Effect of organic acid vapors on the alteration of soda silicate glass

Organic acids were previously shown to be involved in the alteration of historic soda silicate glasses in humid atmospheres under museum storage conditions. The present study investigates the role of these pollutants on the visual, compositional and structural modification of soda silicate glasses. Replica glasses aged in humid or humid/acidic atmospheres under accelerated conditions were examined and compared using light microscopy, electron microprobe and Raman spectroscopy. The characteristic modifications induced by each atmosphere are described. In the acid polluted atmosphere the leaching process created a layer that retained the transparency of the glass but with a chemical structure hydrated and more polymerized following the loss of alkali and the associated non-bridging oxygens, and the formation of new bridging bonds. In an unpolluted humid atmosphere, the dissolution process caused disruption of the silicate network at the glass surface and formation of an opaque gel layer. The hydrated silicate species and the cations in this gel layer subsequently polymerized to form a new amorphous material, hydrated and more depolymerized than the original glass. This investigation confirms that organic acid pollutants are responsible for the modifications observed on altered historic soda silicate glasses in the collections of the National Museums of Scotland.     

The Debye-Falkenhagen theory of electrical relaxation in glass

The Debye-Falkenhagen-Tomozawa theory (DFT theory) of electrical relaxation in glass is reviewed. This theory interprets the principal electrical relaxation in ionically conducting glasses in terms of relaxation of Debye-Huckel ion atmospheres. Electrical relaxation data is presented to demonstrate that in typical alkali silicate glasses the concentration of free ions is too great for the DFT theory to hold. Further data in a series of borosilicate glasses containing Na₂O at the 0.01 mol% level offers evidence for the validity of the theory in the dilute alkali regime. However, a quantitative fit to the theory can only be made under the assumption that less than 8% of the sodium in the glass is present as free ions at 400°C. This result is discussed in terms of the Bjerrum theory of ionic association.     

Melt crystallization of zinc alkali phosphate glasses

Melt crystallization of two zinc alkali phosphate glasses was studied with X-ray diffraction (XRD) experiments to accelerate efforts to melt process these glasses with organic polymers. The inorganic glasses differed markedly in chemical durability (water sensitivity) and crystallization rates. They were studied at room temperature prior to and after melt processing with XRD experiments and in situ at melt temperatures without flow in a novel differential scanning calorimeter/XRD apparatus. The glasses were found to be amorphous at room temperature and semi-crystalline above their glass-transition temperatures. Higher temperatures and shear (mixing) rates increased the crystallization rate of the glasses. The non-durable (water-sensitive) glass was observed to contain significant levels of crystalline matter after melt processing at 400°C. This process-induced crystallization of the glasses must be controlled, possibly during processing and/or glass formulation, otherwise it may lead to formation of unwanted phase-separated defects in the glass. If high levels of the crystalline matter are present during melt processing, they may lead to irreversible plugging of the processing equipment.     

Distributions of copper and CuBr in CuBr nanocrystallite-dispersed glasses prepared by copper staining

CuBr nanocrystallite-dispersed glasses were prepared by incorporation of copper into bromide ion-containing borosilicate glass using the technique of copper staining. The copper ion incorporation process was mainly controlled by ionic diffusion from the surface to the interior of the glass. The depth profiles of Cu and CuBr concentration were examined by energy dispersive X-ray analysis and by reference to the change in absorption intensity assigned to the CuBr exciton band along the depth. While the Cu concentration was found to decrease monotonically, the CuBr concentration profile showed a maximum at a distance of 10-50 μm from the glass surface. Although the depth reached by the copper ions became greater with increasing heat-treatment time, the depth at which CuBr was precipitated was found to be saturated. This means that regions were found in the glasses in which no CuBr crystallites precipitated, although migration of Cu ions to these regions had taken place.     

Low frequency storage and loss moduli of soda-silica glasses in the transformation range

The storage and loss moduli of sodium silicate glasses in the transformation range are presented. The data cover the frequency range from 10^?3 to 1 rad/sec. Using linear viscoelastic theory, the frequency-temperature dependence is separated into master curves for the storage and loss moduli at the glass transition temperature and shift factor data describing the shift of the curves with temperature along the frequency scale. These binary glasses are concluded to be thermorheologically simple. The relationship between the shape of the master curves and the configurational entropy is shown, and various available theories for the shift factor data are discussed.     

Sub-critical crack growth rate of soda-lime-silicate glass and less brittle glass as a function of fictive temperature

Sub-critical crack growth rates of soda-lime-silicate glass and less brittle glass with different fictive temperatures were compared using the DCDC method under both dry and humid atmospheres in order to investigate the origin of the unique mechanical features of the less brittle glass developed by Ito and his collaborators. In both dry and humid atmospheres, the crack velocity of the soda-lime-silicate glass was slower than that of the less brittle glass. For both glasses, the glass sample with higher fictive temperature showed a slower crack growth rate under both dry and humid atmospheres. These observations can be explained by the tendency for the plastic flow at the crack tip; the soda-lime-silicate glass is expected to show easier plastic flow under tension than the less brittle glass, and also the samples with higher fictive temperatures are expected to show easier plastic flow, leading to greater fracture toughness, K_IC, and slower crack growth rate.     

Optical hole burning studies in europium doped oxide glasses

Europium doped sodium borate, silicate, borosilicate, germanate and tellurite glasses have been prepared by melt quenching technique. Optical spectroscopy techniques were used to characterize the divalent and trivalent ions. Optical hole burning technique was used to characterize rare-earth ion doped glasses for optical data storage. The hole burning mechanisms, which depend on the glass composition and the preparation methods used, are discussed.     

Water penetration mechanisms in nuclear glasses by X-ray and neutron reflectometry

To determine the water diffusion at the early stage of the alteration, X-ray and neutron reflectometry have been performed on altered simplified glasses and the SON68 glass (an inactive R7T7-type French nuclear glass). For the first experiment, the simplified and SON68 glasses were altered at pH 3 and pH 6 and characterized by X-ray reflectometry as a function of the alteration duration. The evolutions of the electron density profile obtained from the reflectivity curves simulations have allowed the determination of the layers compositions. At the beginning of the alteration and for pH 3, the altered surface layer is constituted of a dealkalized zone. Upon alteration progress, the water diffuses inside the layer and hydrolyzes the Si–O–B bonds. For the second experiment, glasses were altered in D₂O (pD 3) and analyzed in D₂O saturated cell. After a D₂O/H₂O substitution, the samples were characterized one more time in H₂O saturated cell. The evolution of the scattering length density shows that in the first stage of the alteration, the layer is constituted of two parts: a dealkalized glass and a dealkalized and boron depleted glass where water has diffused. According to the glass composition and after few hours of alteration, this dealkalized glass part can disappear.     

Effect of rare-earth elements on the plasma etching behavior of the RE–Si–Al–O glasses

The effect of rare-earth elements on the plasma etching behavior of oxide glasses were investigated to develop the window glass for a plasma processing chamber in the semiconductor industry. Aluminosilicate glasses with various rare-earth elements (Y, Gd and La) were prepared and their optical transmittance and plasma etching depth were evaluated. The plasma etching behavior of the glasses was estimated by X-ray photoelectron spectroscopy analysis at the fluorine plasma exposure surface of the glasses. The rare-earth element in the glass was highly related to various properties such as density, molar volume, mechanical properties and plasma etching depth. The cationic field strength of the rare-earth element more strongly affected the plasma etching depth of the glasses than the sublimation point of the fluorine compounds and this may be related to the plasma etching condition.     

Effect of composition on the short-term and long-term dissolution rates of ten borosilicate glasses of increasing complexity from 3 to 30 oxides

Ten borosilicate glass compositions consisting of a ternary sodium borosilicate containing increasing numbers of some of the key elements (Al, Ca, Zr, Ce) present in nuclear glasses were leached in pure water at 90 °C and monitored for up to 14 years. They were then characterized to establish correlations between the glass composition and the short- and long-term alteration rates. We first qualitatively explain the variations of the initial dissolution rate by structural considerations. Then we evidence a qualitative inverse correlation between the initial and residual rates. This counterintuitive result is in fact related to the effect of gel reorganization on the diffusive properties of the passivating layer. Since no equilibrium can be reached between glass and solution, these long-term experiments help in understanding how glasses behave once the solution is saturated with respect to the main glass formers. Very efficient synergy between Ca and hardener elements (Al or Zr) leads to the lowest residual rates, compared with glasses having only one of the two categories of elements. We also confirm the detrimental effect of precipitation of silicate minerals on the residual rate.     

Silica and silica-titania glasses prepared by the sol-gel process

Clear monolithic samples of silica and silica-titania glasses were prepared by the sol-gel process from alkoxides as starting materials. The effects of the composition of the initial alcoholic solutions on the gelation of the silica materials and the effects of using different titanium compounds on the formation of silica-titania gels and glasses were investigated. DTA and TGA revealed losses of water and organic volatiles during heat treatment of the gels at lower temperatures (up to 400°C) and the glass transformation and crystallization behaviour at higher temperatures (up to 1500°C). The effects of using atmospheres with varying oxygen contents on the DTA peaks caused by oxidation reactions were also studied.Structural changes occurring during heat treatment were monitored by infra-red spectroscopy which indicated that the water contents of the glasses after heat treatment to 900°C were about 1000 ppm. Transmission electron microscopy of ion beam thinned foils of a 80 SiO₂20TiO₂ composition showed a microstructure of extremely fine pores for heat treatments up to 1000°C. However, after extended heat treatments above 950–1000°C, the porosity appeared to decrease and a high concentration of fine crystallites of anatase (approximately 100 Å in diameter) embedded in a silica-rich glass matrix were obtained.     

Water concentration profile in silica glasses during surface crystallization

Water concentration profiles in silica glasses during surface crystallization at 1400°C in air were determined by IR spectroscopy with a microscope attachment. Three types of silica glasses with different water contents were examined. Some glass samples initially experienced hydration or dehydration depending upon the original water content. During crystallization, water concentration was highest at the crystal–glass interface and decreased with depth from the interface. Furthermore, water concentration at the interface increased with increasing heat-treatment time for crystallization. The observed water concentration profiles were consistent with the theoretical prediction by Smoluchowski based upon water diffusion modified by water expulsion from the crystal phase. A time-dependent crystal growth rate was also observed for some samples and this behavior appears related to the variation of water content in glasses.     

Glass formation and structure of Na2SSiO2 and Na2SB2O3 glasses

Glass-forming regions of the systems Na₂SSiO₂ and Na₂SB₂O₃ have been investigated in order to clarify whether Na₂S could be substituted for Na₂O in sodium silicate or borate glasses, and the results were interpreted in terms of the structures of silicate and borate glasses. No difference was found in the glass-forming range of SiO₂ content between the Na₂SSiO₂ and Na₂OSiO₂ systems, and the red color of Na₂SSiO₂ glasses suggests that the formation of polysulfides in the glass structure is probably due to the entrance of sulfur ions in the non-bridging sites of the glass network. On the other hand, not all of the sulfur added to the glass batches could be retained in the Na₂SB₂O₃ glasses and the amount remaining in the glass products changed depending upon the amount of sodium ions in the glasses. Only a trace of sulfur was observed in the glasses containing less than 13 mol% of Na₂S in the batches, but the sulfur content in the glasses increased steeply with sodium content up to 35 mol%, reached the maximum and then decreased slowly with sodium content. The insolubility of sulfur in the glasses with low sodium content was interpreted based on the compositional dependence of basicity of alkali-borate glasses, and the change in solubility of sulfur with sodium concentration was explained based on the well-known boron anomaly caused by the change in the coordination state of boron and on the formation of non-bridging oxygens or sulfurs in the glass structure.     

Inter-relationships between composition and near surface mechanical properties of silicate glasses

The surfaces of silicate glasses undergo hydration in normal atmospheric environments. The hydrated region will have different mechanical properties to the bulk glass and this work assesses the inter-relationships between composition and the near surface mechanical properties of silicate glasses through the use of nanoindentation. The effect of glass composition and hydration on the near surface mechanical properties is considered for poorly and highly durable silicate glasses. With poorly durable glasses the hydrated layer depth is much greater than the indentation depth and thus the results obtained on these glasses are used to help interpret the more complex results obtained on more durable glasses where the hydrated layer is smaller than the indentation depth. Based on the results the application of nanoindentation for measuring the near surface mechanical properties of glasses and studying hydration is discussed.     

Hydration of soda-lime glass

The hydration of soda-lime glass is studied using resonant nuclear reactions to measure the hydrogen and sodium profiles of hydrated glasses. The rate of growth of the surface layer of hydrated glass is initially proportional to the square root of time as is characteristic of diffusion controlled processes. After longer exposure a steady-state hydration profile is observed, which indicates that in addition to the diffusion controlled reaction there is a slow etching of the glass surface. The measured hydration profiles are discussed in relationship to the Doremus model of interdiffusing ions, which is found to be in good agreement with the data. This model is also discussed in relationship to measured hydration profiles of vacuum heated samples of hydrated glass.     

Differential etching of chalcogenides for infrared photonic waveguide structures

Chemical etching rates for two different chalcogenide glass compositions, As₄₀S₆₀ and As₂₄S₃₈Se₃₈, were studied using sodium hydroxide based etchant solutions. Etching was performed using a variation of standard photolithographic masking and wet-etching techniques. Variations in etch rate with NaOH concentration and glass composition were observed. The depth of etch was characterized using an optical profilometer. Etch rate differences as large as three orders of magnitude between these two glasses were observed at low NaOH concentration (0.053 M). We present a single variable etch rate curve of etch depth per time (nm/s) versus NaOH overall solution concentration (in M) for these two different chalcogenide glasses. This technology shows promise for fabricating photonic structures and has potential applications in fabricating novel photonic bandgap structures that will function in the long-wave infrared (LWIR) regime.     

Phosphate glass dissolution in aqueous solutions

Rates of aqueous dissolution are reported for a series of phosphate glasses having the composition (50 ? X)M₂O·(X)CaO·50P₂O₅. Dissolution reactions involving the consumption of H⁺ and OH^? were monitored using pH stat titration techniques, solution analyses using inductively coupled plasma emission, and depth profiling of corroded glass surfaces for H and other elements using elastic recoil detection analysis and Rutherford backscattering. These analytical results indicate that the phosphate glasses dissolve uniformly due to acid- or base-catalyzed hydration of the polymeric phosphate network. The rate and nature of this hydration appears to be controlled by the surface pH and/or charge which develops at the glass/ solution interface. The implication of these results on dissolution models for both the phosphate and silicate glasses is discussed.     

Aging in chalcohalide glasses: Origin and consequences

The application of chalcogenide and chalcohalide glasses is limited by their uncontrolled drift in properties over time due to aging processes. In the present work, we perform aging experiments on some chalcohalide glasses in oxidizing, inert and reducing atmospheres and afterwards we measure the elemental concentration depth profiles in the surface layer of the glasses by using secondary neutral mass spectroscopy. The results show that anionic diffusion processes occur in the glasses during aging. The aging process leads to a decrease in microhardness of the studied glasses, which is attributed to both physical aging (i.e., structural relaxation) and chemical aging (i.e., compositional change of the surface layer).     

An investigation of the local iron environment in iron phosphate glasses having different Fe(II) concentrations

The local environment around iron ions in iron phosphate glasses of starting batch composition 40Fe₂O₃-60P₂O₅ (mol%) melted at varying temperatures or under different melting atmospheres has been investigated using Fe-57 Mössbauer and X-ray absorption fine structure (XAFS) spectroscopies. Mössbauer spectra indicate that all of the glasses contain both Fe(II) and Fe(III) ions. The quadrupole splitting distribution fits of Mössbauer spectra show that Fe(II) ions occupy a single site whereas Fe(III) ions occupy two distinct sites in these glasses. When melted at higher temperatures or in reducing atmospheres, the Fe(II) fraction in the glass increases at the expense of Fe(III) ions at only one of the two sites they occupy. The pre-edge feature in the XAFS data suggests that the overall disorder in the near-neighbor environment of iron ions decreases with increasing Fe(II) fraction. The XAFS results also show that the average iron-oxygen coordination is in the 4-5 range indicating that iron ions have mixed tetrahedral-octahedral coordination.     

Chemical attack of optical glass surface by formic acid vapor

The surface deterioration of glass by the attack of formic acid vapor was observed by an optical microscope, an ellipsometer, an X-ray diffractometer and an electron microprobe X-ray analyzer. The refractive index and thickness of the anomalous surface film formed on the glass were measured by means of ellipsometry. In the weathering of SF-3 and KzFS-2 glasses, the presence of water vapor in the atmosphere is necessary to produce stains on the glass surface. In the SF-3 glass with a SiO₂ network, the diffusion of Pb²⁺ and the formation of fine crystalline lead formate play important roles. In the KzFS-2 glass with a B₂O₃ network, both the destruction of the B₂O₃ network and the formation of fine crystals of boric acid play important roles. The diffusion of Pb²⁺ is not so important.