Ion migration study in acid-leached soda–lime–silica glass by thermally stimulated depolarization current analysis

Ionic conductivity in silicate glasses is a major issue in the energy sector due to its detrimental effect on electric energy generation and storage and has received increasing attention over the past years. In this study, surface modification of soda–lime–silica (SLS) float glass via acid-leaching treatment (pH 1) was implemented to understand the impact on ionic transport. The acid-leaching treatment created a sodium-depleted “silica-like” structure in the near-surface region with depths of 110 ± 20 nm for the air-side and 93 ± 2 nm for the tin-side of the SLS glass. Using the thermally stimulated depolarization current technique, two thermally activated relaxation peaks were found to be associated with different ion migration mechanisms. The first peak (P1) with activation energy of ∼0.85 eV was attributed to dc conduction of Na⁺ ions through the glass bulk. A second overlapping peak (P2) at a higher temperature was found to be related to a more limited Na⁺ ion migration through the acid-leached structure, due to H⁺ conduction, or a coupled contribution of both mechanisms.     

Enhanced luminescence of manganese in singly doped white light zinc phosphate glass

On the basis of a kind of zinc phosphate oxynitride glass matrix with a broadband blue light, a series of manganese single-doped glasses were obtained. A broader red emission with the higher intensity belonging to the Mn²⁺ ion was observed in this glass matrix. The mechanism of the emission from Mn²⁺ ions was clarified through Mn³⁺ as an “energy acquisition probe” to replace complex dynamic luminescence discussion, which was a fit explanation for the differences in luminescence behavior of Mn ions in prepared glasses at different degrees of redox. The research results indicated that the prepared manganese-doped glass was a potential candidate as phosphor-converted white-light-emitting diodes. An encapsulated white-light-emitting diode device based on this glass with 276 nm ultraviolet chip was achieved. It showed the CIE values of (0.33, 0.35), high CRI (Ra = 86), and low color temperature (5228 K).     

ELECTROLYTICAL REPLACEMENT OF SODIUM BY AMMONIUM IN GLASS*

A review is given of the exchange of ions (1) in glasses containing water, (2) on the hydrated surfaces of ordinary glasses, and (3) in commercial glasses with and without the application of an electrical field, and it is shown that the ammonium ion offers unique features. It may be electrolytically introduced into soda glasses without impairing their structure as much as other ions. Because of the volatility of ammonium compounds, it may be removed easily, leaving a glass of higher silica content. Such glasses could be obtained in some experiments, but the soda probably cannot be entirely removed.     

Hydronium Ions in Soda‐lime Silicate Glass Surfaces

The presence of leachable alkali ions, or their hydrated sites in the glass, is believed to be a determining factor for the interfacial water structure at the glass surface, influencing the surface properties of glass. The interfacial water structure on soda‐lime silicate glass in humid ambience at room temperature was analyzed with sum‐frequency‐generation (SFG) vibration spectroscopy, which can probe the interfacial water layer without spectral interferences from the gas phase water. The soda‐lime glass surface exposed to water vapor shows three sharp SFG peaks at 3200, 3430, and 3670 cm^?1 in SFG, which is drastically different from the SFG spectra of the water layers on the fused quartz glass surface and the liquid water/air interface. The sharp peak at 3200 cm^?1 is believed to be associated with the hydronium ions in the Na⁺‐leached silicate glass surface. The 3200 cm^?1 peak intensity varies with the relative humidity, indicating its equilibrium with the gas phase water. It is proposed that the hydronium ions in the Na⁺‐leached sites produce compressive stress in the silicate glass surface; thus the growth of hydronium ions with increasing humidity might be responsible for the increased wear resistance of soda‐lime glass surfaces in near‐saturation humidity conditions.     

Evaluating the role of composition and local structure on alkali out-diffusion in glasses for thin-film solar cells

The presence of alkali ions has reportedly improved the performance of CIGS/CZTS–based thin-film solar cells. The out-diffusion of the alkali ion, in particular, Na, from the glass substrate offers a facile scalable route of supplying the alkali ions during the growth of the absorber layer. In this work, we demonstrate the diffusion of different alkali ions (Li/Na/K) from composition tuned glasses with intentionally incorporated excess alkali ions into a thin Mo film, typically used as a bottom electrode in solar cells. We also evaluate the physical, mechanical, and thermal properties of the glasses for suitability as a substrate in thin-film deposition. The out-diffusion of alkali ions to the overlayer is found to be critically influenced by the composition and the local structure of the glasses. The Na ions exhibit the highest extent of diffusion among the alkali ions present in glass substrates, while that for the K-ions is the lowest. For the glasses with mixed alkali ions, the presence of Li facilitated the out-diffusion of Na, whereas K ions appear to inhibit the same. Differently with the existing reports, we show that the activation energy and the presence of Ca ions as additional modifiers play a crucial role in the transport mechanism of the ions. In addition, the synthesized glasses exhibit hardness of the order 5-7 GPa, density ~2.55 g cm^-3. The glass transition temperature lies between 535 and 580°C and the coefficient of thermal expansion 8.5-10 ppm/K, which is highly suitable for use as substrates in thin-film solar cells.     

Chemical durability of borosilicate pharmaceutical glasses: Mixed alkaline earth effect with varying [MgO]/[CaO] ratio

Glass for pharmaceutical packaging requires high chemical durability for the safe storage and distribution of newly developed medicines. In borosilicate pharmaceutical glasses which typically contain a mixture of different modifier ions (alkali or alkaline earth), the dependence of the chemical durability on alkaline earth oxide concentrations is not well understood. Here, we have designed a series of borosilicate glasses with systematic substitutions of CaO with MgO while keeping their total concentrations at 13 mol% and a fixed Na₂O concentration of 12.7 mol%. We used these glasses to investigate the influence of R = [MgO]/([MgO] + [CaO]) on the resistance to aqueous corrosion at 80°C for 40 days. It was found that this type of borosilicate glass undergoes both leaching of modifier ions through an ion exchange process and etching of the glass network, leading to dissolution of the glass surface. Based on the concentration analysis of the Si and B species dissolved into the solution phase, the dissolved layer thickness was found to increase from ~100 to ~170 nm as R increases from 0 to 1. The depth profiling analysis of the glasses retrieved from the solution showed that the concentration of modifier ions (Na⁺, Ca²⁺, and Mg²⁺) at the interface between the solution and the corroded glass surface decreased to around 40%–60% of the corresponding bulk concentrations, regardless of R and the leaching of modifier cations resulted in a silica-rich layer in the surface. The leaching of Ca²⁺ and Mg²⁺ ions occurred within ~50 and <25 nm, respectively, from the glass surface and this thickness was not a strong function of R. The leaching of Na⁺ ions varied monotonically; the thickness of the Na⁺ depletion layer increased from ~100 nm at R = 0 to ~200 nm at R = 1. Vibrational spectroscopy analysis suggested that the partial depletion of the ions may have caused some degree of the network re-arrangement or re-polymerization in the corroded layer. Overall, these results suggested that for the borosilicate glass, replacing [CaO] with [MgO] deteriorates the chemical durability in aqueous solution.     

Relative Acidities of Glasses Containing Al2O3 and TiO2 as Determined by the Oxygen Electrode

The oxygen electrode has been utilized to determine the relative acidities of sodium and potassium silicate glasses containing alumina and titania in the temperature range 300° to 500° C. The acidity of a potassium or sodium silicate glass is increased by substituting alumina or titania for the soda or potassia. The first additions of alumina tend to increase the acidity of both glasses by forming A1O₄ tetrahedra which utilize a portion of the nonbridging oxygen ions to fulfill the coordination requirements. The results indicate further that the Ti⁴⁺ ion is in both fourfold and sixfold coordination in the sodium and potassium glasses. Titania increases the acidity when it is in sixfold coordination but tends to decrease it when in fourfold coordination. Both titania and alumina increase the acidity of the potassium glasses more than that of the sodium glasses. This is interpreted on the basis that the oxygen network of the potassium glass, being initially the looser, is tightened more than that of the sodium glass. However, the polymerization of the A1O₄ tetrahedra at the higher alumina concentrations causes a loosening of the oxygen network. Previous assumptions that the oxygen electrode reaction is independent of the metal used for the electrodes have been verified by reproducing the data using platinum foil as the electrode material in place of silver foil.     

Optical properties of bismuth tellurite glasses doped with holmium oxide

The study of polarizability, optical basicity, and electric susceptibility carried out on the new and very rare set of bismuth - tellurite glasses doped with Ho³⁺ ions were fabricated by the conventional melt quenching process. The non-crystalline nature was confirmed by X-ray diffractometer measurements. Physical properties such as rare earth ion concentration, interionic distance, polaron radius, and average tellurium - tellurium separation were investigated by appropriate formulae. By UV absorption spectra, optical properties of Ho³⁺ ions doped glasses were found in the wavelength limit from 400 to 700 nm. The optical properties like optical dielectric constant, electronic polarizability, metallization criterion, electronegativity, optical basicity, and electric susceptibility were measured with appropriate mathematical relations. The impact of Ho³⁺ ions on nonlinearity in optical parameters discloses bismuth tellurite glass as a new applicant for holmium doped fiber amplifier applications.     

Transport of potassium ions in niobium phosphate glasses

The influence of Nb₂O₅ on the structure and ionic conductivity of potassium phosphate glasses was investigated in glasses with composition xNb₂O₅–(100-x)[0.45K₂O–0.55P₂O₅], x = 10–47 mol%. The Raman spectra of glasses reveal a transition from predominantly orthophosphate to predominantly niobate glass network with increasing Nb₂O₅ content. In the glass structure, niobium forms NbO₆ octahedra which are interlinked with phosphate units for the glass containing 10 mol% Nb₂O₅, but for higher Nb₂O₅ content they become mutually interconnected via Nb-O-Nb bonds. The transport of potassium ions was found to be strongly dependent on the structural characteristics of the glass network. While the mixed niobate-phosphate glass network hinders the diffusion of potassium ions by providing traps that immobilize them and/or by blocking the conduction pathways, predominantly niobate glass network exhibits a rather facilitating effect which is evidenced in the trend of DC conductivity as well as in the features of the frequency-dependent conductivity and typical hopping lengths of potassium ions.     

Hydration and reaction mechanisms on sodium silicate glass surfaces from molecular dynamics simulations with reactive force fields

Recent development of reactive force fields have enabled molecular dynamics simulations of interactions between silicate glasses and water at the atomistic scale. While multicomponent silicate glasses encompass a wide variety of compositions and properties, one common structural feature in these glasses is the combination of the network structure that is made up of silica tetrahedra linked through corner sharing interspersed with network modifiers like alkali and alkaline-earth ions that break up the Si–O–Si linkages by forming nonbridging oxygen. In reactions with water, ion exchange between alkali ions in the glass and proton or hydronium in the solution, as well as hydrolysis reaction of the Si–O–Si linkages and subsequent silanol formation, is observed and well documented. We have used a set of recently developed reactive force field to investigate the reactions between water and the surfaces of silica and sodium silicate glasses of different compositions for reactions up to 8 nanoseconds. Our results indicate sodium leaching into water and diffusion of water molecules up to 25 Å into the glass surface. We examined the structural and compositional changes inside the glass and around the diffused ions and use these to explain the rates of silanol formation at the surface. We also observed proton transport in the glass which has an indirect influence on the silanol formation rates. While the surface of the glass was rough to start with, it undergoes further modification into a hydrated gel-like structure in the glass for up to 5 Å in the higher alkali containing glasses. It was found that the leached sodium ions remain close to the interface and that fragments of silicate network from the surface is capable of dislodging from the bulk glass and enter the aqueous solution. These simulations thus provide insights into the formation and structure of an alteration layers commonly observed in multicomponent silicate glasses corroded in aqueous solutions.     

Mechanochemical Wear of Soda Lime Silica Glass in Humid Environments

The mechanochemical wear of multicomponent glasses was studied under controlled humidity conditions using a reciprocating ball‐on‐flat tribometer. For dry conditions, the surfaces were extensively damaged by scratching for all of the glasses, while for humid conditions the wear behavior varied with the glass composition suggesting a chemical effect on scratch behaviors of glass surfaces. The wear of soda lime silica (also called sodium calcium silicate) glass was suppressed with increasing humidity, while the borosilicate and barium boroaluminosilicate glasses showed an increase in wear volume with increasing humidity. The unique humidity dependence of the observed mechanochemical wear of soda lime silica glass supports the hypothesis that hydronium ion formation in the sodium‐leached sites of the soda lime glass enhances its wear resistance.     

Neutron diffraction study of antibacterial bioactive calcium silicate sol-gel glasses containing silver

Bioactive sol-gel calcia-silica glasses can regenerate damaged or diseased bones due to their ability to stimulate bone growth. This capability is related to the formation of a hydroxyapatite layer on the glass surface, which bonds with bone, and the release of soluble silica and calcium ions in the body fluid which accelerates bone growth. The addition of silver ions imbues the glass with antibacterial properties due to the release of antibacterial Ag⁺ ion. The antibacterial activity is therefore closely dependent on the dissolution properties of the glasses which in turn are related to their atomic-level structure. Structural characterization of the glasses at the atomic level is therefore essential in order to investigate and control the antibacterial properties of the glass. We have used neutron diffraction to investigate the structure of silver-containing calcia-silica sol-gel bioactive glasses with different Ag₂O loading (0, 2, 4, 6 mol%). The presence of the silver had little effect on the host glass structure, although some silver metal nanoparticles were present. Results agreed with previous computer simulations.     

Influence of glass composition on photoluminescence from Ge2+ or Ag nano-cluster in germanate glasses for white light-emitting diodes

Germanium glass has attracted much interest because of its potential application as the optical waveguides and communication devices. In this work, germanium glass was prepared, exhibiting the blue luminescence at the 410 nm from the Ge²⁺. The influence of SiO₂ addition in the germanate glass on the 410 nm luminescence of the Ge²⁺ was observed. The SiO₂ addition promoted the formation of Ge²⁺, which is because the Si⁴⁺ ions can deprive the O²⁻ ions from the Ge⁴⁺ ion caused by the lower optical basicity of Si⁴⁺ ions than Ge⁴⁺ ion. The germanium glasses containing the Ag nano-clusters were prepared using ion-exchange method. The influence of SiO₂ concentration on the size of Ag nano-clusters was observed, which stabilize the size distribution and lead to the miniaturization of Ag nano-clusters. The Ag nano-clusters size dependence of their photoluminescence was observed in germanate glasses, and the tunable photoluminescence of Ag nano-clusters was obtained by controlling the size of Ag nano-clusters. It is noticed that the Ag nano-clusters formed in the germanate glass showed the white light emission characteristic excited at the blue chip, exhibiting the practical application as the blue converted white light-emitting diodes.     

PbO-Fe2O3-P2O5系统半导体玻璃的电导性能研究

研究了(0.4-x)PbO—xFe2O3—0.6P2O5半导体玻璃的电导性能。首先熔制了SF系列玻璃,测定了玻璃的氧化还原指数和电导率,并计算了铁离子浓度和铁离子的平均距离。讨论了玻璃组成、熔制条件以及氧化还原指数对电导的影响,揭示了它们的电导性质不仅与组成有关,而且与铁离子的氧化-还原状态有关。随着熔制温度的升高,氧化还原指数提高,从而使电导增加。研究表明,该半导体玻璃的电导机制符合Mott的小极化子跳跃理论。     

IR Practical Extinction Coefficients of Water in Alkali Lime Silicate Glasses Determined by Nuclear Reaction Analysis

Infrared spectroscopy (IR) is widely used to determine the water concentration in glasses, whereas determination of the IR practical extinction coefficient is necessary to deduce the absolute water concentration of glasses on the basis of Beer–Lambert law. From the nuclear reaction analysis data, the IR practical extinction coefficients of water were successfully determined for the alkali lime silicate glasses with different levels of sodium/potassium cation (Na/K) ratio. The two‐band method is well‐known to be useful for the determination of the water concentration in some alkali lime silicate glasses. It is proved here that the two‐band method is not applicable to the variety of composition for alkali lime silicate and soda lime aluminosilicate glasses, whereas it is valid for the similar composition of soda lime silicate glasses [SLS: Composition (in mol%) 16Na₂O·10CaO·74SiO₂]. The single‐band procedure with the IR practical extinction coefficient is crucial for the determination of the precise water concentration in the wide variety of glass composition although the determination of the IR practical extinction coefficient is troublesome. It also appears that the ion radius of alkali affects the IR practical extinction coefficient and the chemical state of OH group in glasses.     

Evaluation of novel composition (SiO2–CaO–Na2O–P2O5, SrO–CuO) degradable amorphous silicate glasses properties and comprehensive characterization of the thermal features

The current work presents and discusses the findings of a comprehensive study on the structural, chemical and thermal properties of SrO and CuO incorporated SiO₂–CaO–Na₂O–P₂O₅ amorphous silicate glass with a novel composition. Here, fundamental features (experimental density, oxygen density, and hardness) of all glasses were determined and chemical as well as phase composition of the glasses was verified with XRF and XRD, respectively. Moreover, the thermal behavior (viscos flow and crystallization kinetics) of amorphous silicate glass was investigated by non-isothermal methods using DTA analysis. The activation energies of glass transition (E_g) were calculated in the range of 546–1115 kJ/mol by Kissinger method, whereas the activation energies of crystallization (E_c) were calculated in the range of 164–270 kJ/mol by three different methods (Kissinger, Ozawa, Yinnon and Uhlmann). Avrami exponent (n) values ranged from 1.17 to 3.28 demonstrated that amorphous silicate glasses have different crystallization mechanism. Working temperature, which is one of the parameters indicating glass stability, increased with the incorporation of Sr and Cu from 187 °C to 245 °C. The initial dissolution measurement has been applied to study the degradability behavior of Sr and Cu incorporated amorphous glasses in vitro. Quantitative evaluation of Si⁴⁺ (0.156–0.373 kV), Ca²⁺ (0.043–0.332 kV), Na⁺ (0.044–0.329 kV), P⁵⁺ (0.057–0.289 kV), Sr²⁺ (0.134–0.385 kV), and Cu²⁺ (0.090–0.203 kV) depending on the ion activation energy (E_a-ion) and ion concentration at different temperature values (24, 37 and 55 °C) was performed in contact with Tris-HCl solution by ICP-OES analysis. The results revealed that investigated glasses were degradable and incorporation of Sr and Cu affected the glass initial dissolution. Overall, investigated glasses are suitable for various application such as hot-working production, glass-ceramic manufacturing, and glass or glass-ceramic scaffolds fabrication, due to wide working temperature ranges and high crystallization tendencies of the developed glasses.     

Photoluminescence of Tb3+/Sm3+ ions co-activated in SrO - Na2O - WO3 - tellurite glasses for multicolor laser applications

A novel series of Tb³⁺, Sm³⁺ single doped and Tb³⁺/Sm³⁺ co-incorporated tungsten tellurite glasses were synthesized by melt quenching technique and corresponding structural as well as luminescence features of the prepared glasses have been reported here. Spectral overlapping between the luminescence spectra of Tb³⁺ ions and the excitation spectra of Sm³⁺ ions manifests that the energy transfer process takes place from Tb³⁺ ions to Sm³⁺ ions. By using the dual excitations at 377 and 484 nm, the titled co-doped glasses emit green light of wavelength 542 nm along with reddish – orange colour light at 599 nm. In addition to this, there is no possibility of reverse energy transfer which is validated with the help of excitation at 403 nm (Sm³⁺ ions) as major evidence. The lifetimes of all co-doped glasses decline with increasing Tb³⁺ doping level in the ligand matrices, indicating the energy migration process takes place from Tb³⁺→ Sm³⁺. The chromaticity coordinates of all synthesized co-doped glasses lie in yellowish-orange region of CIE1931 diagram and it shifts to deep yellow region when Tb³⁺ ion concentration varies. Our findings propose that the titled glasses can be used as visible laser materials for multicolor laser applications.     

Enhancement of mechanical properties and chemical durability of Soda-lime silicate glasses treated by DC gas discharges

We report for the first time a study on non-contact thermal poling of soda lime silicate glasses using DC gas discharge. In this work, the formation of a glow discharge is evidenced during the thermal poling treatment (longer than 30 minutes). The hardness and the chemical durability of glasses poled under different conditions (contact or non-contact) and atmospheres (nitrogen or air) are measured and compared to that of un-poled reference glass. The results reveal enhanced mechanical and chemical properties for samples poled under nitrogen as compare to air poled or soda lime silicate glass samples. A structural and chemical analysis of surface of the glass using IR-reflectance measurement and ToF-SIMS is also presented. The formation of a “silica-like” layer on the surface of nitrogen poled glasses is observed, which is likely associated with the enhancement of surface properties. On the other hand, the introduction of protons beneath the surface of glasses poled under air leads to the formation of a hydrated alkaline earth silica layer. Based on the observations a mechanism behind the sustainability of the plasma under DC conditions is proposed.     

Enhanced near-infrared to green upconversion from Er3+-doped oxyfluoride glass and glass ceramics containing BaGdF5 nanocrystals

In this work, effect of glass composition as well as ceramization on visible and near-infrared (NIR) luminescence properties along with their decay dynamics of Er³⁺ ions has been compared considering two different oxyfluoride glasses yielding BaF₂ and BaGdF₅ nanocrystals. Both the glass systems have exhibited an intense normal and upconversion green emission under ultraviolet (378 nm) and NIR (978 nm) excitations, respectively. A remarkable enhancement of these emission intensities is observed for gadolinium-(Gd) containing glasses. Interestingly, NIR fluorescence intensity from Er³⁺ ions at 1540 nm has showed marginal decrease in gadolinium-containing glass which is attributed to occurrence of strong excited-state absorption (ESA) due to higher fluorine content ensuing an augmentation of upconversion green emission with a concomitant decrease in NIR emission. The quadratic dependence of upconversion green emission intensity on its pump power for all the samples revealed biphotonic absorption process from ground-state ⁴I_15/2 to the excited-state ⁴I_11/2 followed by ESA of second photon to the ⁴F_7/2 level. The intense green upconversion emission as well as enhanced NIR fluorescence lifetimes indicate the suitability of these glass/glass ceramics for upconversion lasers and amplification in the third telecom window.     

Manganous-Manganic Equilibrium in Alkali Borate Glasses

The manganous-manganic equilibrium was studied in potassium, sodium, and lithium borate glasses. The glasses were analyzed chemically for total and trivalent manganese. The manganese equilibrium shifts more toward the oxidized state when the alkali concentration in the glass is increased and/or when the molar equivalent of lithia is replaced by soda and soda is replaced by potash. A linear relation between log (Mn³⁺/Mn²⁺) and mole percent alkali oxide was observed. Straight lines were obtained for lithium, sodium, and potassium borates. The disadvantages of using a concentration equilibrium constant where the glass composition is varied are discussed.