Local structure of network modifier to network former ions in soda‐lime alumino‐borosilicate glasses

The structure of soda‐lime alumino‐borosilicate glass was studied using molecular dynamics simulations of samples of varying compositions containing ~20 000 atoms each. Pair distribution functions (PDFs) of cations to oxygen were used for comparison to available experimental data to evaluate consistency between simulations and experiment. Additional PDFs and coordination of the network forming cations (Al/B/Si) to network modifiers (Ca/Na) were examined, which is difficult to measure experimentally. The results are consistent with available experimental data regarding cation‐oxygen bond lengths and network former to oxygen coordination numbers. Si and Al are predominantly 4‐coordinated, with a small concentration of overcoordinated species similar to experimental data. B varied as 3‐coordinated, BO₃, and 4‐coordinated, BO₄, as a function of the amount of Ca²⁺ and Na⁺ present, the ratio of Al₂O₃ to B₂O₃, and the fictive temperature of the sample, similar to experimental data. The simulations provide new information regarding the locations on the network modifiers to the +3 cations, Al and B. For instance, one Al ion can have multiple Na within 4 Å, but also the Na can be within 4 Å of several +3 cations. Such results would indicate a greater complexity of local structure that goes beyond the stoichiometric one +1 modifier ion near one +3 network former or one +2 modifier near two +3 formers in tetrahedral sites.     

钠钙玻璃熔窑应慎用全氧燃烧技术

通过对普通空气助燃熔窑和全氧燃烧熔窑的对比分析,指出在国内以火力发电为主的现状下,对熔化率高、熔化能耗低及产品产值不高的普通钠钙玻璃熔窑,采用全氧燃烧技术后不能节能,氮氧化物减排效果不明显,成本也有所提高,目前应慎重选用全氧燃烧技术;对于熔制质量要求高、熔化能耗较大及产品产值高的特种玻璃,采用全氧燃烧技术后节能和NOx减排明显,成本降低,经济效益和社会效益好,可考虑逐步推行全氧燃烧技术。     

Differences in indentation and wear behaviors between the two sides of thermally tempered soda lime silica glass

Thermal tempering is an industrial process widely used to make soda lime silica (SLS) glass panels stronger and tougher. During the tempering process, the upper and bottom sides of the glass may experience different cooling rates, and thus, their properties could be different. This study characterized changes in surface composition and subsurface glass network structures as well as indentation and wear resistance properties of the air- and tin-sides of 6-mm-thick SLS window panels faced toward the upper and sliding roller sides during thermal tempering. The results showed that although the chemical and structural differences detected with X-ray photoelectron spectroscopy and specular reflection infrared spectroscopy are subtle, there are large differences in nanoindentation behaviors and mechanochemical wear properties of the SLS glass surface. The findings of this study provide further insights into the performance difference between the air- and tin-sides of the SLS glass panel treated with thermal tempering.     

Effect of humidity on friction,wear, and plastic deformation during nanoscratch of soda lime silica glass

Physical flaws and defects on glass surfaces are known to reduce the mechanical strength and chemical durability of glass. The formation of surface defects depends not only on the mechanical conditions of the physical contact but also on the environment in which the contact is made. In this study, the nanoscratch behavior of soda lime silica (SLS) glass was investigated in 10% and 60% relative humidity (RH) conditions. Based on the evolution of friction and scratch depth, the deformation of SLS glass surface could be divided into four regimes: elastic deformation and recovery (E), RH-independent mild plastic deformation (P-1), RH-dependent intermediate plastic deformation (P-2), and RH-independent severe plastic formation (P-3). It is quite surprising to observe that plastic deformation of the glass surface has dependence on RH of the environment (outside the glass) because plastic deformation is the process occurring below the surface (inside the glass) by the externally applied load. From this result, it can be inferred that frictional energy dissipation mode at the sliding interface, which is a function of adsorbed water molecules, influences the subsurface deformation mode. Although friction, wear, and subsurface deformation/damage are all coupled, there is no direct one-on-one correlation among them.     

Origin of the Static Fatigue Limit in Oxide Glasses

Oxide glasses exhibit slow crack growth under stress intensities below the fracture toughness in the presence of water vapor or liquid water. The log of crack velocity decreases linearly with decreasing stress intensity factor in Region I. For some glasses, at a lower stress intensity, K_o, log v asymptotically diminishes where there is no measurable crack growth. The same glasses exhibit static fatigue, or a decreasing strength for increasing static loading times, as cracks grow and stress intensity eventually reaches the fracture toughness. In this case, some glasses exhibit a low stress below which no fatigue/failure is observed. The absence of slow crack growth under a low stress intensity factor is called the fatigue limit. Currently, no satisfactory explanation exists for the origin of the fatigue limit. We show that the surface stress relaxation mechanism, which is promoted by molecular water diffusion near the glass surface, may be the origin of the fatigue limit. First, we hypothesize that the slowing down of slow crack growth takes place due to surface stress relaxation during slow crack growth near the static fatigue limit. The applied stress intensity becomes diminished by a shielding stress intensity due to relaxation of crack tip stresses, thus resulting in a reduced crack velocity. This diminishing stress intensity factor should result in a crack growth rate near the static fatigue limit that decreases in time. By performing Double Cantilever Beam crack growth measurements of a soda‐lime silicate glass, a decreasing crack growth rate was measured. These experimental observations indicate that surface stress relaxation is causing crack velocities to asymptotically become immeasurably small at the static fatigue limit. Since the surface stress relaxation was shown to take place for various oxide glasses, the mechanism for fatigue limit explained here should be applicable to various oxide glasses.     

Chemical structure and mechanical properties of soda lime silica glass surfaces treated by thermal poling in inert and reactive ambient gases

This study employed thermal poling at 200°C as a means to modify the surface mechanical properties of soda lime silica (SLS) glass. SLS float glass panels were allowed to react with molecules constituting ambient air (H₂O, O₂, N₂) while sodium ions were depleted from the surface region through diffusion into the bulk under an anodic potential. A sample poled in inert gas (Ar) was used for comparison. Systematic analyses of the chemical composition, thickness, silicate network, trapped molecular species, and hydrous species in the sodium‐depleted layers revealed correlations between subsurface structural changes and mechanical properties such as hardness, elastic modulus, and fracture toughness. A silica‐like structure was created in the inert gas environment through restructuring of Si–O–Si bonds at 200°C in the Na‐depleted zone; this occurred far below T_g. This silica‐like surface also showed enhancement of hardness comparable to that of pure silica glass. The anodic thermal poling condition was found so reactive that O₂ and N₂ species can be incorporated into the glass, which also alters the glass structure and mechanical properties. In the case of the anodic surfaces prepared in a humid environment, the glass showed an improved resistance against crack formation, which implies that abundant hydrous species incorporated during thermal poling could be beneficial to improve the toughness.     

Synergy between surface mechanochemistry and subsurface dissolution on wear of soda lime silica glass in basic solution

The polishing of oxide glass in aqueous solution is sensitive to not only the mechanical conditions applied by abrasives but also the chemistry of solution. This study elucidates the synergistic interactions of mechanical and chemical effects—especially, the synergetic effects of surface mechanochemical wear and subsurface dissolution are studied by measuring the material removal rate of soda lime silica (SLS) glass upon rubbing with a Pyrex glass ball in noncorrosive (neutral pH) in corrosive solutions (pH 10 and 13 NaOH) as a function of sliding speed. Based on the synergetic model of surface wear and subsurface dissolution, it is found that the mechanochemical surface reaction dominates the wear behavior of SLS glass in neutral and pH 10 solution conditions; the wear of SLS glass in pH 10 is enhanced, compared to the neutral pH case, due to the presence of OH^- ions at the sliding interface. In the case of pH 13, the dissolution of the densified subsurface region, which is formed due to interfacial friction during the surface wear, becomes significant, further enhancing the material removal yield. The finding provides an insight for designing an efficient polishing process in manufacturing of oxide glass materials with a good surface finish.     

Effect of heat treatment on the surface chemical structure of glass: Oxygen speciation from in situ XPS analysis

Compositional changes in unleached and acid‐leached soda‐lime silicate surfaces were tracked with in‐vacuo heating and X‐ray Photoelectron Spectroscopy. Surface oxygen speciation was determined using a stoichiometry‐based algorithm via elemental composition, instead of the typical O 1s peak‐fitting approach. Accurate surface hydroxyl quantification is shown to require dehydration at temperatures near 200°C. On the unleached surface, no change in surface hydroxyl density (~2.5 OH/nm²) is observed in the temperature range of 200°C‐500°C after the initial dehydration. However, repolymerization in the network (non‐bridging oxygen→bridging oxygen) is observed due to volatilization of sodium. The acid‐leached surface undergoes sodium out‐diffusion from the bulk at sub‐T_g temperatures with laterally resolved inhomogeneity and shows a reduction in the concentration of hydroxyls from 4.5 OH/nm² (200°C) to 3.2 OH/nm² (500°C) accompanied by an increase in bridging oxygen. These results suggest that when [OH] > 2.5~3/nm², vicinal OH undergo dehydroxylation with evolution of water, whereas when [OH] < 2.5/nm², most OHs are non‐interacting and isolated (at temperatures below T_g). Furthermore, at temperatures exceeding 300°C, sodium has enough thermal energy to desorb in vacuum and diffuse from the bulk (depending on the abundance & local structure).     

Powder-fed directed energy deposition of soda lime silica glass on glass substrates

Novel glass processing by powder-fed directed energy deposition was explored as a method of adding glass décor to glass surfaces and bottles. Consistent, semitransparent, single-line tracks of soda lime silica glass could be processed onto glass substrates of the same composition, without significant cracks forming in the substrate. A suitable processing window was found with laser power and scan speed showing independent effects on processing. Consideration of processing surface conditions and reduction of laser transmission through transparent substrates was necessary, and the use of an adhesive tape layer aided adhesion of glass feedstock to substrate surfaces. The work demonstrates the potential for a one-step method of glass bottle decoration for the packaging industry, with scope to create 3D designs of high geometric complexity and customizability on glass substrates, thereby adding value to glass packaging by brand differentiation without the high costs associated with molds and tooling.     

Differences in surface failure modes of soda lime silica glass under normal indentation versus tangential shear: A comparative study on Na+/K+-ion exchange effects

The effects of exchanging Na⁺ with K⁺ on the mechanical and mechanochemical properties of a soda lime silica (SLS) glass were investigated. It is known that replacing smaller modifier ions with bigger ions in the silicate glass network, at temperatures below the glass transition (T_g), produces a compressive stress in the subsurface region that enhances resistance to mechanical damages. This study found that when Na⁺ ions in SLS are exchanged with K⁺ ions at 400°C, the hardness, indentation fracture toughness, and crack initiation load of the surface are increased, which is consistent with the chemical strengthening effect. However, the resistance to mechanochemical wear in a near-saturation humidity condition (relative humidity RH = 90%) is deteriorated. When K⁺ ions are exchanged back with Na⁺ ions at 350°C, the wear resistance in high humidity conditions is recovered. These results indicate that the improvement of mechanical properties under indentation normal to the surface is irrelevant with the resistance to mechanochemical wear under tangential shear at the surface. Based on the analysis of the surface chemical composition, silicate network structure, and hydrogen-bonding interactions of hydrous species in the subsurface region, it is proposed that the leachable Na⁺ associated with non-bridging oxygen and subsurface hydrous species in the silicate network play more important roles in the mechanochemical wear of SLS at high RH.     

Review: Elaboration,structure, and mechanical properties of oxynitride glasses

Oxynitride glasses are glasses where threefold coordinated nitrogen atoms substitute for twofold oxygen ones, hence resulting in a larger interatomic cross-linking degree. Such glasses were first observed at the grain boundary in silicon nitride ceramics, where they govern the high-temperature behavior. Later, they were prepared as bulk materials and motivated numerous researches, thanks to their large viscosity, glass transition range, elastic moduli, hardness, and fracture toughness among inorganic and non-metallic glasses. In different chemical systems that were investigated, the synthesis routes and the sources for these exceptional mechanical properties are reviewed. Oxynitride glasses are not easy to process and suffer from the loss of transparency as nitrogen is incorporated over some critical content. Nevertheless, they are attractive “specialty” glasses in various niche areas, thanks to their large refractive index and dielectric constant, improved chemical durability, high softening point, etc., and majorly to their exceptional mechanical properties.     

The origin of the heterogeneous distribution of bismuth in aluminosilicate laser glasses

As one kind of novel and burgeoning laser materials, bismuth‐doped silicate glasses have aroused increasing attention for the super broadband near‐infrared (NIR) emission. However, the large optical scattering loss, resulting from optical heterogeneity in glass color and refractive index, limits their further applications in telecommunication system. Thus, it is urgent to uncover the essence of heterogeneity in Bi‐doped silicate glasses and subsequently improve glass optical performance. It will give us some hint to homogenize the glass component and Bi active centers so as to boost the development of Bi‐based glass materials. Here, taking 1 typical Bi‐doped calcium aluminosilicate glass as an example, we revealed the origin of the optical heterogeneities in glass color and refractive index through the NIR emission spectra, electron probe microanalyzer (EPMA) of elements and X‐ray photoelectron spectroscopy (XPS) of Bi 4f_5/2, Bi 4f_7/2, and Al 2p. The inhomogeneous distribution of Bi and aluminum components is responsible for the heterogeneity in this glass system. In addition, we found that tetrahedral coordinated aluminum favors the existence of Bi NIR centers, consequently resulting in enhanced Bi NIR emissions. Furthermore, based on our results and the role of Al³⁺ in glass network, we demonstrate the homogenizing of glass component by finely tuning glass composition. This work will enrich the understanding of Bi‐doped laser glass and provide a guideline for the design of component‐derived Bi‐doped silicate glasses and fibers with efficient NIR emission and high optical quality.     

Solubility of Gases in Vitreous Silica Described by a Distribution of Dissolution Energies

The solubility of gases in vitreous silica complies well with Henry's Law at low pressures. Deviations observed at high pressures have been explained by site saturation, i.e., the number of dissolved molecules approaches the number of available sites that are assumed to have all the same energy of solution. In the present study, the observed deviations from Henry's Law are explained by a gradual saturation of sites of increasing energy. Experimental data of the solubility of hydrogen, helium, and neon in vitreous silica can be described by a Gaussian distribution of dissolution energies and Fermi-Dirac statistics. The solubility of hydrogen in metallic glasses, as well as the solubility of small molecules in glassy polymers, has been interpreted, and now, glasses in vitreous silica fit into this general concept of small particles in amorphous matrices.     

稀土离子掺杂钠钙硅玻璃的光学性能和光谱特性

通过分光光度计和荧光光谱仪分别测试了几种稀土离子在钠钙硅玻璃中的光学性能和光谱特性,总结了不同稀土离子的吸收峰、发射峰及对应的能级跃迁。结果表明:Ce、Sm、Eu、Tb和Dy 5种稀土离子吸收紫外光并发射可见荧光;Sm、Dy和Yb 3种稀土离子吸收近红外光。     

The origin of anomalous water diffusion in silica glasses at low temperatures

Anomalous water diffusion into SiO₂ glass was observed in a low temperature range, below ~850°C, under a constant water vapor pressure of 355 Torr (47.3 kPa). Both the effective water diffusion coefficient and water solubility exhibited an anomalous time dependence. For example, water solubility in the low temperature range increased initially, achieving much higher values than expected based on extrapolation from higher temperature data, and then decreased with time toward an equilibrium value. This phenomenon was reported earlier, but a complete explanation was not possible; a new model is presented based upon glass surface compressive stress generation and subsequent surface stress relaxation. Water diffusion can promote stress generation and stress relaxation, both of which affect the reaction between diffused molecular water and the glass structure. By considering these stress effects, the anomalous water diffusion behavior in silica glass is explained. Furthermore, the same model can account for the reversal of external tensile and compressive stress effects on water solubility and diffusivity in silica glass observed after a few hours of heat treatment at 650°C in 355 Torr water vapor pressure.     

X‐ray tomography of feed‐to‐glass transition of simulated borosilicate waste glasses

High‐level waste feed composition affects the overall melting rate by influencing the chemical, thermophysical, and morphological properties of a cold cap layer that floats on the molten glass where most feed‐to‐glass reactions occur. Data from X‐ray computed tomography imaging of melting pellets comprised of a simulated high‐aluminum feed reveal the morphology of bubbles, known as the primary foam, for various feed compositions at temperatures between 600°C and 1040°C. These feeds were formulated to make glasses with viscosities ranging from 0.5 to 9.5 Pa s at 1150°C, which was accomplished by changing the SiO₂/(B₂O₃+Na₂O+Li₂O) ratio in the final glass. Pellet dimensions and profile area, average and maximum bubble areas, bubble diameter, and void fraction were evaluated. The feed viscosity strongly affects the onset of the primary foaming and the foam collapse temperature. Despite the decreasing amount of gas‐evolving components (Li₂CO₃, H₃BO₃, and Na₂CO₃), as the feed viscosity increases, the measured foam expansion rate does not decrease. This suggests that the primary foaming is not only affected by changes in the primary melt viscosity but also by the compositional reaction kinetic effects. The temperature‐dependent foam morphological data will be used to inform cold cap model development for a high‐level radioactive waste glass melter.     

Nucleation, growth and detachment of neighboring bubbles over miniature heaters

This work investigates how simultaneous CO₂ bubbles desorb from water and n-heptane when these liquids become supersaturated with dissolved CO₂. Supersaturation is imposed locally by a miniature heater so bubbles grow at adjacent sites across the heater. To suppress buoyancy, experiments are performed at low gravity conditions. The number of nucleation sites and nucleation time delay depend on liquid properties and heating power. Simultaneous bubbles do not grow at exactly the same rate and calculations show that this corresponds to slightly different bubble temperatures. Moreover, they exhibit smaller growth rates than single bubbles at similar conditions, an indication that they compete for dissolved CO₂. As bubbles expand into the surrounding cold liquid, the heater's temperature decreases in a fashion implying the inception of Marangoni convection. Simultaneous bubbles detach due to g-jitters but following different ways in the two liquids. However, they always detach together and at smaller sizes than single bubbles do. A temperature triggered destabilization of contact lines is deemed responsible for this.     

Spatial and temporal scaling of unequal microbubble coalescence

We numerically study coalescence of air microbubbles in water, with density ratio 833 and viscosity ratio 50.5, using lattice Boltzmann method. The focus is on the effects of size inequality of parent bubbles on the interfacial dynamics and coalescence time. Twelve cases, varying the size ratio of large to small parent bubble from 5.33 to 1, are systematically investigated. The “coalescence preference,” coalesced bubble closer to the larger parent bubble, is well observed and the captured power‐law relation between the preferential relative distance χ and size inequality γ, , is consistent to the recent experimental observations. Meanwhile, the coalescence time also exhibits power‐law scaling as , indicating that unequal bubbles coalesce faster than equal bubbles. Such a temporal scaling of coalescence on size inequality is believed to be the first‐time observation as the fast coalescence of microbubbles is generally hard to be recorded through laboratory experimentation. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1441–1450, 2017     

Experimental study of bubble formation in a glass-forming liquid doped with cerium oxide

This work aims to study the mechanisms of oxygen bubble formation coming from redox reaction of a polyvalent element incorporated in a glass melt. Borosilicate glass composition is selected for its use as a glass matrix for nuclear waste conditioning. Cerium is selected as a polyvalent element as it may be found in nuclear waste. The chosen material is characterized in terms of physical properties which influence bubble formation and growth. A postmortem optical microscope approach is used to observe bubbles in the investigated material after thermal treatment for varying temperatures (900°C-1100°C) and durations. To support the understanding of oxygen bubble formation, cerium speciation by X-ray absorption near-edge structure (XANES) and bubble gas composition are experimentally evaluated. In this article, we indicate how bubbles are formed in the investigated glass melt system. It is also demonstrated that the mechanisms that govern bubble evolution are fundamentally the same and that the plot's optimum points are strongly influenced by the temperature. These last statements are confirmed by considering some bubble features, such as bubble mean density and bubble mean diameter evolutions, and normalizing the experimental time using a characteristic residence time (t_η) obtaining thereafter a dimensionless time, which is a function of the glass melt properties obtained by the physical characterizations. The impact of temperature and time on bubble formation is described.