Effects of the cluster surface on the electronic shell structure: faceting,roughness and softness

Several simple models have been used to study the effects of the surface on the electronic shell structure in metal clusters. The main results are as follows: The icosahedral clusters have the same electronic shell structure as the sphere up to about 1000 atoms. The surface roughness causes the distribution of the level spacings to be a Wigner distribution. By varying the softness of the potential we can obtain potentials where the simplest classical orbits are the five-point star or even the three-point star.This paper was originally submitted in connection with the 2nd. Int. Conference on Atomic and Nuclear Clusters held in Santorini from 28. June–2. July 1993 and is published here as a regular article after an independent refereeing procedure according to the standards of Z. Phys. D     

Two-dimensional model of a rough surface and spatial distribution of the desorbed species

We consider the angular distribution (AD) of species desorbed from a rough surface described by various distribution functions (DF) of the surface topography. It is shown that the width of the AD of the desorbed flow depends mainly on the roughness coefficient and is almost independent of the DF, except for the indirect dependence through . It is established that the secondary reflection of desorbed species from an uneven surface (with 1.2) has no appreciable effect on the form of the AD. Taking two models as examples, it is shown that anisotropy in the surface topology leads to anisotropy in the AD of the desorbed species.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2699–2704, December, 1990.     

Infrared reflection studies of ceramics: characterization of SiC layers on graphite substrates

Summary Technical CVD-grown silicon carbide (-SiC) layers on graphite substrates have been studied by infrared spectroscopy. Specular reflectance spectra were measured at oblique incidence, and for the same experimental conditions such spectra were simulated starting from oscillator parameters which basically determine the optical behaviour of the material. Both the roughness of the surface and the roughness of the interface within the coated material, have considerable influence on the spectra. Modelling these zones as gradient layers on the basis of effective-medium approximations, convincing agreement between experiment and simulation can be obtained. In this way the effective dielectric function of the layer, as well as its thickness, are derived. Certain features within the reststrahlen band can be assigned to the excitation of surface phonons which strongly depend on the morphology of the layer.     

Positron spectroscopy of rehydrated pyrogeneous silica surface

Positron annihilation method has been used for investigating amorphous nonporous pyrogeneous silica of high purity. The influence of water adsorption on the structure of the silanol surface is shown. The effect of swelling, that is an increase of interglobular free volume at intermediate degrees of silica hydration has been observed.     

Automated Scanning Probe Microscopy as a New Tool for Combinatorial Polymer Research: Conductive Carbon Black/Poly(dimethylsiloxane) Composites

A systematic investigation into the surface properties of siloxane rubber/carbon black (CB) nanocomposites has been performed, using an automated scanning probe microscope. In this way the influence of CB concentration and curing rate of the siloxane rubber matrix on roughness and conductivity of the composites was studied. Decreasing the curing rate while keeping the CB concentration resulted in a decrease in both roughness and surface conductivity, which can be explained by an additional siloxane‐rubber layer formed during curing.

     

New simple method of measuring the surface glass transition temperature of polymers

A lap‐shear joint mechanical testing method has been probed to measure the surface glass transition temperature (T) of the thick bulk films of high‐molecular‐weight polymers. As T, the temperature transition “occurrence of autoadhesion–nonoccurrence of autoadhesion” has been proposed. The influence of chain flexibility, of molecular architecture, of polymer morphology, and of chain ends concentration on the T has been investigated. The correlation between the reduction in T with respect to the glass transition temperature of the bulk (T) and the intensity of the intermolecular interaction in the polymer bulk in amorphous polymers has been found. The effect of surface roughness on T has been discussed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2012–2021, 2010     

Investigation of electronic structure of impurity and defect centers on the surface of silica by the MNDO method

The electronic structure of cluster models of fragments of a. silica surface with defect centers [stressed disiloxane bridges, radical (Si, SiO) and ionic (Si⁺, SiO^–) groups] and impurity centers (boron and aluminum atoms) has been investigated by the MO-LCAO-SCF method in the MNDO approximation. It has been shown on the basis of an analysis of the energetics of the defect structures (with complete optimization of the geometry of the clusters) that the dehydroxylation of silica with the formation of radical and ionic centers is energetically significantly more favorable than is the formation of disiloxane bridges. The influence of impurity boron and aluminum atoms on the properties of the surface fragments of SiO₂ has been considered. It has been shown that the migration of impurity boron atoms, which isomorphously replace silicon atoms in the lattice, from the bulk to the surface of silica is energetically unfavorable.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 4, pp. 407–418, July–August, 1988.     

Oxygen evolution on electrodes of different roughness: an electrochemical noise study

Rough and porous Ni layers have been obtained by cathodic deposition from a NiCl₂, NH₄Cl solution, at high current density. Characterisation by SEM has shown that they consisted of micro-dendrites separated by pores with a typical diameter of 1 m. In addition, circular hollows (10–100 m in diameter) were found on the deposit surface; their density varied with the deposition current density and deposition charge. The surface roughness of the Ni deposits, measured by EIS, was found to increase roughly linearly with the deposition charge, and to be little dependent on current density, provided a threshold value was exceeded. The oxygen evolution reaction has been studied on these electrodes by simultaneous real-time measurements of potential and electrolyte resistance fluctuations. The analysis of the electrochemical noise indicated that the dimensions of oxygen bubbles detaching from the electrodes slightly increased with the deposit surface roughness. It is not clear, however, whether or not this increase was associated with the effect of the small (1 m) or the large (10–100 m) features on the electrode-bubble interactions.     

Thermogravimetric determination of specific surface area for soil colloids

A simple and easy method based on differential drying of samples at different temperatures has been proposed for quantitative determination of the specific surface areas of colloidal disperse systems. The following fundamental dependence of moisture thermodynamic potential [ψ] on absolute drying temperature T is used in the method: ψ = Q–aT, where Q is the specific heat of evaporation and a is a parameter related to the initial temperature and relative air humidity in an external thermodynamic reservoir (laboratory apartment). Gravimetric data on moisture mass fraction W and the value of ψ have been used to plot Polanyi potential curves W(ψ) for the studied samples. The curves have been employed to calculate the isotherms of moisture sorption. The capacity of a monolayer and the effective specific surface area have been determined from these isotherms in terms of the BET theory. The surface area estimated from the published results of classical experiments is about 1000 m²/g. The problem of the “absolute zero of humidity,” which is of great importance for determining the properties of colloidal disperse bodies normalized with respect to the solid phase mass, has been discussed.     

Thin films of nematic liquid crystal on liquid substrate. Bulk and surface structures,surface and line tensions

Summary The structure of a liquid crystal (L.C) thin film on water has been studied optically and the molecular orientation at its interfaces has been deduced. The surface tension shift corresponding to the orientations of the molecules either normal or parallel to the free surface has been deduced. From the study of the formation and of the stability of holes in the thin film we deduce the order of magnitude of the line tensionx. This tension originates in the elastic deformation of LC in the neighbourhood of the hole.     

Modification of surface properties of high and low density polyethylene by Ar plasma discharge

Structural changes induced by Ar plasma discharge in low and high density polyethylene (LDPE and HDPE) were studied by different techniques. AFM and SEM methods were used to determine surface morphology, the changes in chemical structure were followed using FTIR and UV-vis spectroscopy. The content and the depth profile of incorporated oxygen was determined by RBS method. The degree of polymer ablation was determined gravimetrically. Standard goniometry was used to determine contact angle and to follow aging of plasma modified polymer. As a result of plasma treatment a lamellar structure or spherulites appear on the surface of HDPE and LDPE, respectively. Pronounced increase of the surface roughness is observed on HDPE contrary to LDPE. Plasma treatment for 400 s leads to the ablation of the surface layer of about 0.6 and 1 μm thick for LDPE and HDPE, respectively. Plasma treatment results in oxidation of the polymer surface layer which is more pronounced in HDPE. Concentration maximum of incorporated oxygen lies 25 nm beneath the sample surface in both polymer types. After exposure to plasma discharge carbonyl, carboxyl and amide groups were detected in the polymer surface layer together with CC bonds either in aromatic or in aliphatic structures. Immediately after the plasma treatment strong decline of the contact angle is observed, the decline being larger in HDPE. Later, in aged specimens the contact angle increases rapidly. The increase, which may be due to rearrangement of degraded structures, is stronger in the specimens exposed to plasma for longer times.     

Chemical structure and surface activity

Surface tension measurements on aqueous solutions of 2-alkyl-2-methyl-1,3-dioxolanes, 2-alkyl-4-methyl-1,3-dioxolanes, and 2-alkyl-1,3-dioxanes at a temperature of 293.2 K are presented. The surface tension isotherms obtained were used to calculate some adsorption parameters, i. e. the efficiency of surface tension reduction, pC₂₅, surface excess concentration, , and surface area,A, per molecule in the adsorption layer. The Temkin adsorption isotherm equation was used to calculate standard free energy of adsorption, G ⁰ _=0.5 . The increments for a methylene group in the alkyl chain, G ^o [–CH₂–], and for the residual part of the molecule, G ^o [W], were also determined.The results obtained show that: (i) an increase in alkyl chain length at the C-2 carbon atom of the ring by one methylene unit brings about a marked increase in surface activity; (ii) the introduction of a methyl group into the 1,3-dioxolane ring (i. e., at C-2 or C-4 atom) has a weaker effect on surface activity of alkyl-substituted 1,3-dioxolanes, and (iii) the contribution of the 5- and 6-membered 1,3-dioxacyclane rings to a total surface activity of, respectively, 2-alkyl-1,3-dioxolanes and 2-alkyl-1,3-dioxanes is similar.     

Optimization of silicon dioxide surface functionalization protocol for designing the receptor layer of a biosensor for detecting explosives

The development of the receptor layer of the biosensor for detecting explosive compounds is described. The covalent modification has been chosen for immobilizing E. coli nitroreductase on the gate oxide of the ion-sensitive field effect transistor (ISFET) that is comprised of silicon dioxide. The self-assembled monolayer technique has been used for immobilization. This method assumes the usage of different silanes and spacer molecules for activating the surface of SiO₂. Two different immobilization strategies have been compared, one using asymmetric spacers (3-maleimidobenzoic acid N-hydroxysuccinimide ester (MBS) and 4-(4-maleimidophenyl)butyric acid N-hydroxysuccinimide ester (SMPB)) and another using a symmetric glutaric dialdehyde linker both accompanied by appropriate silanes. For the first method, the dependence of functionalization efficiency on silane concentration has been studied. The sufficient density of enzyme molecules on the surface of SiO₂ has been achieved at a concentration of silane of 0.0015%. The type of asymmetric linker has no influence on immobilization efficiency. The method implying glutaric dialdehyde results in higher activity of the immobilized enzyme. For this method, the immobilization procedure has been optimized. The method has been adapted for immobilization of E. coli nitroreductase inside the channel of a microfluidic system on the surface of ISFET. For this purpose, (3-aminopropyl)triethoxysilane (APTES) has been changed to the corresponding silatrane, and the concentration of the enzyme has been increased to 30 μg/mL. The optimized procedure has been successfully used to develop a biosensor for detecting explosives.     

Photoactivation of aromatic molecules on the surface of magnesium oxide

The influence of ultraviolet radiation on the state of molecules of aromatic hydrocarbons adsorbed from the gaseous phase onto magnesium oxide has been studied from the electronic absorption spectra (in diffuse reflected light) and electron paramagnetic resonance. Depending on the temperature of the preliminary vacuum treatment of the polycrystalline magnesium oxide, at least three types of molecular photoproducts were observed: paramagnetic products (for 600 C), nonparamagnetic products (for 400 and 900 C), and products identified as singly-charged radical-anions, converted into negative dimers in an excess of the hydrocarbon. A bathochromic shift of the absorption band maxima of the radical-anions is observed in the series BeO, MgO, CaO, and BaO. The mechanism of the photoformation of molecular ions and the nature of the surface defects on magnesium oxide are discussed.This work was carried out under the direction of Academician A. N. Terenin.     

Peculiarities of the formation of track-etched membranes by the data of atomic force microscopy and X-ray scattering

Atomic force microscopy (AFM) is employed to obtain information on the main stages of the preparation of ultrafiltration track-etched membranes based on poly(ethylene terephthalate) (PET). The surface structure of initial commercial samples of PET films and the same films irradiated with various fluxes of accelerated heavy ions and subsequently treated with alkaline that results in the formation of pores owing to track etching is studied. It is shown that the order of the aforementioned stages of the formation of track-etched membranes with various porosities (from 0.02 to 6%) at a typical pore size of about 50 nm leads only to slight changes in surface structural parameters and does not fundamentally affect the polymer structure formed by spherulites with sizes that are comparable with the pore sizes. In this case, nearly the same content of the crystalline phase in the initial film and track-etched membrane are identified by large-angle X-ray scattering. The picture of X-ray scattering by track-etched membranes at small angles fully corresponds to the scattering on cylindrical pores with a diameter of about 50 nm. The analysis of the set of roughness profiles of the surfaces of initial films and track-etched membranes obtained by the AFM technique makes it possible to determine and introduce—in addition to standard parameters of the surface, the mean value of roughness and its standard deviation the correlation length characterizing the mean distance at which the memory of the roughness value is lost. It is shown that treatments resulting in the formation of track-etched membranes favor an increase in the values of roughness and practically do not affect the mean correlation length, thus supporting the conclusion of the invariance of the main structural parameters of the PET surface.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 2, 2005, pp. 248–258.Original Russian Text Copyright © 2005 by Solovieva, Timofeeva, Erina, Vstovsky, Krivandin, Shatalova, Apel, Mchedlishvili, Timashev.     

Distribution and thickness of the surface contaminations on STM tungsten tips,studied by AES/SEM and ARXPS

The combination of Auger electron spectroscopy (AES), scanning electron microscopy (SEM) and angle resolved X-ray photoelectron spectroscopy (ARXPS) has been applied to the analysis of the distribution of elements at the surface region of electrochemically etched tungsten tips and the determination of the thickness of a layer with oxygen and carbon contamination. Auger line profiling revealed a homogeneous distribution of oxygen and significant enrichment of carbon on the W tip between 0 and 1.5 m from the top. The thickness of the contamination layer on various W materials, electrochemically etched, was found to be 1.35±0.15 nm as measured using ARXPS, and was estimated to be about 1–3 nm as measured by AES.     

A review of factors that affect contact angle and implications for flotation practice

Contact angle and the wetting behaviour of solid particles are influenced by many physical and chemical factors such as surface roughness and heterogeneity as well as particle shape and size. A significant amount of effort has been invested in order to probe the correlation between these factors and surface wettability. Some of the key investigations reported in the literature are reviewed here.It is clear from the papers reviewed that, depending on many experimental conditions such as the size of the surface heterogeneities and asperities, surface cleanliness, and the resolution of measuring equipment and data interpretation, obtaining meaningful contact angle values is extremely difficult and such values are reliant on careful experimental control. Surface wetting behaviour depends on not only surface texture (roughness and particle shape), and surface chemistry (heterogeneity) but also on hydrodynamic conditions in the preparation route. The inability to distinguish the effects of each factor may be due to the interplay and/or overlap of two or more factors in each system. From this review, it was concluded that:

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Surface geometry (and surface roughness of different scales) can be used to tune the contact angle; with increasing surface roughness the apparent contact angle decreases for hydrophilic materials and increases for hydrophobic materials.

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For non-ideal surfaces, such as mineral surfaces in the flotation process, kinetics plays a more important role than thermodynamics in dictating wettability.

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Particle size encountered in flotation (10-200 μm) showed no significant effect on contact angle but has a strong effect on flotation rate constant.

There is a lack of a rigid quantitative correlation between factors affecting wetting, wetting behaviour and contact angle on minerals; and hence their implication for flotation process. Specifically, universal correlation of contact angle to flotation recovery is still difficult to predict from first principles. Other advanced techniques and measures complementary to contact angle will be essential to establish the link between research and practice in flotation.     

Fourier transform spectroscopy of surface polariton bragg reflection in gratings

Periodic gratings on metal surface have been used for surface polariton decay length measurements for 5–15m wavelength by means of a commercial Fourier-transform spectrometer. The effect of different grating parameters as well as that of the spectrometer light beam configuration on transmission spectra has been investigated. Gaps in the transmission spectrum due to Bragg reflection have been studied in details.     

Wettability of Microstructured Hydrophobic Sol-Gel Coatings

The formation of appropriate surface patterns on hydrophobic surfaces leads to a general change in their wettability and the contact angle increases substantially. Such coatings are of great technical interest, especially if aqueous media are concerned as in the prevention of ice-adhesion. For this reason various fluorine containing nanocomposite coatings have been developed by sol-gel processing.The morphology of these hydrophobic surfaces has been controlled by varying the content of silica particles regarding size, degree of aggregation, and concentration. The wettability is characterized by the measurement of dynamic contact angles against water. The complete range of different wettability regimes is accessible, i.e. smooth surfaces (both low advancing contact angle and hysteresis between advancing and receding contact angle), surfaces within the Wenzel regime (high advancing contact angle and hysteresis), and superhydrophobic surfaces (high advancing contact angle and low hysteresis). The wettability is correlated with the surface roughness as determined using a profilometer or AFM.The wettability of superhydrophobic surfaces is greatly dependent on the surface tension of the liquid. By comparison of the tiltangle _t of a smooth and a superhydrophobic surface, a critical surface tension _c is identified, where _t (smooth surface) = _t (microstructured surface). The microstructured surface provides a better run-off of liquids _lg > _c 55 mN·m^–1.     

Surface treatment of langmuir-blodgett layers of poly (3-hexadecylthiophene) and stearic acid and their properties oaffected by gases

The influence of certain gases on the properties of thermally treated and -irradiated Langmuir-Blodgett (LB) films of poly (3-hexadecylthiophene) and stearic acid has been studied. Both the heat and -radiation brought about some structural surface layer changes, leading to temporal variations of the course of the in-plane conductivity of films affected by the presence of applied gases.