Structural and thermal characterization of CaO–MgO–SiO2–P2O5–CaF2 glasses

The influence of varying the CaO/MgO ratio on the structure and thermal properties of CaO–MgO–SiO₂–P₂O₅–CaF₂ glasses was studied in a series of eight glass compositions in the glass forming region of diopside (CaMgSi₂O₆)–fluorapatite [Ca₅(PO₄)₃F]–wollastonite (CaSiO₃) ternary system. The melt-quenched glasses were characterized for their structure by infrared spectroscopy (FTIR) and magic angle spinning (MAS)-nuclear magnetic resonance (NMR) spectroscopy. Silicon is predominantly present as Q² (Si) species, while phosphorus tends to coordinate in orthophosphate environment. The sintering and crystallization parameters of the glasses were obtained from differential thermal analysis (DTA) while crystalline phase fractions in the sintered glass–ceramics were analyzed by X-ray diffraction adjoined with Rietveld refinement. Diopside, fluorapatite, wollastonite and pseudowollastonite crystallized as the main crystalline phases in all the glass–ceramics with their content varying with respect to variation in CaO/MgO ratio in glasses. The implications of structure and sintering behaviour of glasses on their bioactivity were discussed.     

Mechanical Properties of Anisotropic Metaphosphate Glass

The effect of anisotropy on the mechanical properties was investigated for a chain‐structured metaphosphate glass (12.5Li₂O–12.5Na₂O–12.5K₂O–12.5Cs₂O–50P₂O₅ mol%). Anisotropic glasses with different birefringence values were prepared with a fiber elongation method. The strength and Young's moduli of the glasses were measured with a three‐point bending method. It was found that the strength and Young's modulus increased with increasing birefringence, reaching about 160% and 140%, respectively, compared with the values for the isotropic glass. The enhancement of the mechanical properties was attributed to the orientation of ‐P‐O‐P‐ chains in the glass.     

THE EFFECT OF BORIC OXIDE ON THE DEVITRIFICATION OF THE SODA-LIME-SILICA GLASSES. THE QUATERNARY SYSTEM,Na2O-CaO-B2O3-SiO21

Commercial glasses of the soda-lime-silica types do not consist solely of these three oxides, but in addition contain significant amounts of other constituents which arc introduced incidentally as impurities or deliberately for some beneficial influence. Such minor additions may have either a favorable or unfavorable influence on the tendency of the glass to devitrify, and an investigation into the effect of such minor components is desirable. Previous results with MgO and with A1₂O₃ have shown that a systematic study of a four-component system is necessary to the understanding of its devitrification relations, and that arbitrary and fragmentary excursions into such a system give little insight into the general effect of the minor constituent and may be misinterpreted to erroneous conclusions as to the effect of this constituent on glasses of slightly different composition. Accordingly, in taking up the study of the effect of B₂O₃ on the devitrification of the soda-lime-silica glasses, it was added to 21 glasses in and near the field of devitrite, Na₂O·3CaO·6SiO₂, in the ternary system, Na₂O–CaO-SiO₂, in amounts up to about 5%. In all cases the liquidus temperature was lowered, and the tendency toward devitrification reduced. Both of these effects are desirable and add to the thermal stability of the glass. With glasses containing 10% CaO, initially in the field of tridymite or so near to it that a small addition of B203 brings the resulting glass into the tridymite field, this initial lowering is replaced by an increase in the liquidus temperature which passed through a maximum at from 4 to 6% B₂O₃. With all other glasses the lowering continues, and the rate of decrease is greatest with glasses originally in the field of Na₂O·2CaO·3SiO₂. An exploration of the quaternary system showed that no new compounds are formed in any mixture that can be obtained by adding B203 in amounts up to 50% to any mixture in or near the devitrite field. It also indicated the probability that a narrow band of immiscible liquids is formed, extending across the ternary system, CaO-B₂O₃–SiO₂, and including the mineral danburite, CaO·B₂O·2SiO₂, but probably not extending far into the quaternary system. The fields of wollastonite and of Na₂O·2CaO·3SiO₂ were found to sweep out regions in the quaternary system extending over the square, Na₂O·SiO₂-Na₂O·B₂O₃-CaO-B₂O₃-CaOSO₂, and the field of Na₂O·CaO·SiO₂ was found to extend over the middle of this square, and is probably adjacent to the fields of wollastonite and of Na₂O· 2CaO·3SiO₂. A compound is formed between Na₂O·B₂O₃ and CaO·B₂O₃. There is included a general survey of the literature relative to the effect of B203 on the properties of glass.     

Liquidus Temperature of SrO-Al2O3-SiO2 Glass-Forming Compositions

Despite the important role of strontium aluminosilicate glasses in various technologies, there is no available phase diagram for this ternary system in the ACerS-NIST Phase Equilibria Diagrams Database. Establishing the liquidus surface (liquidus temperature T_liq and primary devitrification phase) is crucial for glass composition design, because the liquidus temperature is intimately connected with the glass-forming ability of the melt. In this work, we have determined the liquidus surface by X-ray diffraction phase analyses of isothermally reacted samples from powder mixtures of 24 compositions. In the composition range of interest for industrial glasses, T_liq tends to decrease with increasing strontium-to-alumina ratio. We find that cristobalite, mullite, and slawsonite are the dominant devitrification phases for the compositions with high SiO₂, SiO₂+Al₂O₃, and SrO contents, respectively. By comparison with the phase diagrams for CaO-Al₂O₃-SiO₂ and MgO-Al₂O₃-SiO₂ systems, we have found that for the highest [RO]/[Al₂O₃] ratios, T_liq exhibits a minimum value for R = Ca. Based on the phase diagram established here, the composition of glass materials, for example, for liquid crystal display substrates, belonging to the SrO-Al₂O₃-SiO₂ family may be designed with a more exact control of the glass-forming ability by avoiding the regions of high liquidus temperature.     

Topological hardening through oxygen triclusters in calcium aluminosilicate glasses

Molecular dynamics simulations and topological constraint theory are used to study the impact of oxygen triclusters in the calcium aluminosilicate glass system at ratios of 0.6, 1, 1.5, 2, and 4 [Al₂O₃]/[CaO]. Negligible percentages (less than ~3%) of five-coordinated Al structures are found at all ratios. Up to ~27% three-coordinated oxygens, also known as triclusters, are found at the highest ratio of [Al₂O₃]/[CaO]. A topological constraint model, which considers additional constraints provided by triclusters, is created to predict the glass transition temperature, hardness, and Young's modulus. The models are used to elucidate the role of triclusters in glass properties. Analysis of topological constraints shows that triclusters can potentially increase the glass hardness within the calcium aluminosilicate system. The results are also compared to oxynitride glasses. Triclusters show the same ability as nitrogen to increase the glass hardness but are less effective at increasing the Young's modulus.     

Microscopic Origins of Compositional Trends in Aluminosilicate Glass Properties

Revealing and understanding the microscopic origins of the macroscopic properties of aluminosilicate glasses is important for the design of new glasses with optimized properties. In this work, we study the composition‐structure‐property relationships in 20 MgO/CaO sodium aluminosilicate glasses upon Al₂O₃‐for‐SiO₂ and MgO‐for‐CaO substitutions. We find that some properties (density, molar volume, Young's modulus, and shear modulus) are linear through the investigated range of Al₂O₃ compositions, while others (refractive index, coefficient of thermal expansion, Vickers hardness, isokom temperatures, and liquid fragility index) exhibit a change in the slope around the composition with [Al₂O₃] = [Na₂O], which is especially pronounced for the glasses containing MgO. We discuss these phenomena based on structural information obtained by NMR spectroscopy and topological considerations.     

EFFECT OF ALUMINA ON DEVITRIFICATION OF SODIUM OXIDE-DOLOMITE LIME-SILICA GLASSES*

The effect of the substitution of A1₂O₃ for the oxides of sodium, silicon, calcium, and magnesium in the ratio in which they occur in dolomite on the liquidus temperatures and phase relations for glasses lying within the composition range, Na₂O 12 to 16%, CaO-MgO 0 to 20%, SiO₂ 63 to 78%, and A1₂O₃ 0 to 10%, has been determined. The results on 116 individual determinations are given. Devitrite is the primary phase in very few glasses. Several glasses were found which cannot be devitrified. A comparison of devitrification temperatures of calcite and dolomite-lime glasses is made.     

Revealing structural role of ZrO2 in silicate glasses from macroscale property by rigid-unit packing fraction method

The structural role of an oxide as a former and modifier can have significant effects on the chemical durability and mechanical properties of the glass. Some oxides with high-field strength cations, for example, MgO and ZrO₂, are often labeled as a third group—intermediate, due to their either undetermined or dual structural roles dependent on the glass compositions. Based on our recent modification of the Makishima–Mackenzie (MM) model using the rigid-unit Packing Fraction (RUPF), we analyzed a series of novel zirconia-containing bioactive glasses. The RUPF-based MM-model provides better prediction of the elastic moduli of these new glasses in comparison to experimental measurements. At the same time, the structural role of zirconia can be determined by comparison with calculations by assuming various structural roles and those from experiments. We reveal that ZrO₂ acts as the network former in phosphosilicate glasses, which leading to significant increase in packing fraction and consequent increase in Young's modulus. The recent experimental and atomistic simulation results support the glass former role of zirconia in silicate glasses. This method is general and applicable to other oxides in glasses.     

Effects of nitrogen and fluorine on crystallisation of Ca-Si-Al-O-N-F glasses

The effect of nitrogen and fluorine substitution on the crystallisation of a new generation of oxyfluoronitride glasses in the Ca-Si-Al-O-N-F system has been studied. Glasses were nucleated for 5 h at the nucleation temperature of Tg + 50 °C and crystallised for 10 h at the maximum crystallisation temperature (900-1050 °C depending on the glass composition) determined from differential thermal analysis. For the oxide glass, crystallisation results in formation of wollastonite (CaSiO₃), gehlenite (Ca₂Al₂SiO₇) and anorthite (CaAl₂Si₂O₈) along with a small amount of residual glass. For crystallisation of oxyfluoride glasses (0 equiv.% N), when fluorine content increases, cuspidine (Ca₄Si₂O₇F₂) is the major crystalline phase at the expense of gehlenite while in oxyfluoronitride glasses containing 20 equiv.% N, gehlenite is always the dominant crystalline phase at different fluorine contents. At constant fluorine content (5 equiv.%), an increase in nitrogen content favours the formation of gehlenite rather than anorthite or wollastonite suggesting that this phase may be able to accommodate N into its crystal structure. While a small amount of nitrogen substitution for oxygen can be assumed in the gehlenite structure, the residual glass in the glass-ceramic is expected to be very N-rich. In terms of properties, hardness is shown to be more sensitive to changes in microstructure, phase morphology and crystal size compared with elastic modulus which is related to the amounts of constituent phases present.     

Environment-dependent indentation recovery of select soda-lime silicate glasses

Indentations made on silicate glasses can easily be affected by the environment. In the present work, indentations were made on select commercial float glasses as well as on experimental soda-lime silicate glasses using a 1 mm diameter spherical tungsten carbide ball-mounted Brinell indenter. Recovery of indentations made on the glass samples was measured in different environments, namely, 100 °C, room temperature/room humidity and 100% relative humidity, as a function of time by using a Zygo laser non-contact profiliometer. Elastic (Young's modulus, bulk modulus, shear modulus and Poisson's ratio) and indentation (Vickers hardness, fracture toughness, brittleness and fracture surface energy) properties of the glasses were also determined by a pulse-echo and Vickers indentation methods, respectively, to correlate with the recovery of indentations. The elastic properties and Vickers hardness are directly proportional to the packing ions present in the glass structure and the strength of an individual bond, whereas the brittleness and fracture toughness more likely depend on molar volume of the glasses. According to the applied environment, a recovery rate of indentations follows the order: room temperature/room humidity <100% relative humidity <100 °C, regardless of glass composition. The reason for higher recovery rate of indentations is attributed to the structural relaxation, which is promoted by a thermodynamic driving force at 100 °C, and stored strain energy in deformation zone, allowing the indentations to regain their original configurations at certain points.     

A modified B2O3 containing Li2O-Al2O3-SiO2 glass with ZrO2 as nucleating agent - Crystallization and microstructure studied by XRD and (S)TEM-EDX

Glass-ceramics based on lithium-alumo-silicate glasses are commercially important for a wide range of applications, due to their special properties, like a vanishing thermal expansion. In order to tailor these properties, the composition of the glass and the temperature/time schedule are crucial factors. For the industrial production of most lithium-alumo-silicate glasses, high melting temperatures are required due to the high viscosities of the respective melt compositions. In this study, a simplified lithium-alumo-silicate glass composition with ZrO₂ as nucleating agent, on the basis of the commercially available Robax^® composition, is studied. Adding boron oxide leads to lower viscosities of the glass melt and notably lower melting temperatures may be supplied. The resulting glass is investigated using X-ray diffraction and transmission electron microscopy. During the crystallization process, phases such as ZrO₂ and β-quartz types are formed. The microstructure of the glass ceramics is notably coarser than that of glass-ceramics which are obtained from lithium-alumo-silicate glasses of standard compositions. EDX-analyses indicate a considerable enrichment of chemical elements in comparatively small areas of the microstructure. Especially boron oxide is found to be enriched in the residual glass of the investigated glass-ceramics.     

Mechanical,gamma rays and neutron radiation transmission properties for some ZnO–TeO2–P2O5-ZnX glasses

Oxyhalide glasses are utilized in the process of immobilizing nuclear waste and function as scintillating agents for the purpose of radiation detection. The objective of this study is to examine the enhanced mechanical and radiation attenuation characteristics of newly developed oxyhalide glasses by incorporating zinc-iodide. This study investigates the synthesis process, mechanical properties, and experimental gamma-neutron radiation transmission properties. A halogen-free base glass, consisting of an oxide mixture of P₂O₅, TeO₂, and ZnO, was synthesized. Following that, the initial glass composition was further strengthened by the addition of zinc bromide (ZnBr₂), zinc chloride (ZnCl₂), zinc fluoride (ZnF₂), and zinc iodide (ZnI₂) in a successive manner. The experimental configuration entailed positioning circular glass samples between a 133Ba radioisotope and a Canberra High Purity Germanium (HPGe) detector. The determination of attenuation coefficients is achieved through the measurement of individual attenuation properties. Afterwards, theoretical approaches are utilized to determine the mechanical characteristics of halogenated glasses, including Young's modulus (Y), Bulk modulus (K), Shear modulus (G), Longitudinal modulus (L), and Poisson's modulus (v). The results of the study suggest that the implementation of the halogenation process on the P₂O₅–TeO₂–ZnO base composition led to a significant enhancement in the examined properties. The incorporation of zinc-iodide in the halogenation process resulted in a significant improvement in the gamma absorption properties. The utilization of zinc in the halogenation process demonstrates multifunctional capabilities, which involve the potential to enhance various glass properties, including durability and gamma-ray absorption properties. It can be concluded that zinc-iodide demonstrates enhanced halogenation capabilities in comparison to zinc bromide, zinc chloride, and zinc fluoride.     

Compositional effects on the crosslink density of Ca–(Mg)–(Y)–Si–Al–oxyfluoronitride glasses

The effects of fluorine and nitrogen substitution for oxygen in aluminosilicate glasses, effectively oxyfluoronitride (OFN) glasses, modified by calcium, calcium–yttrium or calcium–magnesium on thermal and physical/mechanical properties have been compared. Thus, 42 glasses in the Ca–(Mg)–(Y)–Si–Al–O–(N)–(F) system have been prepared and characterized with respect to density (ρ), molar volume (MV), compactness (C), free volume (FV), glass transition temperatures measured by DTA (T_g,DTA) and dilatometry (T_g,dil), dilatometric softening point (T_DS), microhardness (μHv) and Young's modulus (E). Gradients of property variation with nitrogen or fluorine substitutions for oxygen are similar for all three different oxyfluoronitride glass systems and are comparable with those reported for other OFN glasses, again indicating independent and additive effects of nitrogen and fluorine. In attempting to further understand how fluorine affects the cross‐link density (CLD) in OFN glasses, it becomes apparent that it is necessary to allow for a greater contribution by aluminum in a modifier role as fluorine content is increased. This modified calculation of CLD values results in good linear fits between T_g and CLD values. This analysis clearly demonstrates and endorses the concepts that thermal properties are related to CLD while physical/mechanical properties are dependent on glass compactness.     

Elasticity,hardness, and fracture toughness of sodium aluminoborosilicate glasses

Due to an increasing demand for oxide glasses with a better mechanical performance, there is a need to improve our understanding of the composition-structure-mechanical property relations in these brittle materials. At present, some properties such as Young's modulus can to a large extent be predicted based on the chemical composition, while others—in particular fracture-related properties—are typically optimized based on a trial-and-error approach. In this work, we study the mechanical properties of a series of 20 glasses in the quartenary Na₂O–Al₂O₃–B₂O₃–SiO₂ system with fixed soda content, thus accessing different structural domains. Ultrasonic echography is used to determine the elastic moduli and Poisson's ratio, while Vickers indentation is used to determine hardness. Furthermore, the single-edge precracked beam method is used to estimate the fracture toughness (K_Ic) for some compositions of interest. The compositional evolutions of Vickers hardness and Young's modulus are in good agreement with those predicted from models based on bond constraint density and strength. Although there is a larger deviation, the overall compositional trend in K_Ic can also be predicted by a model based on the strength of the bonds assumed to be involved in the fracture process.     

Designing optical glasses by machine learning coupled with a genetic algorithm

Engineering new glass compositions have experienced a sturdy tendency to move forward from (educated) trial-and-error to data- and simulation-driven strategies. In this work, we developed a computer program that combines data-driven predictive models (in this case, neural networks) with a genetic algorithm to design glass compositions with desired combinations of properties. First, we induced predictive models for the glass transition temperature (T_g) using a dataset of 45,302 compositions with 39 different chemical elements, and for the refractive index (n_d) using a dataset of 41,225 compositions with 38 different chemical elements. Then, we searched for relevant glass compositions using a genetic algorithm informed by a design trend of glasses having high n_d (1.7 or more) and low T_g (500 °C or less). Two candidate compositions suggested by the combined algorithms were selected and produced in the laboratory. These compositions are significantly different from those in the datasets used to induce the predictive models, showing that the used method is indeed capable of exploration. Both glasses met the constraints of the work, which supports the proposed framework. Therefore, this new tool can be immediately used for accelerating the design of new glasses. These results are a stepping stone in the pathway of machine learning-guided design of novel glasses.     

CHANGES IN THE INDICES OF REFRACTION AND LIQUIDUS OF A BARIUM CROWN GLASS PRODUCED BY THE PARTIAL SUBSTITUTION OF SOME OXIDES*

Optical glasses with high indices of refraction and Abbe values are very desirable for wide angle lenses. In order to determine the range of compositions in which glasses of this type could be produced, oxides of lithium, beryllium, calcium, boron, lanthanum, or thorium were substituted for barium oxide or silica in a three-or-four component base glass. Substitutions were made on a mole-for-mole basis. The indices of refraction for the C, D, F, and G lines and the liquidus were determined for each glass. Experimental glasses with indices of refraction (n_D) and Abbe values from 1.600 to 1.714 and 62.2 to 52.7, respectively, were made in small platinum crucibles.     

The role of MgO on the structural properties of CaO–Na2O(MgO)–P2O5–CaF2–SiO2 derived glass ceramics

The effect of increasing MgO/Na₂O replacements (on mole basis) on the crystallization characteristics of glasses based on the CaO–Na₂O(MgO)–P₂O₅–CaF₂–SiO₂ system were studied by using DTA, XRD, and SEM. The crystallization characteristics of the glasses, the type of crystalline phases formed and the resulting microstructure were investigated. The main crystalline phases formed after controlled heat-treatment of the base glass were diopside, wollastonite solid solution, fluoroapatite and sodium calcium silicate phases. The increase of MgO at the expense of Na₂O led to decrease the amount of sodium calcium silicate phase. The Vicker's microhardness values (5837–3362 MPa) of the resulting glass–ceramics were markedly improved by increasing the MgO-content in the glasses. The obtained data were correlated to the nature and concentration of the crystalline phases formed and the resulting microstructure.     

DEVITRIFICATION CHARACTERISTICS OF ALKALI-LEAD OXIDE-DOLOMITE LIME-SILICA GLASSES*

The devitrification characteristics of the field of compositions, which includes the commercial lime crystal glasses, were investigated. Tridymite was found to crystallize from glasses containing as low as 62% of SiO₂. Tridymite, devitrite, diopside, sodium disilicate, and an unidentified compound were found to be primary phases. Potassium oxide (K₂O), in general, lowers the liquidus temperature when it replaces Na₂O.     

Blends of poly[3,3-bis(chloromethyl)oxetane] with poly(vinyl acetate). I. Thermal and mechanical properties

Blends of poly[3,3-bis(chloromethyl)oxetane] (Penton) with poly(vinyl acetate) were prepared. Compatibility, morphology, thermal behavior, and mechanical properties of blends with various compositions were studied using differential scanning calorimetry (DSC), dynamic mechanical measurements (DMA), tensile tests, and scanning electron microscopy (SEM). DMA study showed that the blends have two glass transition temperatures (T_g). The T_g of the PVAc rich phase shifts significantly to lower temperatures with increasing Penton content, suggesting that a considerable amount of Penton dissolves in the PVAc rich phase, but that the Penton rich phase contains little PVAc. The Penton/PVAc blends are partially compatible. DSC results suggest that PVAc can act as a β-nucleator for Penton in the blend. Marked negative deviations from simple additivity were observed for the tensile strength at break over the entire composition range. The Young's modulus curve appeared to be S-shaped, implying that the blends are heterogeneous and have a two-phase structure. This was confirmed by SEM observations. © 1992 John Wiley & Sons, Inc.     

Formation and Properties of Ln-Si-O-N Glasses (Ln = Lanthanides or Y)

Homogeneous Y-Si-O-N glasses containing 15 or 20 eq% nitrogen (N) were prepared from compositions with Y/Si ratios in the vicinity of that of the lowest eutectic point on the Y₂O₃–SiO₂ phase diagram. The liquidus on the phase diagram shifted toward lower temperatures by incorporation of N. The density, the elastic moduli, and the glass transition temperature of the Y-Si-O-N glasses increased with incorporation of N. This is due to the closer packing of atoms in the glasses by the substitution of N, which is in three-fold coordination with Si, for O which is in two-fold coordination, and the stronger covalent nature of the Si–N bond compared with the Si–O bond. The coefficient of thermal expansion of the Y-Si-O-N glasses increased with increasing Y content, because the discontinuity of the glass network developed with increasing nonbridging anions by the introduction of Y. In contrast, the glass transition temperature and the elastic moduli increased with Y content due to the high coordination of Y for O, and the relatively high cationic field strength of Y. Furthermore, the effect of cationic field strength on properties of Ln-Si-O-N glasses (Ln = lanthanides or Y) is discussed.