EPMA analysis of float glass surfaces

This work concentrates on the setting-up of conditions for the quantitative analysis of the composition profiles of major and minor components of float glass surfaces with an electron probe micro-analyser. Since surfaces are modified for depths of 10–50 m, they have been studied both in polished cross-section and perpendicularly to the electron beam by varying its energy to investigate the near-surface region (0–3m). The results demonstrate that combined use of the two methods supplies complete and continuous information on the quantitative distribution from large depths to the first layers of the float surfaces. The experimental conditions, sample preparation, in-depth and lateral resolutions, precision and accuracy of the methods are also investigated.     

Trace analysis of ceramic surfaces by laser ionization mass spectrometry

Summary Laser ionization mass spectrometry (LIMS) is an analytical method for the simultaneous determination of concentrations of trace elements in solid samples and for the analysis of layers with thicknesses >1 m. This laser-induced surface analytical method is limited by the laser focus and crater depth of the laser system applied. Results of mass spectrometric trace analysis on a silicon carbide surface, ZrO₂ and high-T_c superconducting ceramics are discussed.     

Melting of monatomic glass with free surfaces

Melting of monatomic glass with free surfaces has been studied by molecular dynamics simulations in models with Lennard-Jones-Gauss interatomic potential. Models have been heated up from a glassy state toward a normal liquid state. Atomic mechanism of melting has been analyzed via monitoring spatio-temporal arrangements of liquid-like atoms occurred during heating process. Liquid-like atoms are detected via the Lindemann criterion of melting. It is clear that the transition from glass into supercooled liquid of our "ordinary" glass with free surfaces exhibits a non-heterogeneous behavior, i.e., although liquid-like atoms initiate/grow mainly in the surface shell, significant amount of liquid-like atoms also initiates/grows simultaneously in the interior during heating process. We found three characteristic temperatures of melting of glass with a free surface. Temperature dependence of structure and various thermodynamic quantities of the system upon heating is also presented and discussed.     

Laser desorption-ionization of polycyclic aromatic hydrocarbons from glass surfaces with ion mobility spectrometry analysis

Polycyclic aromatic hydrocarbons (PAHs) were analyzed as adsorbates on borosilicate glass at levels from 40 pg (5.5 pg mm⁻²) to 7 μg (1 μg mm⁻²) using laser desorption-ionization (LDI) in air at ambient pressure and 100 °C with ion characterization by mobility spectrometry. Gas-phase positive ions with distinctive mobilities were produced from six PAHs using an unfocused beam at 266 nm, 6 mJ pulse⁻¹ and 10 Hz from a Nd-YAG laser. The ions produced were identified as M⁺ using mass spectrometry (MS) with a LDI source at atmospheric pressure. The mobility spectrometry drift tube provided low memory effects and allowed observation of time-resolved intensity profiles for ion signals, and changes in this behavior with loading level suggested intermolecular interactions from multilayer formation. Mobility peaks were broader than those seen in gas-phase reactions, and this was attributed to Coulombic repulsion caused by the small volume near the surface where ionization would take place. An ion shutter in the drift tube could be synchronized with the laser pulse to offer additional specificity using tandem mobility separation; further, resolution was improved in mixtures of PAHs with similar mobilities. Negative ions were also detected, though these were mass-identified as ions formed from air through the capture of electrons released from the PAHs; no M⁻-ions were observed in air. Limits of detection ranged from sub-pg to low-ng for individual PAHs.     

Characterizing the adsorption of proteins on glass capillary surfaces using electrospray-differential mobility analysis

We quantify the adsorption and desorption of a monoclonal immunoglobulin-G antibody, rituxamab (RmAb), on silica capillary surfaces using electrospray-differential mobility analysis (ES-DMA). We first develop a theory to calculate coverages and desorption rate constants from the ES-DMA data for proteins adsorbing on glass capillaries used to electrospray protein solutions. This model is then used to study the adsorption of RmAb on a bare silica capillary surface. A concentration-independent coverage of ≈4.0 mg/m(2) is found for RmAb concentrations ranging from 0.01 to 0.1 mg/mL. A study of RmAb adsorption to bare silica as a function of pH shows maximum adsorption at its isoelectric point (pI of pH 8.5) consistent with literature. The desorption rate constants are determined to be ≈10(-5) s(-1), consistent with previously reported values, thus suggesting that shear forces in the capillary may not have a considerable effect on desorption. We anticipate that this study will allow ES-DMA to be used as a "label-free" tool to study adsorption of oligomeric and multicomponent protein systems onto fused silica as well as other surface modifications.     

Surface analysis of sol-gel coatings on glass by secondary neutral mass spectrometry

Secondary neutral mass spectrometry (SNMS) has been used to profile coatings of the systems SiO₂ and 65SiO₂.20TiO₂.15ZrO₂ (STZ). The coatings have been deposited on float glass and heat insulating glass by dip coating from alkoxide solutions. The microporous gel coatings have been densified by heat treatment. The SBM method (separate bombardment mode) has been applied to characterize the systems and the HFM method (high frequency mode) to check for matrix effects in the SBM depth profiles. Both methods show sodium diffusion from the float glass substrate into the STZ coating and no significant sodium diffusion into the SiO₂ coating. Measurements of the coatings on the heat insulating glass indicate that the SnO₂ interlayer acts as a diffusion barrier. The diffusion of sodium from the float glass substrate into the STZ coating during consolidation has been analyzed by SBM-SNMS. The sputtering rate decreases with increasing consolidation. Due to large differences between sputtering rates of the substrate and of the microporous coatings, the calibration of sodium intensities from time to depth at the interface has not been possible. However, a correlation between the final temperature of heat treatment and the depth of the Na₂O depletion in the substrate surface under the coating can be obtained.     

Characterization of oxide coatings on glass

Some representative characteristics of oxide films deposited on glass by different techniques have been briefly described as well as several relevant methods of thin-film analysis to determine these quantities. The most powerful information obtained by some analytical techniques have been given, and some typical problems that may occur during the analysis of oxidic thin films have been discussed. With a few selected results, the potential of some modern methods has been demonstrated.     

Characterization of oxide coatings on glass

Some representative characteristics of oxide films deposited on glass by different techniques have been briefly described as well as several relevant methods of thin-film analysis to determine these quantities. The most powerful information obtained by some analytical techniques have been given, and some typical problems that may occur during the analysis of oxidic thin films have been discussed. With a few selected results, the potential of some modern methods has been demonstrated.     

Physicochemical characterization of biological glass coatings

Metallic implants are widely used in orthopaedic surgery but metal release has been reported by several authors. High metallic ion concentration in surrounding tissues may play a major role in therapeutic failure. We have investigated in vivo and in vitro two biological glasses (BVA and BVH) used as coatings of metal implants. Physicochemical characterization was made by several complementary methods, particularly particle induced x‐ray emission (PIXE) and energy‐dispersive x‐ray spectroscopy (EDXS) associated with electronic microscopy. Analyses clearly show the differences of behaviour between both glasses. The BVA glass is bioactive, i.e. it develops a direct chemical bond between prosthesis and bone by the formation of a calcium phosphate layer at its surface. These structural and compositional modifications are caused by hydrolysis of the glass. After its dissolution BVA glass is replaced by bone, which ensures better integration of the implant in the bone site. The BVH glass is not bioactive and is used as a cement to isolate the metal implant from the biological environment, but the coating disaggregates with implantation time and glass grains migrate through the bony lacuna network. Copyright © 2003 John Wiley & Sons, Ltd.     

Bacterial adhesion to glass and metal-oxide surfaces

Metal oxides can increase the adhesion of negatively-charged bacteria to surfaces primarily due to their positive charge. However, the hydrophobicity of a metal-oxide surface can also increase adhesion of bacteria. In order to understand the relative contribution of charge and hydrophobicity to bacterial adhesion, we measured the adhesion of 8 strains of bacteria, under conditions of low and high-ionic strength (1 and 100 mM, respectively) to 11 different surfaces and examined adhesion as a function of charge, hydrophobicity (water contact angle) and surface energy. Inorganic surfaces included three uncoated glass surfaces and eight metal-oxide thin films prepared on the upper (non-tin-exposed) side of float glass by chemical vapor deposition. The Gram-negative bacteria differed in lengths of lipopolysaccharides on their outer surface (three Escherichia coli strains), the amounts of exopolysaccharides (two Pseudomonas aeruginosa strains), and their known relative adhesion to sand grains (two Burkholderia cepacia strains). One Gram positive bacterium was also used that had a lower adhesion to glass than these other bacteria (Bacillus subtilis). For all eight bacteria, there was a consistent increase in adhesion between with the type of inorganic surface in the order: float glass exposed to tin (coded here as Si-Sn), glass microscope slide (Si-m), uncoated air-side float glass surface (Si-a), followed by thin films of (Co(1-y-z)Fe(y)Cr(z))3O4, Ti/Fe/O, TiO2, SnO2, SnO2:F, SnO2:Sb, A1(2)O3, and Fe2O3 (the colon indicates metal doping, a slash indicates that the metal is a major component, while the dash is used to distinguish surfaces). Increasing the ionic strength from 1 to 100 mM increased adhesion by a factor of 2.0 +/- 0.6 (73% of the sample results were within the 95% CI) showing electrostatic charge was important in adhesion. However, adhesion was not significantly correlated with bacterial charge and contact angle. Adhesion (A) of the eight strains was significantly (P < 10(-25)) correlated with total adhesion free energy (U) between the bacteria and surface (A = 2162e(-1.8U)).Although the correlation was significant, agreement between the model and data was poor for the low energy surfaces (R2 = 0.68), indicating that better models or additional methods to characterize bacteria and surfaces are still needed to more accurately describe initial bacterial adhesion to inorganic surfaces.     

Elevate the corrosion potential of Zn coatings using ceramic nanoparticles

Journal of Solid State Electrochemistry - It was observed that adding TiC nanoparticles (NPs) to zinc coating increased its corrosion resistance. To understand the beneficial role of TiC...     

Thermometric and potentiometric titrations of modified glass surfaces

Glass surfaces modified with N-2-aminoethyl-3-aminopropyltrimethoxysilane have been titrated with copper(II) by constant rate thermometric titration and by manual potentiometric titration with Gran plot end-point location. The results indicate that the titrant reacts with the bound ligand in a two-step process, with the thermometric titration responding to the first step and the potentiometric titration responding to the combined steps.     

Influence of powder-characteristics on the microstructure of ceramic plasma spray coatings

Summary The relationship between the properties of plasma spray powders and the resultant coating has been investigated. ZrO₂ powders, differing in grain size, state of agglomeration and morphology, have been used and coating properties such as microstructure, porosity, roughness, hardness, and wear resistance are described. Agglomerated powders cause high porosity, while sphericalized particles yield very dense layers. The homogeneity of an agglomerate is also responsible for the homogeneity of the microstructure of the coating. By selecting powders with defined characteristics it is possible to produce plasma spray coatings with defined properties; the microstructure of the layers can be varied over a wide range.     

Dielectrophoretic micropatterning with microparticle monolayers covalently linked to glass surfaces

Two-dimensional micropatterns of microparticles were fabricated on glass substrates with negative dielectrophoretic force, and the patterned microparticles were covalently bound on the substrate via cross-linking agents. The line and grid patterns of microparticles were prepared using the repulsive force of negative dielectrophoresis (n-DEP). The template interdigitated microband array (IDA) electrodes (width and gap 50 mum) were incorporated into the dielectrophoretic patterning cell with a fluidic channel. The microstructures on the glass substrates with amino or sulfhydryl groups were immobilized with the cross-linking agents disuccinimidyl suberate (DSS) and m-maleimidobenzoyl-N-hydroxy-succinimide ester (MBS). Diaphorase (Dp), a flavoenzyme, was selectively attached on the patterned microparticles using the maleimide groups of MBS. The enzyme activity on the patterned particles was electrochemically characterized with a scanning electrochemical microscope (SECM) in the presence of NADH and ferrocenylmethanol as a redox mediator. The SECM images proved that Dp was selectively immobilized onto the surface of microparticles to maintain its catalytic activity.     

Oxidation of CO in microchannels of ceramic membranes modified with oxide catalytic coatings

Ceramic and cermet membranes containing catalytic coatings in the internal volume of their channels were obtained. A relationship between the permeability and kinetic regularities of CO oxidation describing the transmembrane flow of gases was studied. The pre-exponential factor and apparent activation energy change as the loading of the membrane channels by the catalyst proceeds. The study of gas permeability through the membranes showed that the catalyst with a loose branched surface is distributed in the membrane microchannels. The reaction rate constant increases in parallel with an increase in the relative fraction of the catalyst surface. The CO oxidation rate is assumed to depend statistically on the number of active sites, which increases with filling of the membrane channels by the catalytic material.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2613–2619, December, 2004.     

On the synthesis of glass and glass-crystalline black-blue facing on thin ceramic

By x-ray phase analysis the optimal temperature is established for the spinel formation in the oxide system Co₂O₃-Fe₂O₃ at the producing ceramic black-blue pigment and the phases playing the role of basic chromophores. The synthesized pigments provide the glass facing with black-blue color and strong flashing (up to 86%) and with semi-dull fine crystalline facture based on the developed unfritted glaze characterized by strong and stable color in a wide range of roasting temperature.     

XPS and SIMS investigations on plasma-treated glass surfaces

Commercially available float-glass samples were exposed to ion bombardment in an HF-plasma. This should form an SiO₂-rich layer close to the surface of the samples. From XPS-investigations it was found that treatment times between 2 and 4 min in Ar plasma lead to a pronounced depletion of alkalis. Further FAB-SIMS depth profiles gave additional information about the extension of the layers with altered stoichiometry.