constant current STM image of the alkane region of alkane-substituted metal porphyrins is attributed to a combination of changes in alkane configuration relative to the ring and associated changes in electronic coupling with HOMO and LUMO.     

Elasticity of cardiac cells on the polymer substrates with different stiffness: an atomic force microscopy study

Influences of substrate stiffness on mechanical properties of cardiac myocytes and fibroblasts were investigated by cell elasticity measurement with atomic force microscopy. The cells were cultured on collagen-coated polyacrylamide substrates with gradient rigidity. While cardiac myocytes showed no evident change in cell elasticity on different substrates, cardiac fibroblasts displayed the non-monotonic dependence on substrate stiffness with a maximum elastic modulus. Moreover, the elasticity change of cardiac fibroblasts with substrates stiffness was found to be regulated by actin filaments. Study of the effect of substrate stiffness on cell elasticity for different cardiac cells provides new information for the better understanding of cardiac physiology and pathology.     

Photoemission study of the electronic structure of size-selected transition metal clusters deposited on Ag(110)

We report on a photoemission study (XPS, UPS) of the evolution of the electronic structure with cluster size of Ni_n, Pd_n, Pt_n(n=1–15) mass-selected clusters deposited in submonolayer quantities on a Ag(110) single crystal surface. The monodispersed clusters display individual discrete electronic structure features of the Ni3d, Pd4d and Pt5d emission. With increasing cluster size the increasing splitting between the bonding-like and antibonding-like d-states reflects the molecular interaction. The shift of the center of gravity of the d-state spectrum towards the Fermi energy and its concomittant broadening indicate the trend to transition-metal formation.     

Comparison of sessile drop and captive bubble methods on rough homogeneous surfaces: a numerical study

Quasi-static experiments using sessile drops and captive bubbles are the most employed methods for measuring advancing and receding contact angles on real surfaces. These observable contact angles are the most easily accessible and reproducible. However, some properties of practical surfaces induce certain phenomena that cause a built-in uncertainty in the estimation of advancing and receding contact angles. These phenomena are well known in surface thermodynamics as stick-slip phenomena. Following the work of Marmur (Marmur, A. Colloids Surf., A 1998, 136, 209-215), where the stick-slip effects were studied with regard to sessile drops and captive bubbles on heterogeneous surfaces, we developed a novel extension of this study by adding the effects of roughness to both methods for contact angle measurement. We found that the symmetry between the surface roughness problem and the chemical heterogeneity problem breaks down for drops and bubbles subjected to stick-slip effects.     

Backscattered electrons from gold surface films deposited on silicon substrates: a joint experimental and computational investigation to add new potentiality to electron microscopy

This paper addresses the problem of the thickness determination of thin gold overlayers deposited on silicon bulk substrates by looking at the electron backscattering coefficient involved in scanning electron microscopy (SEM). A Monte Carlo code, used to calculate the backscattering coefficient, together with a simple experimental setup, which uses a conventional SEM, allow to determine thin film thickness (in the range 25–200 nm) with an estimated accuracy of 20%. This adds obviously new potentiality to SEM. Copyright © 2012 John Wiley & Sons, Ltd.     

Molecular simulations of wetting of a rough surface by an oily fluid: effect of topology, chemistry, and droplet size on wetting transition rates

The goal of this work is to study via molecular simulations the wetting kinetics of a rough surface by an oily fluid. We use forward flux sampling to compute the wetting transition rate and elucidate the transition mechanism of a small droplet on a surface of nails. The nails provide the re-entrant geometry necessary to keep the droplet in the nonwetted, composite state. The effects of nail height, droplet size, and surface chemistry are investigated. Because the droplet must touch the bottom surface to transition, increasing the nail height is an effective way to increase the barrier to wetting for both phobic and slightly philic drops, although as the fluid becomes very philic, chemistry dominates and the effect of nail height disappears. Generally, smaller drops transition more easily. Overall, our results suggest that nonwettability could be practically enhanced by promoting the "kinetic" trapping of the system in the nonwetted state.     

Comments on the wetting behavior of non-porous substrates for ceramic coated-conductor applications

This work gives an overview of the possibilities to improve the wetting behavior of precursors for coated conductors on non-porous substrates. Within this work, all coatings were performed on a metallic Ni–W/La₂Zr₂O₇/CeO₂ substrate using water-based Y, Ba, Cu containing precursors. The results described in this paper can be used for different technologies of chemical solution deposition, as there are ink jet printing, dip coating, spin coating etc. Starting from the forces involved during wetting, a separation between solid and liquid modifications was made. This study revealed that if a good cleaning procedure of the substrate, whether or not combined with a targeted modification of the precursor is applied, water-based solutions can be used without restriction towards their wetting behaviour leading to a sustainable technology within the coating industry. Within this work, special attention is given to (1) fast determination of the substrate cleaning procedure quality by the creation of wetting envelopes and (2) the use of a screening design of experiment to study the effects of intrinsic solution factors, such as precursor formulation, influencing the coating behavior. All modification discussed are expandable to all kinds of precursors and substrates.     

Structure and topography of molecular assemblies on solid substrates by infrared spectroscopy and scanning tunneling microscopy

Recently we have combined infrared spectroscopy and atomic resolution scanning tunneling microscopy (STM) to probe the local structure and intermolecular arrangement of molecules within thin films. IR spectroscopy provides spatially averaged information about orientation of the molecules with respect to the surface and about intermolecular arrangement within the crystallographic unit cell. STM data yields a local picture of molecular packing within the film. The requirements of an atomically flat (over distances of hundreds of angstroms) conducting substrate for the STM are fulfilled by an epitaxially grown film of gold on a cleaved mica substrate which also provides a good infrared reflective surface, enabling IR and STM measurements on identical samples. Systems investigated include Langmuir-Blodgett films of cadmium arachidate and self-assembled films of octadecyltrichlorosilane.