Chiral discrimination within disordered adlayers on metal surfaces

Using a novel non-linear optical technique enantiomeric excess within a translationally disordered overlayer on a metal surface has been monitored for the first time.     

Electrochemistry of metal adlayers on metal chalcogenides

Electrodeposition of metal adlayers on semiconductor metal chalcogenides (CdSe, CdS, PbTe, PbSe, PbS, Bi₂Te₃) is reviewed. Cathodic underpotential deposition of metal adlayer on metal chalcogenide is the electrochemically irreversible surface limited reaction. The irreversibility of the upd increases in the row from tellurides to selenides and further to sulfides. The underpotential shift on chalcogenide nanoparticles increases with particle size. Metal upd on chalcogenides is applied as a means of measurement of electroactive surface area of chalcogenide electrodes. The method is especially advantageous for multicomponent systems with other component not supporting upd, such as CdSe-TiO₂, CdSe-ZnO. Differences of voltammetric profiles of Pb upd on Bi₂Te₃ and Te are applied for detection of Bi₂Te₃ surface contamination by elemental tellurium. The further tasks in the electrochemistry of metal adlayers are their incorporation as interlayers in layered chalcogenides and electrodeposition of superlattices.

Graphical abstract

     

Thin metal films on quasicrystalline surfaces

Thin metal films with a thickness of one or over one monolayer formed on quasicrystalline surfaces were studied using reflection high-energy electron diffraction, X-ray photoelectron spectroscopy, X-ray photoelectron diffraction and scanning tunneling microscopy. The substrates were the 10f surface of d-Al–Ni–Co and the 5f surface of i-Al–Pd–Mn. The metals deposited were Au, Pt, Ag and In. None of these metals forms any ordered layer by deposition onto clean quasicrystalline surfaces. However, if a submonolayer of In is present atop the 10f surface, an epitaxial layer of multiply-twinned AuAl₂ crystals is formed by Au deposition and subsequent annealing. This is also the case for Pt deposition, but not for Ag deposition. Although the surfactant effect of In is also observed in the case of Au deposition on the 5f surface of i-Al–Pd–Mn, the ordered layer formed is a film of Au–Al alloy with icosahedral symmetry. No ordered films are formed by Pt or Ag deposition onto the 5f surface, regardless of the presence of an In-precovered layer. A Sn film monolayer induced by surface diffusion was also studied.     

Microanalysis of corrosion films on metal surfaces by Raman spectroscopy

Summary The chemical composition of corrosion films on the surface of metals used in electrical microrelays has been studied by Raman spectroscopy. On the surface of a zinc coated armature one formate species could be detected whereas on the surface of a spring composed of a copper-nickel-zinc alloy the formation of two different formate species was observed. The above formate formation resulted from contamination of the used lubricant by formic acid.

---

Mikroanalyse von Korrosionsfilmen auf Metalloberflächen mit Hilfe der Raman-Spektroskopie

Zusammenfassung Die chemische Zusammensetzung von Korrosionsfilmen auf der Oberfläche von Metallen aus elektrischen Mikrorelais wurde mit Hilfe der Ramanspektroskopie untersucht. Auf der Oberfläche eines verzinkten Ankers wurde Formiat festgestellt und auf der Oberfläche einer Feder aus einer Kupfer-Nickel-Zink-Legierung wurden zwei verschiedene Arten Formiat nachgewiesen. Die Bildung dieser Formiate ergab sich aus der Verunreinigung eines Schmiermittels mit Ameisensäure.

     

Hybrid films prepared from latex particles incorporating metal oxide nanoparticles

Metal oxide (ZrO₂) nanoparticle-dispersed polymer films (hybrid latex films) were prepared from polymer particles incorporating ZrO₂ nanoparticles (hybrid latex dispersion). The hybrid latex dispersions were synthesized by miniemulsion polymerization. The resulting films were transparent, and they derived their properties from the ZrO₂ nanoparticles. The refractive indexes of the films increased with the ZrO₂ content. Surface-modified ZrO₂ nanoparticles were dispersed successfully in a polymer matrix containing phosphoric acid groups, which interacts with the surfaces of the ZrO₂ nanoparticles and increases the compatibility between the polymer and ZrO₂.     

Study on functionalization of metal surfaces. III. Photopolymerization of monomer films on metal surfaces

The three kinds of monomer films on metal surfaces were deposited by adsorption from a solution of 6-polymerizable substituents-1,3,5-triazine-2,4-dithiol monosodium salts (RTDN); the polymerizable substituents such as cis-9-octadecenylamino, di(cis-9-octadecenyl)amino, and p-vinylbenzyl(cis-9-octadecenyl)amino groups were selected in view of the polymerization activity of unsaturated groups in the substituents and the packing degree of monomer molecules. The monomer films were estimated to consist of mainly 6-substituents-1,3,5,-triazine-2,4-dithione (3H, 5H) and to be multimolecular layers that are considerably cross-packed and ordered. The monomer films on metal surfaces were polymerizable under a UV light irradiation in air atmosphere to give polymer films. In the photopolymerization, azobis(isobutyronitrile) (AIBN) was very effective for increasing the monomer conversion and the polymerization rate. The optimum concentration of AIBN in monomer films was very small, about 0.025 mol %. The monomer conversion was influenced by the kind of monomers, namely, the polymerization activity and the packing degree. The effect of the packing degree was especially remarkable. The monomer conversion decreased with an increase in the thickness of monomer films. This is because the polymerization was initiated by oxygen and AIBN, which were diffused into the inner of monomer films. The possibility of polymerization of the unsaturated groups and the thione groups in monomer molecules under UV light irradiation is discussed.     

Cu-deposits on Mg metal surfaces promote electron transfer reactions

The enhancement of the electron transfer processes in the Grignard reagent formation-type ring silylation and the defluorination–silylation of perfluoroalkyl benzenes by Cu(0)-deposited Mg metal were confirmed. Microscopic analysis and substituent effects implied a different reduction process in the presence of Cu-deposited Mg metal than in the presence of bare Mg metal.     

Molecular adsorption on ZnO(1010) single-crystal surfaces: morphology and charge transfer

While ZnO has excellent electrical properties, it has not been widely used for dye-sensitized solar cells, in part because ZnO is chemically less stable than widely used TiO(2). The functional groups typically used for surface passivation and for attaching dye molecules either bind weakly or etch the ZnO surface. We have compared the formation of molecular layers from alkane molecules with terminal carboxylic acid, alcohol, amine, phosphonic acid, or thiol functional groups on single-crystal zinc oxide (1010) surfaces. Atomic force microscopy (AFM) images show that alkyl carboxylic acids etch the surface whereas alkyl amine and alkyl alcohols bind only weakly on the ZnO(1010) surface. Phosphonic acid-terminated molecules were found to bind to the surface in a heterogeneous manner, forming clusters of molecules. Alkanethiols were found to bind to the surface, forming highly uniform monolayers with some etching detected after long immersion times in an alkanethiol solution. Monolayers of hexadecylphosphonic acid and octadecanethiol were further analyzed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and electrochemical measurements. AFM scratching shows that thiols were bound strongly to the ZnO surface, suggesting the formation of strong Zn-S covalent bonds. Surprisingly, the tridentate phosphonic acids adhered much more weakly than the monodentate thiol. The influence of organic grafting on the charge transfer to ZnO was studied by time-resolved surface photovoltage measurements and electrochemical impedance measurements. Our results show that the grafting of thiols to ZnO leads to robust surfaces and reduces the surface band bending due to midgap surface states.     

Investigation of Biopag films adsorbed on metal and ceramic surfaces by X-ray photoelectron spectroscopy

Using X-ray photoelectron spectroscopy, it was found that the treatment of aluminum, nickel, and ceramic surfaces with a 1% Biopag aqueous solution (Biopag, poly(hexamethylene guanidine chloride)), was synthesized at the Institute of Ecological and Technological Problems in accordance with TU (Specifications) 9392-020-41547288-02) results in the formation of thin polymer films on the surfaces. The chemical composition of the films was determined. It was shown that the chemical composition of the films is changed on long standing in air. Microbiological tests were carried out, and the minimum suppressing concentration toward Pseudomonas aeruginosa was determined. It was shown that the Biopag films aged for 6 months retain up to 84% of their initial activity.     

Field evaporation and field desorption from HTSC single-crystal surfaces

The problems of field evaporation (FE) and field desorption (FD) from surface of oxide high-temperature superconductors (HTSC) of 123, 2212 and 2223 type are discussed. Wide-angle atom probe, usual time-of-flight atom probe and field ionization magnet mass-spectrometer have been used in these experiments. The main purpose of the investigation was to search for effects connected with phase transition. Therefore, the experiments were carried out over a wide range of temperatures: from T of solid nitrogen to room T.

Composition of pure, contaminated and deep corroded surface and typical species of FE and FD spectra have been studied. The bond energies between some atoms (or clusters) and the surface have been estimated on the basis of experimental results and FE theory. From these estimations, and from discovering of correlated ion pairs, it was concluded that the redistribution of local bonds should be taken into consideration in this case. The increase of FE rate was observed at cryogenic temperatures. Various versions are discussed to explain these effects. Some of them are connected with phase transition.

A detailed study of FD of water protonized clusters is performed and the catalytic activity of HTSC crystal surfaces is discussed.     

Superhydrophobic surfaces from various polypropylenes

Superhydrophobic surfaces were prepared from solutions of isotactic polypropylenes of various molecular weights using soft chemistry. Varying the conditions of the experiments (polymer concentration and initial amount of the coated solution) allowed us to optimize the superhydrophobic behavior of the polymer film. Results show that decreasing the concentration and/or film thicknesses decreases the probability to get superhydrophobicity for all polypropylenes tested. Measurement and analysis of advancing and receding contact angles as well as estimation of surface homogeneity were performed. Similar results were obtained with syndio- as well as atactic polypropylenes.     

pH-dependent electron transfer from re-bipyridyl complexes to metal oxide nanocrystalline thin films

Photoinduced interfacial electron transfer (ET) from molecular adsorbates to semiconductor nanoparticles has been a subject of intense recent interest. Unlike intramolecular ET, the existence of a quasicontinuum of electronic states in the solid leads to a dependence of ET rate on the density of accepting states in the semiconductor, which varies with the position of the adsorbate excited-state oxidation potential relative to the conduction band edge. For metal oxide semiconductors, their conduction band edge position varies with the pH of the solution, leading to pH-dependent interfacial ET rates in these materials. In this work we examine this dependence in Re(L(P))(CO)3Cl (or ReC1P) [L(P) = 2,2'-bipyridine-4,4'-bis-CH2PO(OH)2] and Re(L(A))(CO)3Cl (or ReC1A) [L(A) = 2,2'-bipyridine-4,4'-bis-CH2COOH] sensitized TiO2 and ReC1P sensitized SnO2 nanocrystalline thin films using femtosecond transient IR spectroscopy. ET rates are measured as a function of pH by monitoring the CO stretching modes of the adsorbates and mid-IR absorption of the injected electrons. The injection rate to TiO2 was found to decrease by 1000-fold from pH 0-9, while it reduced by only a factor of a few to SnO2 over a similar pH range. Comparison with the theoretical predictions based on Marcus' theory of nonadiabatic interfacial ET suggests that the observed pH-dependent ET rate can be qualitatively accounted for by considering the change of density of electron-accepting states caused by the pH-dependent conduction band edge position.     

Melting behavior of drawn films from polyethylene single-crystal mats

Drawing of mats of linear polyethylene single crystals prepared from dilute solution is possible at temperatures above about 90°C. The structure and properties of the drawn specimens are much different from those ordinary drawn bulk polymer. Drawn mats have been investigated by differential scanning calorimetry. The characteristic experimental results are: (a) a broad melting curve, (b) considerable superheating depending on the rate of heating, (c) constancy of the melting point and the heat of fusion with annealing, (d) deviation from the relation between the heat of fusion and the density obtained for the drawn bulk specimens, (e) appearance of two melting peaks in samples annealed at temperatures above about 130°C. These results imply that the structure of the drawn mat is characterized by a larger number of the tie chains connecting the neighboring crystals (the structure postulated in earlier papers) than is the case in ordinary drawn bulk polymer. It can be concluded that the transformation of a fringed micellar type of structure to the folded lamellar structure may be difficult during annealing unless crystals melt and then recrystallize during cooling.     

Contact angles on metal and polymer surfaces in mass transfer environments

Contact angles of pure and binary liquid mixtures measured where the surrounding vapor is not in equilibrium with the liquid are reviewed. Two physical situations were examined which simulated conditions of distillation and condensation. An explanation was afforded as to why at low concentrations when mass transfer took place, some binary mixtures exhibited poor wetting characteristics on metal surfaces but not on polymers. Furthermore, under condensation conditions, the dropwise-filmwise transition was shown to occur at the contact angle of 90° for real systems.     

Inverse photoemission from metal surfaces

Ultraviolet inverse photoemission spectroscopy (IPES) is a technique for exploring unoccupied electronic states, particularly in the energy range between the Fermi level and vacuum level, a range inaccessible in ordinary photoemission. Theories of inverse photoemission and its special instrumentation requirements are outlined. IPES measurements on clean metal surfaces have revealed an abundance of new Shockley surface states and the Rydberg series of image states converging on the vacuum level. Empty surface states of d-like character have also been seen. The systematics of the occurrence of surface states (including image states) associated with s,p bulk band gaps are well described by a simple adaptation of multiple-reflection theory. This model is propounded and its implications discussed with regard to effective masses, surface corrugation, and determination of the surface barrier potential. IPES measurements on adsorbate-covered metal surfaces have revealed antibonding levels (O on Ni surfaces being the prime example) and valuable information on empty molecular levels (the 2π state in adsorbed CO and NO being the prime example). A straightforward Blyholder interpretation is modified by considerations of electronic relaxation and screening in the emission process. We compare and contrast the role of these effects in photoemission and inverse photoemission. Polarization selection rules and molecular shape resonances are also discussed.     

PEC films prepared from Chitosan-Alginate coacervates

Chitosan-alginate polyelectrolyte complex (PEC) have been prepared in situ in beads and microspheres. This study examines the preparation of suitable chitosan-alginate coacervates for casting into homogeneous PEC films for potential applications in packaging, controlled release systems and wound dressings. Coacervation between chitosan and alginate was rapid, but the rate may be controlled with the addition of water miscible organic solvents. Compared with ethanol and PEG200, acetone was the more promising solvent moderator. Suspensions of fine, uniformly dispersed coacervates were produced by a dropwise addition of 0.25% w/v chitosan solution (solvent: 1: 1 v/v of 2% acetic acid and acetone) into 0.25% w/v sodium alginate solution in water under rapid agitation. The PEC films were transparent and flexible. They exhibited high permeability to water vapor, but resisted complete dissolution in 0.1 M HCI, distilled water and pH 7.4 phosphate buffer solution. Microscopic heterogeneity in the films could be reduced by immersion in aqueous media, but this was accompanied by modifications in the thickness, permeability and mechanical property of the films.     

Assessment by XPS and electrochemical techniques of two molecular organosilane films prepared on stainless‐steel surfaces

The ability of silane groups to chemosorb on mechanically polished stainless‐steel surfaces has been investigated. Accordingly, tridecafluoro‐1,1,2,2‐tetrahydrooctyltrichlorosilane and the tridecafluoro‐1,1,2,2‐tetrahydrooctyltriethoxysilane, two organosilanes of similar chain length terminated with hydrophobic non‐reactive functions, have been tested as probe molecules. X‐ray photoelectron spectroscopy characterization, optical microscopy imaging, electrochemistry and contact angle measurements have been performed to characterize bare and modified samples. Results reported in this work show the influence of time of immersion and coupling agent reactive group on self‐assembled monolayer formation. It emerges that silanization by triethoxysilanes in millimolar solutions is not suitable for producing chemically bonded organic films with high density. Copyright © 2004 John Wiley & Sons, Ltd.     

Electro-switchable surfaces for heavy metal waste treatment: Study of polyacrylic acid films grafted on gold surfaces

This paper focuses on using electrochemical-pH-switchable polymer films as active surfaces for heavy metal waste treatment. Polyacrylic acid (PAA) was grafted at open air and room temperature on gold substrates. As a broad-range chelating material, PAA can capture heavy metal ions at low concentration. The release of the metal ions from the grafted-PAA film was obtained under electro-induced-acidification by applying an anodic potential at the electrode to promote a localized water electrolysis. Such electrochemical-switchable films can be part of a secondary step-treatment after conventional ion exchange process or precipitation for treatment of aqueous effluents in order to reach very low concentration in heavy metal ions without production of secondary effluents.     

Properties and structures of films drawn from polyethylene single-crystal mats

The properties and structures of polyethylene films drawn from mats of single crystals were investigated in comparison with films drawn from bulk polymer. The most important result obtained is that the structural reorganization stimulated by mechanical stress and annealing occurs with much greater difficulty in the mat-drawn film. The chief mechanical characteristics of the film are a very low extensibility and a very high modulus. Structural characteristics, such as the double-orientation of the crystalline region and the morphology of the crystals, do suffer no substantial changes during annealing at high temperatures. This stability of the structure can be related to the characteristic fine structure of the mat-drawn film in which there are a much larger number of tie chains, connecting neighboring crystals, than in the bulk-drawn specimen. Relaxation of the amorphous region and a notable increase in long spacing take place in the mat-drawn sample as in ordinary bulk-drawn samples. However, the morphological changes of the crystals accompanied by the folding back of chains seem to take place with great difficulty during annealing even in the vicinity of the melting point.