Corrosion of metal films in ice: the dynamics of the conductivity of films

A decrease in the conductivity of copper, aluminum, iron, and silver films brought in contact with ice as ice underwent thermally stimulated structural relaxation and of a copper film in contact with water undergoing crystallization was studied. Conductivity decrease was found to be irreversible and caused by metal corrosion.     

Structure of association in surface films

Association complexes which from on the polar groups of surface-active compounds during the spreading process on surfaces are described. In the hydration complexes of the interface 1, 2, 4, 9, 16 etc. water molecules surround the hydrophilic group. With the compression of a monolayer spread on water, complexes of higher water contents, out of which the water is pressed, are in thermodynamic equilibrium with the complexes of lower content thus formed.The association equilibrium described apply both to monomear and to polymer compounds, as is shown using the example of polydimethylsiloxane. The principles of the surface structures are discussed with the aid of surface tension, film pressure, space requirement, contact angle and heats of association.     

Photoactive additives for cross-linking polymer films: Inhibition of dewetting in thin polymer films

In this report, we describe a versatile photochemical method for cross-linking polymer films and demonstrate that this method can be used to inhibit thin polymer films from dewetting. A bifunctional photoactive molecule featuring two benzophenone chromophores capable of abstracting hydrogen atoms from various donors, including C-H groups, is mixed into PS films. Upon exposure to UV light, the bis-benzophenone molecule cross-links the chains presumably by hydrogen abstraction followed by radical recombination. Photoinduced cross-linking is characterized by infrared spectroscopy and gel permeation chromatography. Optical and atomic force microscopy images show that photocrosslinked polystyrene (PS) thin films resist dewetting when heated above the glass transition temperature or exposed to solvent vapor. PS films are inhibited from dewetting on both solid and liquid substrates. The effectiveness of the method to inhibit dewetting is studied as a function of the ratio of cross-linker to macromolecule, duration of exposure to UV light, film thickness, the driving force for dewetting, and the thermodynamic nature of the substrate.     

Thin films of Ag nanoparticles prepared from the reduction of AgI nanoparticles in self-assembled films

A novel method for the preparation of thin films of Ag nanoparticles is reported. Using mercaptoacetic acid as the stabilizing agent, AgI nanoparticles were prepared in aqueous solution. And based on electrostatic interactions, the thiol-passivated AgI nanoparticles were assembled in a self-assembled film by alternative deposition with a cationic polyelectrolyte. Then the AgI nanoparticles in the composite film were reduced by NaBH(4), which resulted in the formation of a thin film of Ag nanoparticles. UV-visible spectra and X-ray photoelectron spectroscopy data confirmed the transformation from AgI to Ag. Atomic force microscopy (AFM) showed that the formed Ag nanoparticles distributed on the film homogeneously. Surface-enhanced Raman spectroscopy (SERS) measurement indicated that the prepared thin films could be used as effective SERS substrates. The reduction process was also carried out by UV light at selective surface regions, which resulted in the formation of patterned nanoparticle arrays.     

Fluorescence in thin liquid films

The fluorescence properties of Rhodamine B in thin liquid films, formed from a number of anionic, cationic and non-ionic surfactant solutions, were investigated. Laser excitation was used and the emission was monitored over a period of time. Drainage profiles with light and dark fluorescence fringes were recorded with plane-polarized radiation. Change of polarization caused profound changes in the appearance of the profiles. The distribution of dye molecules between surfaces of the film and its interior was assessed and found to be related to the speed of film drainage. Expressions were established for the relation between fluorescence fringes and film thickness at different orientations of the film surface to the emission measurement direction.     

Cracking in drying latex films

Thin films of latex dispersions containing particles of high glass transition temperature generally crack while drying under ambient conditions. Experiments with particles of varying radii focused on conditions for which capillary stresses normal to the film deform the particles elastically and generate tensile stresses in the plane of the film. Irrespective of the particle size, the drying film contained, simultaneously, domains consisting of a fluid dispersion, a fully dried packing of deformed spheres, and a close packed array saturated with water. Interestingly, films cast from dispersions containing 95-nm sized particles developed tensile stresses and ultimately became transparent even in the absence of water, indicating that van der Waals forces can deform the particles. Employing the stress-strain relation for a drying latex film along with the well-known Griffith's energy balance concept, we calculate the critical stress at cracking and the accompanying crack spacing, in general agreement with the observed values.     

Surface forces in wetting films

A short review of various components of surface forces acting in a non-symmetrical system such as wetting films is presented here. Experimental results are compared with modified DLVO theory, which includes, besides dispersion and electrostatic, structural (solvation) forces caused by a change in liquid structure in conditions of confined geometry. The peculiarities of disjoining pressure isotherms and conditions of the film stability of non-polar and polar simple liquids, as well as of aqueous solutions of electrolytes and surfactants, are systematically considered from a historical perspective.     

Amphiphilic nanostructures in foam films

The revised articles outline the potential of microscopic foam film instrumentation as an investigation tool in studying the amphiphilic nanostructures in aqueous surfactant solutions. The impact of amphiphilic nanostructures on the drainage behaviour and stability of foam films is traced for surfactant solutions of concentrations orders of magnitude above CMC (micellar solutions) to about two orders of magnitude lower than CMC (premicellar solutions). It is found that in the high-concentration domain the micellar entities affect mainly the stability of the films. In the low-concentration domain, the presence of smaller crumbly aggregates (premicelles), plays a significant role for the kinetic stability of the films. Through the mechanism of Marangoni effect, an enhanced coupling of the specific film hydrodynamics and the mass transfer of the surfactant is obtained. The result is a sharp rise in the kinetic stability of the foam films. The importance of this trend of research is related to providing better insight into the self-assembling phenomena and into the factors that determine the drainage and the stability of thin liquid films. The results have potential and actual applications in food, cosmetic and pharmaceutical industries, as well as in biology and medicine.     

Polydiacetylene nanowires in ultrathin films

In this paper the results of studies carried out on thin films of new poly[bis(carbazol-9-ylmethyl)diacetylene]s (PCDAs) are reported. The preparation of the films has required clever synthesis to make processable the conjugated polymers without degrading their optoelectronic properties. To this end, the parent poly(diacetylene), (polyDCHD), has been modified by introducing long alkyl or acyl chains in the 3 and 6 positions of the carbazole rings. Electronic absorption spectra and linear and nonlinear optical characterization of three types of PCDAs are reported and compared.     

Heterogeneity in styrene-butadiene latex films

Low-Tg styrene-butadiene (SB) latex films were investigated by noncontact atomic force microscopy and scanning electric potential microscopy, revealing a number of different morphologies and electric potential patterns across films cast from the same SB latex dispersions under the same conditions. Surface leveling and charge dispersion throughout the films are, thus, restrained even at temperatures above Tg and the minimum film-formation temperature. An unprecedented electric pattern is observed, in which the particle cores are more positive than the contacting particle outer layers. Different packing patterns, including cubic and hexagonal arrays, coexist in neighboring areas. Zonal centrifugation of the SB latex in sucrose density gradient shows that particles cover a broad range of densities. Thus, film surface heterogeneity is at least partly due to particle heterogeneity. Fractal dimensions of topographic profiles are lower than those of the electric potential profiles, showing that charge mobility is much more restrained than polymer chain motion at the film surface and that it imposes a limit to the charged chain-ends motion.     

Polyoxometalate monolayers in Langmuir-Blodgett films

Langmuir and Langmuir-Blodgett (LB) films of a variety of polyoxometalates of different shapes, sizes, and charges were prepared by taking advantage of the adsorption properties of these polyanions on a positively charged monolayer of an organic surfactant spread on water. Three different aspects were investigated. 1) The electrochemical and electrochromic properties of LB films containing the easily reducible polyoxoanion [P2Mo18O62]6-. Absorbance changes of these LB films deposited onto an ITO substrate have been induced by repeated switching of the applied potential. These changes are due to the formation of the colored reduced forms of the polyanion. Coloration and bleaching of the LB film occur very quickly and are reversible. 2) The preparation of LB films based on magnetic polyoxometalates, such as the Keggin anions, [CoW12O40]6- and [SiMn(OH2)W11O39]6-, or containing magnetic clusters of increasing nuclearities such as [Co4(H2O)2(PW9O34)2]10- and [Co4(H2O)2(P2W15O62)2]16- based on a Co4O16 ferromagnetic cluster, and the polyoxometalates [Co9(OH)3(H2O)6(HPO4)2(PW9O34)3]16- and [Ni9(OH)3-(H2O)6(HPO4)2(PW9O34)3]16- based on a nonanuclear M9O36 cluster. 3) The preparation of LB films of the giant heteropolyoxomolybdate, [Na3(NH4)12][Mo57Fe6(NO)6O174(OH)3-(H2O)24]76 H2O.     

Polyelectrolytes in thin liquid films

The review addresses the influence of polyelectrolytes on the statics and dynamics of thin liquid films. Both, changes of interfacial and bulk properties, contribute to the overall behaviour of thin films formed from aqueous polyelectrolyte solutions. Therefore, the chapter is separated into two parts: polyelectrolytes at film interfaces and polymers in film bulk.     

Electron transport in bipyridinium films

Bipyridinium dications are versatile building blocks for the assembly of functional materials. In particular, their reliable electrochemical response has encouraged the design of electroactive films. Diverse and elegant experimental strategies to coat metallic and semiconducting electrodes with bipyridinium compounds have, in fact, emerged over the past two decades. The resulting interfacial assemblies span from a few nanometers to several micrometers in thickness. They incorporate from a single molecular layer to large collections of entangled polymer chains. They transport electrons efficiently from the electrode surface to the film/solution interface and vice versa. Electron self-exchange between and the physical diffusion of the bipyridinium building blocks conspire in defining the charge transport properties of these fascinating electroactive assemblies. Often, the matrix of electron-deficient bipyridinium dications can be exploited to entrap electron-rich analytes. Electrostatic interactions promote the supramolecular association of the guests with the surface-confined host matrix. Furthermore, chromophoric sites can be coupled to the bipyridinium dications to produce photosensitive arrays capable of harvesting light and generating current. Thus, thorough investigations on the fundamental properties of these functional molecule-based materials can lead to promising applications in electroanalysis and solar energy conversion, while contributing to advances in the basic understanding of electron transport in interfacial assemblies.     

Photoinduced transparency in polypyrrole films

For the first time we have discovered drastic photoinduced effects in the transparency for the pyrrole films. Photoinduced investigations of transparency were performed for the polypyrroles with different number of the pyrrole rings. We have established a considerable increase of the transparency from 70-75% up to 82-84% for the wavelengths of the probing lasers operating within the 530-1040 nm spectral range. The photoexcitation was performed by nanosecond pulsed polarized Nd-YAG laser generating at 1.34 microm. The phototransparent changes are completely reversible and disappear after switching off the laser treatment. The typical relaxation time for the photoinduced transparency is equal to about 10-20 micros and the changes of the transparency are strictly related with the values of state dipole moments of the polypyrroles. As a possible mechanism for explanation of the observed dependences one can consider existence of the charged trapping levels intra the forbidden energy gaps which effectively interact with the electric strength of the external polarized optical field and state dipole moments of the particular polymers.     

Diffusion in ultrathin liquid films

Inhomogeneous molecular diffusion in layered structures of thin liquid films deposited on solid surfaces is observed via wide field single molecule microscopy. The fluorescence dyes Rhodamine 6G and Oregon Green 514 are used to probe the diffusion in tetrakis(2-ethylhexoxy)-silane and polydimethylsiloxane. A broad distribution of diffusion constants is observed which can be attributed to diffusion within distinct layers of the liquid. Comparison with computer simulations shows that diffusion is normal but depends strongly on the distance of the molecules from the solid surface. Diffusion within layers is faster than between the layers and additional temperature activation is necessary to speed up interlayer diffusion.     

Chromatography in thin polyamide films

Summary The applicability of Russian-made samples of polyamide for use as sorbents for the separation of some amino acid derivatives has been shown.M. M. Shemyakin Institute of the Chemistry of Natural Compounds, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 66–68, January, 1971.     

Membrane proteins in thin films

Molecular functions and structural changes of membrane proteins in an aqueous environment can be elucidated by reaction-induced FTIR difference spectroscopy upon photolysis of caged compounds. The achieved detection of IR band changes even due to single amino acid residues is, however, only possible in the presence of very high protein concentrations, implying that a low water content must be present. In general, the films are formed by controlled dehydration of membrane protein suspensions at reduced pressure and low temperature. For the retention of enzymatic activity of Na,K-ATPase, for example, a cosolvent such as glycerol is required. In order to interprete the results obtained by FTIR spectroscopy, it is important to know whether essential properties of the proteins such as hydration are changed upon film formation. Therefore, a differential scanning calorimetry (DSC) study has been carried out with purified Na,K-ATPase and Ca-ATPase in suspension, in form of pellets obtained by high-speed ultracentrifugation and in thin films. As relevant thermoanalytical properties, the endothermic denaturation transitions of the proteins have been studied. For Na,K-ATPase in the presence of 20% glycerol as cosolvent, a single, comparatively narrow endothermic and irreversible denaturation transition with a denaturation enthalpy of about 1.7 MJ mol⁻¹ and transition temperatures of about 65 and 70°C is found in concentrated suspension and in the state of the pellet, respectively. In the case of thin films suitable for IR spectroscopy, a characteristic change is observed in a reproducible manner. The enthalpy change of the remaining transition around 70°C is reduced but an additional transition at about 77°C is observed. Based on control experiments, the new high temperature transition is attributed to a partially dehydrated state of the protein. Furthermore, a comparatively broad endothermic transition around 20°C is found under conditions of high protein concentrations (film), which is tentatively assigned to a transition of the lipid environment of this integral membrane protein. Similar results are found for Ca-ATPase films. In the absence of glycerol, the deoxycholate treated enzyme in suspension exhibits a narrow endothermic main transition at 52°C with a denaturation enthalpy around 0.9 MJ mol⁻¹. For the film of this protein, two almost equally large endothermic transitions are found at 59 and 77°C. Also here, the data are characteristic of partial protein dehydration. These results show clearly that DSC can easily be applied in a sensitive manner to control and characterize the integrity and hydration properties of concentrated protein samples in thin films.     

Wetting films

Wetting films of nonpolar liquids are stabilized due to action of the repulsion dispersion forces. For aqueous films, it is necessary to takes additionally into account action of electrostatical and structural forces.Disjoining pressure isotherms of a thick methastable β -films of electrolyte and surfactant solutions can be quantitavely described on the basis of theory of long-range electrostatical forces. Thicknesses of thinner α-films of water formed as a result of vapour adsorption depend on the surface hydrophilicity and are controlled by the action of structural repulsion forces.