Use of FTIR reflectance spectroscopy to monitor corrosion mechanisms on glass surfaces

Fourier transform infrared (FTIR) reflectance spectroscopy was used to monitor corrosion mechanisms on the surface of lithium disilicate (Li₂O-2SiO₂) glass samples exposed to an aqueous solution for short times. The traditional mechanisms of glass corrosion were observed but a spectral feature was resolved that was previously unreported. This feature consisted of a peak suspected to result partially from a silanol (Si-OH) vibration in the region 800-1050 cm⁻¹ that shifted and reappeared in a cyclic fashion throughout the corrosion process. The behavior of this peak tends to suggest that the creation and condensation of Si-OH groups is the reaction responsible for causing the shift of the main Si-O-Si and Si-O⁻ peaks, a phenomenon which has previously lacked a detailed explanation.     

Acid-base properties of glass surfaces

The adhesion of polymers to inorganic oxides such as glass is very dependent on acid-base interactions between the acidic or basic surface sites of the glass and the basic or acidic functional sites of the polymer. This paper reviews the principles of such interactions, methods of measuring the acidity or basicity of surface sites, and the enhanced mechanical properties of glass-reinforced polymer composites resulting from interfacial acid-base complexation. A new study is presented of the acid-base properties of fiberglass and of surface treatments with silane coupling agents and polyvinyl acetate. It illustrates calorimetric titration methods for assessing surface acidity and basicity, and correlates these findings with angular-dependent X-ray photoelectron spectroscopy (ADXPS).     

Chemical characteristics of float glass surfaces

The regions near the top and bottom surfaces of float glass are chemically different from the bulk glass composition. In addition to the presence of tin oxide at the bottom surface and to a lesser extent at the top surface, differences are found in SiO₂, Na₂O, CaO, SO₃ and Fe₂O₃. The concentrations of Na₂O, CaO and SO₃ are lower at the top surface than in the bulk glass, while SiO₂ is higher. In the case of tin at the bottom surface and iron at both top and bottom surfaces, the components exist in complex concentration gradients. In addition, there are variations in oxidation state for tin, iron and sulfur. Tin appears to exist in both stannous and stannic states near the bottom surface. So far it has been found that iron at the top surface and sulfur at the bottom are largely in reduced states. Some consequences of these effects have been observed in physical and chemical behavior of the surface.     

Stress corrosion of a low-temperature solder glass

The stress corrosion of a typical low-temperature, high-lead vitreous solder glass suitable for sealing TV tubes and other displays was investigated in terms of static, dynamic and button tests. The button tests, which take into account the effects of interactions that occur between various glasses during fabrication of the display assembly, have been found to be extremely useful in selecting sealing glasses for the application, in estimating seal life during product service and in determining the acceleration factors for pretesting the seal prior to use in the field. The time-to-failure of the seal was found to be highly thickness dependent, and, for a given thickness, humidity had a much more pronounced effect than temperature.     

Determination of light-scattering properties of glass surfaces

Glass surfaces were damaged in a defined manner by sandblasting with an adjustable sand blasting machine and subsequent etching with HF. Investigations with the scanning electron microscope (SEM) showed surface defects with an ellipsoidal shape. A quantitative evaluation of the exact profile of these defects was made using mathematical evaluation of stereographic pairs. A new method is described for characterizing surfaces with optical light scattering. In contrast to the usual method of a fixed specimen and a photocell moving on a circle around it, here the specimen revolves on an axis perpendicular to a laser beam and rotates on an axis parallel to it in order to average the scattering over a large area of the surface, thus preventing interferences of the coherent laser beam with surface defects. A theory is described which enables a numerical estimation of roughness parameters using a distribution function of angles of small mirrors to the average surface. In this special case the theory was extended for the special type of defects having an ellipsoidal shape. The results are discussed with respect to creation of surface defects by sandblasting, which are accompanied by subsurface cracks.     

Dealkalization of glass surfaces utilizing HCI gas

Surfaces of silicatee glasses can be dealkalized when exposed to SO₂⁻, chlorine- and fluorine-containing gases. The chemically modified near-surface regions display properties which are different from those of the bulk. Emphasis will be placed on the deakalization mechanism and the improvement of specific surface properties of various industrial glasses.     

Stress corrosion of silicate glass: a review

In the first section of the present paper, some examples, from the field, of the manifestations or consequences of the fatigue of silicate glass are briefly presented. In the second section, the interpretation of fatigue in terms of stress corrosion is reviewed: the role of ambient molecular water is well established. Whatever the details of the mechanism of action of water, it takes place very efficiently in the highly strained material close to the tip of a surface crack. This enables its sub-critical growth to be explained. But it does not explain many other observed effects of the environment on the mechanical behavior of silicate glass, and, in the last section, questions and issues are presented, which would still need to be investigated.     

Characterization of organic adsorbates on model glass surfaces

Model silicate glasses in planar thin film structures are prepared using sol/gel techniques. A typical structure consists of 3.0–12.0 nm of glass on vapor deposited Ag. In this study, a pure silica and a 50/50 binary alumina-silica films are examined. Poly(methyl methacrylate) (PMMA) is adsorbed from chlorobenzene solution onto the surfaces. Infrared reflection (IR) spectroscopy, ellipsometry and quartz oscillator microgravimetry (QOM) are applied to characterize the PMMA/silicate glass interfaces formed. The QOM and IR data show that PMMA adsorption on the pure silica surface is irreversible with respect to removal by pure solvent rinse while on the binary glass surface and on a pure alumina surface, solvent rinses remove the initially adsorbed polymer. These results are interpreted in terms of Bronsted acid-base interactions involving the basic properties of the PMMA C=O group, the acidic nature of the silica and the more basic nature of the alumina containing surfaces. Further evidence for this interpretation is given by the IR spectral data which show broadening of the C=O stretching mode to lower frequencies for the irreversible adsorbed polymer on silica as compared with simulated spectra of non-surface bonding PMMA thin films. This spectral perturbation is interpreted as evidence for a hydrogen bonding interaction between OH groups on the silica surface and the C=O groups. The overall conclusion is that the surface of a 50/50 binary alumina-silica composition is dominated by the basic nature of alumina.     

Particulate erosion of glass surfaces at subsonic velocities

The erosion of borosilicate glass plates through multiple collisions with 70–290 μm glass beads and 1.8 mm water drops is described. The basic element for the initiation of erosion damage by rounded solid particles is the cone fracture. The diameter of the ring and penetration of the conical fracture surface extending into the glass specimens have been measured for various impact conditions. The material removal process near the velocity threshold for cone fracture formation is dependent on the radius of the impacting particle. At intermediate velocities in the subsonic range the damage due to a single water drop impact is much more difficult to identify compared to solid-particle impingement. The observed damage is not coherent and fracture surfaces approximating circular arcs only begin to become evident at velocities considerably higher than that required for preferential erosion of the specimen's surface.     

Alteration and corrosion phenomena in Roman submerged glass fragments

In the present paper the surface analytical techniques of XPS (X-ray photoelectron spectroscopy) and SIMS (secondary ions mass spectrometry) have allowed an understanding of the alteration and corrosion phenomena occurring in Roman glass fragments. The samples come from the seawater archaeological site of the Roman ship Iulia Felix, which sank near Grado (Gorizia, Italy) in the second century A.D. Through XPS the surface concentration of the main chemical elements and their depth profiles have been obtained. Attention has been focused on the oxidation states of the elements, oxygen/silicon ratio, peculiar presence of carbonate salts and concentration trends of some elements in the outer atomic layers. Depth trends of aluminium, calcium, magnesium and carbon were studied also through SIMS depth profiles. The whole set of XPS and SIMS data allows the segregation of particular chemical species and the evolution of the original glass to a multilayer system.     

Interdiffusion of hydrogen and alkali ions in glass surfaces

The Boksay-Doremus theory on the interdiffusion of hydrogen and alkali ions in glasses was extended by taking into account the association of hydrogen ions and non-bridging oxygen ions. In the derivation of the interdiffusion coefficient the bulk composition of the glass is taken into account. Theoretical concentration profiles were compared with experimental data, reported in literature, of alkali-alkaline earth-silicate glasses and of a sodium-aluminium-silicate glass. An essential feature of this extended B-D theory is, that the relative order of chemical durability of alkaline earth containing glasses is found by this theory without assuming excessive changes in individual diffusion coefficients.     

Quantitative AFM analysis of phase separated borosilicate glass surfaces

Phase separated borosilicate glass samples were prepared by applying various heat treatments. Using selective chemical etching we performed AFM measurement on the phase separated glass surfaces. A quantitative roughness analysis allowed us to measure precisely the dependence of the characteristic size of the phase domains on heating time and temperature. The experimental measurements are very well described by the theoretically expected scaling laws. Interdiffusion coefficients and activation energy are estimated from this analysis and are consistent with literature data.     

Adsorption/desorption of water on glass fiber surfaces

The interaction of water with glasses and ceramics has a profound effect on their properties. For many samples, standard analytical techniques are inappropriate or insufficiently sensitive for the detection of associated water. A thermodesorption method with an electrolytic detector is described which permits the measurement of minute quantities of water associated with such samples. Because of the sensitivity of the method, the surface water present on low specific area substrates can be measured. A simple and rapid method for obtaining water adsorption isotherms at low pressures is described. A preliminary investigation of single mode optical fibers demonstrates their substantial adsorptive capacity for water, due to the cladding used. Adsorbed water is also shown to differ on two glasses of similar bulk composition, presumably due to large differences in glass surface composition.     

ESCA examination of tin oxide coatings on glass surfaces

ESCA analysis was carried out on glass surfaces which had been treated with SnCl₄ vapour or with SnCl₄/butyl acetate spray at temperatures of 450–650°C. Two forms of stannic tin werer indentified, one assigned to SnO₂ and the other to Sn in association with one or more of the glass elements. Varying proportions of each form of stannic were obtained, depending on type and temperature of treatment. Two forms of carbon were also found, one due to normal hydrocarbon contamination in the instrument, the other apparently associated with the treatment layer.     

The aging of silicate glass surfaces in humid air

Slicate glass surfaces were observed over several weeks in normally humid laboratory air by atomic force microscopy. Auger spectroscopy and lateral force microscopy measurements were also made. Samples in the study include; vitreous quartz, bulk insulation glass, bulk and fibrous textile e-glass, and bulk container glass. Various features developed on these surfaces are consistent with patterns seen in crystal growth from supersaturated solution. Auger spectroscopy reveals the presence of chemically bound carbon and supports the hypothesis that these crystals are alkali and alkali earth carbonate species. The presence of these crystals is expected to affect the bonding of a coating to silicate surfaces.     

Roughness of glass surfaces formed by sub-critical crack growth

This paper presents a study on the roughness of glass fracture surfaces formed as a consequence of sub-critical crack growth. Double-cantilever-beam specimens were used in these studies to form fracture surfaces with areas under well-defined crack velocities and stress intensity factors. Roughness depends on crack velocity: the slower the velocity, the rougher the surface. Ranging from approximately 1 × 10⁻¹⁰ m/s to approximately 10 m/s, the velocities were typical of those responsible for the formation of fracture mirrors in glass. Roughness measurements were made using atomic force microscopy on two glass compositions: silica glass and soda lime silica glass. For silica glass, the RMS roughness, R_q, decreased from about 0.5 nm at a velocity of 1 × 10⁻¹⁰ m/s to about 0.35 nm at a velocity of 10 m/s. For soda lime silica glass, the roughness decreased from about 2 nm to about 0.7 nm in a highly non-linear fashion over the same velocity range. We attributed the roughness and the change in roughness to microscopic stresses associated with nanometer scale compositional and structural variations within the glass microstructure. A theory developed to explain these results is in agreement with the data collected in the current paper. The RMS roughness of glass also depends on the area used to measure the roughness. As noted in other studies, fracture surfaces in glass exhibit a self-affine behavior. Over the velocities studied, the roughness exponent, ζ, was approximately 0.3 for silica glass and varied from 0.18 to 0.28 for soda lime silica glass. The area used for these measurements ranged from (0.5 μm)² to (5.0 μm)². These values of the roughness exponent are consistent with values obtained when the scale of the measurement tool exceeds a critical size, as reported earlier in the literature.     

A comparison of natural and experimental long-term corrosion of uranium-colored glass

The alteration features of historical U-colored glasses exposed to natural weathering for over 150 years were compared with the experimental alteration of similar glass with ～0.3 wt% of uranium using a long-term (up to 426 days) kinetic laboratory batch leaching test in deionized water. Two types of natural corrosion crusts were identified by a combination of SEM/EDS, HRTEM/SAED, EPMA and XRD: (i) formation of a leached layer (up to ～600 μm thick) depleted in alkalis and enriched in Si with stable concentration of U and Al and (ii) formation of lamellae depleted in alkalis, Si and U and enriched in Al. The presence of newly formed gibbsite (Al(OH)₃) and kaolinite (Al₂Si₂O₅(OH)₄) were confirmed in the second type of corrosion crust by HRTEM. Dissolution of the glass components including uranium was determined during the laboratory leaching test. Several μm thick alkali-depleted alteration zones with stable U content relatively enriched in Si and Al were formed on the glass surface. The PHREEQC-2 modeling also predicted the precipitation of secondary gibbsite and kaolinite in the late stages of the leaching. These phases may form especially when sufficient amounts of Al are available from the environment (e.g., soil). Furthermore, they provide surfaces for sorption and may, in some cases, affect the mobility of U ions released from the glass in dependence on pH and U speciation.