Thermal Analysis of Reactions in Soda–Lime Silicate Glass Batches Containing Melting Accelerants: II, Multicomponent Systems

The glass melting reactions in a multicomponent system (sand–soda ash–calcite–dolomite–feldspar) were studied using data from DTA, TGA, and XRD interactively. The first-formed liquid phase occurred at 700°C from eutectic melting among CaCO₃, Na₂CO₃, and MgO. Further liquid phase formed at the CaCO₃–Na₂CO₃, eutectic at 785°C and a fusion reaction among SiO₂, CaO, and the molten phase at 812°C. Reactions between molten soda ash and silica grains to form a sodium disilicate coating also occurred in this temperature range. The effects of reaction accelerant additions (Na₂SO₄, NaNO₃, NaCI) on batch fusion were analyzed. Sodium chloride was found to be the most effective melting accelerant due to the formation of a NaCI–Na₂CO₃ eutectic liquid phase at ∼636°C, which effectively attacked the silica relic. CO₂ gas release terminated ∼80°C earlier with 1 wt% NaCI additions to the base glass.     

Indentation Creep of Hydrated Soda–Lime Silicate Glass Determined by Nanoindentation

Time-dependent deformation behavior was investigated for soda–lime silicate glass with various water contents, using a nanoindentation technique. The complete indentation curve, loading and unloading part, is analyzed. It is shown that this deformation behavior may be represented in terms of a simple mechanical model analogous to a viscoelastic system. Values for Young's modulus were derived, a retardation spectrum was deduced, and apparent viscosity values were calculated. Structural rearrangements of the glass appear to be responsible for the observed changes of the viscoelastic properties. Water in the glass reduces Young's modulus and yield stress and thus promotes viscous flow.     

Effects of Particle Size on the Fusion of Soda–Lime–Silicate Glass Containing NaCl

The coupled effects of particle size and 1 wt% NaCl additions on the sequence of melting reactions in a multicomponent system (sand–soda ash–calcite–dolomite–feldspar) were studied using data from DTA, DTGA, and XRD interactively. Glass batches varied in average particle size from 250 μm to finer than 45 μm. Milestone events in the fusion process of the coarse particle base glass were elucidated. The termination temperature of the last significant reaction associated with CO₂ release was 35°C lower in the fine particle size batch than with the coarsest batch. Liquid-phase formation at ∼523°C in the batch with 1 wt% NaCl occurred to an increasingly sizable extent with decreasing particle size. This contrasts with a similar effect at ∼630°C for a comparable batch without NaCl via eutectic melting between soda ash and dolomite. Sodium chloride additions significantly enhanced dissolution of CaO relic.     

In Situ Cube-Corner Indentation of Soda–Lime Glass and Fused Silica

Indentation fracture with a cube-corner diamond pyramid on soda–lime silicate glass and fused silica is investigated during the entire indentation cycle in both silicone oil and ambient-air environments. Radial cracks form immediately on loading in all cases. The two-component, elastic-contact + elastic-plastic mismatch (residual) stress field model that has been used successfully to describe radial crack evolution at Vickers indentations fails to describe the fracture response with the cube-corner. The amplitudes of both elastic-contact and residual stress-intensity factors as deduced from these cube-corner experiments are up to a factor of 10 greater than have been previously observed.     

Crack Initiation by Indentation Fatigue in Lead Alkali and Soda–Lime Glass

An indentation technique using a conventional Vickers microhardness tester was used to evaluate fatigue properties of lead-alkali and soda-lime silica glasses. The specimens were indented repeatedly at the same point with subcritical loads until radial cracks were initiated. The number of cycles to initiate the cracks at different subcritical loads demonstrated typical fatigue curves for both glasses. The uniqueness of the experiment was that the diagonal lengths of the deformed cavity were observed to increase with the number of cycles. This increase of the deformed cavity for a certain number of cycles prior to the visibility of crack initiation was analyzed, correlating the elastic-plastic phenomenon and the accumulation of the residual stress in each cycle.     

Leaching Behavior of Sodium from Fine Particles of Soda–Lime–Silicate Glass in Acid Solution

The leaching behavior of Na from soda–lime–silicate glass was investigated by preparing glass powders with average particle diameters of 53 and 19 μm, and leaching in HNO₃ at 90°−140°C. A new theoretical equation for Na leaching from a spherical particle is proposed based on the assumption that a rate-determining process is the three-dimensional self-diffusion of Na in glass. The diffusion constant ( D ) of Na in glass was obtained by fitting the experimental data to a theoretical equation. The values of D and activation energy obtained are comparable to those obtained in other studies on larger particles.     

Optical,FTIR and DC Conductivity of Soda Lime Silicate Glass Containing Cement Dust and Transition Metal Ions

Four soda lime silicate glass samples of composition (70 % SiO₂+ 20 % Na₂O+ 10 % CaO mol %) were prepared after adding 5 wt% cement dust to each sample mixture besides 0.1 wt% of one transition metal (TM) oxide of Fe, Co or Cu. The four samples were melted by a conventional melt-annealing technique at 1400 ^°C for 2.5 h. Density, UV/VIS, FTIR and DC conductivity measurements were performed for each glass. Experimental results indicate that there are only slight differences in the density values. The optical spectra reveal that the TM free sample and the sample containing iron ions have the same spectral features while the samples containing copper or cobalt exhibit distinct characteristic absorption bands due to each TM ion. FTIR spectra reveal characteristic vibrational bands due to stretching and bending modes of the silicate network. DC conductivity data show variations in the values of the studied samples according to the type of TM ions added. All the experimental results were correlated with each other in accordance with the current views on the constitution of the studied glasses.     

Melting and Crystallization of Silicate Systems Relevant to Thermal Barrier Coating Damage

The melting and crystallization behaviors of model calcium–magnesium–alumino‐silicate (CMAS) compositions relevant to the degradation of thermal barrier coatings (TBCs) were investigated. A primary goal was to establish a baseline for studies on CMAS reactions with TBC materials, reported separately, and their potential to mitigate degradation. Ternary calcium alumino‐silicate (CAS) compositions investigated melt below their equilibrium solidus owing to their metastable phase constitution. Additions of MgO or FeO_x have significant effects on the melting behavior, depending on the C:A:S proportions. Amorphization on cooling is commonplace, with MgO, AlO_1.5, and especially FeO_x promoting crystallization. The behaviors of amorphous and crystalline versions of the same CMAS are different and depend on heating/cooling rates, with attendant implications for their interaction with TBCs.     

Sodium Diffusion in Glass: I, Single-Alkali Silicate

The isotope effect for ²²Na/²⁴Na diffusion was measured for three 25-mol% alkali-silicate glasses. A multiple diffusion mechanism wherein the Na ions diffuse both singly (vacancy mechanism) and in pairs (interstitialcy mechanism) provided the best agreement with the experimental data. According to this tentative model, diffusion by Na ion pairs predominates at low temperatures, and the fraction of Na ions diffusing singly increases with increasing temperature. In the glasses investigated, nearly all of the Na ions diffuse singly in the vicinity of the transformation range.     

Glass Formation, Properties and Structure of Soda–Yttria–Silica Glasses

The glass-formation region of the soda–yttria–silica system was determined. The glasses within this region were measured to have a density of 2.4 to 3.1 g/cm³, a refractive index of 1.50 to 1.60, Vickers hardness values of 3.7 to 5.8 GPa, softening temperature between 500° and 780°C, and a coefficient of thermal expansion of 7 × 10^-6/oC to 19 × 10^-6/o C. Aqueous chemical durability measurements were made on select glass compositions while infrared transmission spectra were used to investigate the glass structure and its effect on glass properties. A compositional region was identified which exhibited high thermal expansion, high softening temperatures, and good chemical durability.     

Fundamentals of Glass-to-Metal Bonding: II, Reactions of Tantalum and Sodium Silicate Glass

A compound, identified by X-ray diffraction analysis as sodium metatantalate (Na₂Ta₂O₆), was found at the interface between a sodium silicate glass and tantalum metal which had been heated in vacuum to 1000°C. Thermodynamic calculations, followed by further experimental evidence, were used to determine the chemical reaction between tantalum and sodium silicate which resulted in the formation of Na₂Ta₂O₆. The compound was synthesized by other methods and its structure was investigated.     

Dissolution Rates of Commercial Soda–Lime and Pyrex Borosilicate Glasses: Influence of Solution pH

Dissolution rates of two commercial soda—lime silicate glasses and Pyrex borosilicate glass (Corning 7740) have been measured as a function of pH. The dissolution rate was constant with time and increased with increase in pH from 4 to 9. The activation energy for dissolution was nearly constant with pH for the Pyrex borosilicate glass, and decreased somewhat as pH increased for the soda—lime glasses. The openness of the glass surface influences strongly the rate of dissolution. The solubility of silica as a function of pH increases at pH above 8 but does not seem to be quantitatively related to dissolution rate. Other possible influences on this rate are briefly considered.     

Effect of Melting History on the Mechanical Properties of Glass: I, Role of Melting Time and Atmosphere

The pristine strength of 0.5Li₂O·0.5K₂O·2SiO₂ glass measured in 3-point bending under liquid nitrogen was studied as a function of melting time and atmosphere at a constant melting temperature. The atmosphere over the melt was one of the most important parameters affecting the pristine strength. The most significant time-dependent melting effects and the highest strengths resulted from melting in a dry atmosphere of O₂ or air. In contrast, vacuum-melted and Ar-melted glasses had the lowest strengths. Melting in N₂ or CO₂ led to intermediate strengths. The presence of water vapor in the atmosphere during melting was detrimental to strength in those cases where very high strengths had been obtained with dry gases. The introduction of water vapor into those gases which in the dry state had led to low-strength glasses did not significantly affect the strength. The effects of the atmosphere in leading to oxygen-deficient or excess-oxygen glasses on the formation or dissolution of microheterogeneous regions were correlated with the pristine strengths of the glasses.     

芒硝含率对高碱铝硅酸盐玻璃熔化及澄清的影响

通过高温炉熔制样品,利用徕卡显微镜观察不同芒硝含率下熔制样品中未熔石英砂量以及气泡量;探讨澄清剂在高碱铝硅酸盐中的澄清机理,得出芒硝含率对高碱铝硅酸盐玻璃熔化和澄清的影响规律。     

Internal Friction of Simple Alkali Silicate Glasses Containing Alkaline-Earth Oxides: I, Experimental Results

The internal friction of simple alkali silicate glasses to which systematic alkaline-earth oxide additions were made was investigated. These additions produced two significant results: (1) The two peaks previously reported in alkali silicate glasses were shifted to higher temperatures and decreased in height and (2) a third peak was found in some glasses which became more pronounced with increasing alkaline-earth oxide content. Internal friction measurements of alkali-free silicate and phosphate glasses also are described. In these glasses, peaks were present which closely resembled those found in glasses containing alkali.     

Fundamentals of Glass-to-Metal Bonding: I, Wettability of Some Group I and Group VIII Metals by Sodium Silicate Glass

The degree of wetting of Cu, Ag, Au, Pd, Pt, and Ni by three sodium silicate glasses having 30.8, 33.6, and 36.9% Na₂O was observed in vacuum, helium, hydrogen, oxygen, and air atmospheres. No apparent correlation of the contact angles of the three sodium silicate glasses with the metals studied in the various atmospheres was observed with the position of the metals in the periodic system of elements. It was found that within the range of glass compositions studied, there is no appreciable difference in contact angle for identical conditions. In pure helium no chemical effect of atmosphere itself is possible. The observed variations in contact angle from metal to metal may be related to the polarizing power of the metal, which may be presumed to have the effect of lowering the interfacial tension. At present it is felt that no reaction between pure metal and glass occurs in an inert atmosphere. In oxygen and hydrogen atmospheres chemical reactions are possible, and these reactions result in phenomena that favor spreading. Results are reviewed on a theoretical basis.     

Incorporation of Galvanic Waste (Cr, Ni, Cu, Zn, Pb) in a Soda–Lime–Borosilicate Glass

In the present investigation, a glassing process for galvanic waste (GW) incorporation with a high chemical stability is presented. Glasses with up to 50 wt% of galvanic solid waste by modifications in the basic composition of soda–lime–borosilicate glasses were prepared. After fusing at temperatures up to 1300°C, the glasses were characterized by inductively coupled plasma, scanning electron microscopy/energy-dispersive X-ray spectroscopy, high-temperature microscopy, transmission and reflected light microscopy, nuclear magnetic resonance, X-ray photoelectron spectroscopy, and X-ray diffraction methods. The chemical stability was evaluated by hydrolytic attack assays. Glasses containing up to 40 wt% of GW with a very high chemical stability, similar to bottle glasses, were obtained.     

Thermal Poling of Soda‐Lime Silica Glass with Nonblocking Electrodes—Part 2: Effects on Mechanical and Mechanochemical Properties

The mechanical and mechanochemical properties of soda lime silica (SLS) glass surfaces can vary with the sodium ion (Na⁺) concentration in the subsurface region. Changes in these properties were studied upon modification of Na⁺ concentrations in the SLS glass by thermal poling. In Part‐1, it is found that the Na⁺‐depleted and Na⁺‐gradient layers could be formed at the anode and cathode sides, respectively. Here in Part‐2, we show that Na⁺ ions play a pivotal role in the mechanochemical wear property upon lateral shear stress. The Na⁺‐depleted glass wear more readily as relative humidity (RH) increases, while Na⁺‐gradient glass becomes resistant to wear at high RH. It is also found that the Na⁺‐gradient glass surface has a higher elastic modulus and hardness with very little change in fracture toughness compared to the pristine surface. The Na⁺‐depleted glass surface shows a lower elastic modulus and hardness; but its fracture toughness is significantly improved, which might be due to a larger densification capacity of Na⁺‐depleted layer.     

Thermal Poling of Soda‐Lime Silica Glass with Nonblocking Electrodes—Part 1: Effects of Sodium Ion Migration and Water Ingress on Glass Surface Structure

It is generally well known that not only the sodium itself, but also the non‐bridging oxygen (NBO) sites associated with sodium ions are largely responsible for the surface reactivity of soda‐lime‐silica (SLS) glass. Thermal poling can modify the distribution of sodium in the subsurface region. In this work, a commercial SLS float glass was thermally poled using nonblocking electrodes in air. The Na⁺?depleted anode surface and the Na⁺?gradient cathode surface were characterized using a variety of methods to find the compositional, structural and morphological effects of thermal poling. Of particular significance is the use of nondestructive vibrational spectroscopy methods, which can lead to new and improved understanding of water interactions with sodium and its sites in the glass. It was found that during thermal poling, the Na⁺?depleted glass network on the anode side undergoes condensation reactions of NBO sites accompanied by the increase in concentrations of silanol (SiOH) groups and molecular water species. In contrast, silanol and water species do not increase and the silicate network change is negligible in the Na⁺?gradient cathode side. Vibrational sum frequency generation (SFG) spectroscopy analysis revealed the difference in distributions of hydrous species in the Na⁺?depleted and Na⁺?gradient surfaces. The structural information of the thermally‐poled surfaces provides critical insights needed to understand the mechanical and mechanochemical properties of the Na⁺?concentration modified SLS glass surfaces reported in the Part 2 companion paper.     

Specific Features of Changes in the Properties of One- and Two-Alkali Borate Glasses Containing Water: I. Viscosity, Thermal Expansion, and Kinetics of Structural Relaxation in Binary Alkali Borate Glasses

Alkali borate glasses with different contents of residual water are prepared by varying the synthesis conditions. The temperature dependences of the viscosity and thermal expansion of glasses are obtained. The structural relaxation parameters are calculated from the hysteresis dilatometric curves measured. The water content is determined using the IR absorption spectra in the range of stretching vibrations of hydroxyl groups at room temperature. It is found that an increase in the water concentration in alkali borate glasses leads to a decrease in the viscosity. The character of variations in the viscosity logarithm with a change in the water content depends on the alkali cation concentration. The glass transition temperatures determined from the dilatometric curves for all the studied glasses decrease with an increase in the water content. As the water concentration increases, the thermal expansion coefficient (above and below the glass transition range) and the degree of fragility decrease for glasses containing 25 mol % Na₂O, increase for glasses with an alkali oxide content of 15 mol %, and remain virtually unchanged for glasses involving 5.5 mol % Na₂O. A change in the water content in the concentration range under investigation does not affect the structural relaxation parameters.