Assessment of interatomic parameters for the reproduction of borosilicate glass structures via DFT-GIPAW calculations

Borates and borosilicates are potential candidates for the design and development of glass formulations with important industrial and technological applications. A major challenge that retards the pace of development of borate/borosilicate based glasses using predictive modeling is the lack of reliable computational models to predict the structure-property relationships in these glasses over a wide compositional space. A major hindrance in this pursuit has been the complexity of boron-oxygen bonding due to which it has been difficult to develop adequate B–O interatomic potentials. In this article, we have evaluated the performance of three B–O interatomic potential models recently developed by Bauchy et al [J. Non-Cryst. Solids, 2018, 498, 294–304], Du et al [J. Am. Ceram. Soc. https://doi.org/10.1111/jace.16082 ] and Edèn et al [Phys. Chem. Chem. Phys., 2018, 20, 8192–8209] aiming to reproduce the short-to-medium range structures of sodium borosilicate glasses in the system 25 Na₂O x B₂O₃ (75 − x) SiO₂ (x = 0-75 mol%). To evaluate the different force fields, we have computed at the density functional theory level the NMR parameters of ¹¹B, ²³Na, and ²⁹Si of the models generated with the three potentials and the simulated MAS NMR spectra compared with the experimental counterparts. It was observed that the rigid ionic models proposed by Bauchy and Du can both reliably reproduce the partitioning between BO₃ and BO₄ species of the investigated glasses, along with the local environment around sodium in the glass structure. However, they do not accurately reproduce the second coordination sphere of silicon ions and the Si–O–T (T = Si, B) and B-O-T distribution angles in the investigated compositional space which strongly affect the NMR parameters and final spectral shape. On the other hand, the core-shell parameterization model proposed by Edén underestimates the fraction of BO₄ species of the glass with composition 25Na₂O 18.4B₂O₃ 56.6SiO₂ but can accurately reproduce the shape of the ¹¹B and ²⁹Si MAS-NMR spectra of the glasses investigations due to the narrower B–O–T and Si-O-T bond angle distributions. Finally, the effect of the number of boron atoms (also distinguishing the BO₃ and BO₄ units) in the second coordination sphere of the network former cations on the NMR parameters have been evaluated.     

The evolution of the mold flux melt structure during the process of fluorine replacement by B2O3

This study presented the melt structure evolution of mold flux during the substitution of fluorine by B₂O₃, and a computational model for the degree of polymerization (DOP) for borosilicate structure was developed. The results showed that the reduction of fluorine content would promote the replacement of F in [SiF₆]-octahedral unit by the dissociative free oxygen ions (O²⁻), and release F⁻ ions into the melt to compensate the reduction of F⁻ ions. With the 2 mass% addition of B₂O₃, the original Si–O–Si bond would be disrupted, and connect with [BO₃]-trihedral to form boroxol ring structure containing [BO₂O⁻]-trihedral and [BO₃]-trihedral structural units. Then, the Si–O–B bond that [BO₃]-trihedral links [SiO₄]-tetrahedral in boroxol ring was destroyed with the further addition of B₂O₃, and then the [BO₃]-trihedral could link with the dissociative Q¹(Si) and Q⁰(Si) structural units to transform into [BO₄]-tetrahedral and form a borosilicate long chain. Finally, with 6 mass% addition of B₂O₃, the borosilicate chain would combine with simple borate and borosilicate structures, and a complex borosilicate structure containing boroxol ring with certain symmetry was formed ultimately. Besides, the calculated result of DOP suggested that the DOP of the melt structure improved during the process of fluorine replacement by B₂O₃.     

Role of vanadium oxide on the lithium silicate glass structure and properties

The structural role of V in 28Li₂O–72SiO₂ (in mol%) lithium silicate glass doped with 0.5 mol% V₂O₅ was assessed using ²⁹Si and ⁵¹V Nuclear Magnetic Resonance (NMR), Fourier-transform infrared (FTIR), and X-ray photoelectron (XPS) spectroscopy techniques. Despite the low amount of V₂O₅ used, the structural information obtained or deduced from the statistical analysis of the NMR data could explain the evolution of glass properties after V₂O₅ addition. The XPS results indicated that all vanadium exists in 5+ oxidation state. Both the ²⁹Si NMR and FTIR data point toward an increase in the polymerization of the silicate network, caused by the V₂O₅ acting as network former, capable to form various tetrahedral units (for n = 0, 1, and 2) in the glasses. These units, which are similar to phosphate units, scavenge the Li⁺ ions and cause the silicate network to polymerize. However, in an overall balance, the entire glass network is depolymerized due to the additional nonbridging oxygens contributed by the vanadium polyhedra. The addition of vanadium causes the network to expand and increases the ionic conductivity.     

Structural variations of bioactive glasses obtained by different synthesis routes

Two bioactive glasses with different chemical compositions (mol%) 46.2SiO₂–26.9CaO–24.3Na₂O–2.6P₂O₅ (45S5) and 40SiO₂–54CaO–6P₂O₅ (A2) were synthesized by the use of sol–gel and melt–quenching techniques. The effect of synthesis method on glass structure was investigated using X-ray diffraction, FTIR, Raman, XPS, ²⁹Si and ³¹P MAS–NMR spectroscopic methods. The results show that the synthesis route has significant influence on the glass structure. Both melt–derived A2 and 45S5 glasses exhibit fully amorphous structure, while gel–derived ones, stabilised at 700 °C, reveal the presence of crystalline silicate and phosphate phases. Gel–derived glasses exhibit more polymerized structure compared to melt–quenched ones. Phosphorus is present in the orthophosphate type environment (Q⁰) together with some pyrophosphate (Q¹) species and it does not take part in the formation of Si–O–P bonds. This indicates that phosphorus acts as a glass structure modifier and forms phosphate-rich phase separated from a silica-rich one. The theoretically predicted network connectivity is consistent with the experimental determination only for melt–derived glasses, assuming silicon as the only network former.     

Effect of Niobium Oxide on the Structure and Properties of Melt‐Derived Bioactive Glasses

The effects of adding Nb₂O₅ on the physical properties and glass structure of two glass series derived from the 45S5 Bioglass^® have been studied. The multinuclear ²⁹Si, ³¹P, and ²³Na solid‐state MAS NMR spectra of the glasses, Raman spectroscopy and the determination of some physical properties have generated insight into the structure of the glasses. The ²⁹Si MAS NMR spectra suggest that Nb⁵⁺ ions create cross‐links between several oxygen sites, breaking Si–O–Si bonds to form a range of polyhedra [Nb(OM)_6?y(OSi)_y], where 1 ≤ y ≤ 5 and M = Na, Ca, or P. The Raman spectra show that the Nb–O–P bonds would occur in the terminal sites. Adding Nb₂O₅ significantly increases the density and the stability against devitrification, as indicated by ΔT(T_x ? T_g). Bioglass particle dispersions prepared by incorporating up to 1.3 mol% Nb₂O₅ by replacing P₂O₅ or up to 1.0 mol% Nb₂O₅ by replacing SiO₂ in 45S5 Bioglass^® using deionized water or solutions buffered with HEPES showed a significant increase in the pH during the early steps of the reaction, compared using the rate and magnitude during the earliest stages of BG45S5 dissolution.     

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.     

Environmental influence of high Na2O additions on microstructure and ligand field parameters of Cr3+ inside borosilicate glass

A glass system based on the Na₂O/B₂O₃-doped CrO₃ borosilicate has been prepared by the melt quenching technique. The structure, color, optical absorbance and ligand field parameters were investigated for a wide range of Na₂O additives (20–60 mol%). All X-ray photoelectron spectroscopy (XPS) profiles were used to study the chemical shift states of the glass-constituting elements. Fourier transform infrared (FTIR) analyses explored the internal structure and subnetwork units. Furthermore, from the FTIR results, we concluded the transformation of trigonal borate units (BO₃) to tetrahedral borate units (BO₄) and the possibility of transformation from B₃-O-Si linkages to B₄-O-Si linkages. Despite the fixed CrO₃ content, the doped glasses showed a color transition from green to yellow with additional Na₂O content. The increased intensity of the band at 451–427 nm and the decreased intensity of the band at 619–627 nm are the main reasons for this color transformation. The optical absorption spectra confirmed the existence of Cr³⁺ and Cr⁶⁺ states. A decreasing behavior for the crystal field splitting (10Dq) and an increasing behavior for Racah parameter (B) were obtained with further Na₂O additives. The decreasing behavior of 10Dq was attributed to reduced oxygen concentrations with more Na₂O/B₂O₃ substitutions. The increasing behavior of B reflects the tendency of the bond between the Cr cations and their oxygen ligands towards an ionic nature. Moreover, the Dq/B values indicated that Cr³⁺ cations are in high-field positions for the glass sample containing 20 mol% Na₂O, and Cr³⁺ cations are in intermediate field positions for the glass sample containing 30 mol% Na₂O. However, for the glass samples doped with 40, 50 and 60 mol% Na₂O glass samples, Cr³⁺-cations are in weak field positions. These results of (Dq/B) recommend the glass sample doped with 20 mol% Na₂O for tunable laser applications.     

Effect of topological structure on photoluminescence of PbSe quantum dot‐doped borosilicate glasses

Borosilicate glasses doped with PbSe quantum dots (QDs) were prepared by a conventional melt‐quenching process followed by heat treatment, which exhibit good thermal, chemical, and mechanical stabilities, and are amenable to fiber‐drawing. A broad near infrared (NIR) photoluminescence (PL) emission (1070‐1330 nm) band with large full‐width at half‐maximum (FWHM) values (189‐266 nm) and notable Stokes shift (100‐210 nm) was observed, which depended on the B₂O₃ concentration. The PL lifetime was about 1.42‐2.44 μs, and it showed a clear decrease with increasing the QDs size. The planar [BO₃] triangle units forming the two‐dimensional (2D) glass network structure clearly increased with increasing B₂O₃ concentration, which could accelerate the movement of Pb²⁺ and Se^2? ions and facilitate the growth of PbSe QDs. The tunable broadband NIR PL emission of the PbSe QD‐doped borosilicate glass may find potential application in ultra‐wideband fiber amplifiers.     

Role of Al3+ on tuning optical properties of Ce3+‐activated borosilicate scintillating glasses prepared in air

A colorless Ce³⁺‐activated borosilicate scintillating glass enriched with Gd₂O₃ is successfully synthesized in air atmosphere for the first time. The full replacement of 10 mol% BaO by Al₂O₃, and the partial substitution of 3 mol% SiO₂ by Si₃N₄ in the designed glass composition are crucial for this success. The role of Al³⁺ on tuning the optical properties of Ce³⁺‐activated borosilicate scintillating glass synthesized in air are analyzed by optical transmittance, X‐ray absorption near edge spectroscopy (XANES) spectra, photoluminescence (PL) and radioluminescence (RL) spectra. The results suggest that the stable Ce⁴⁺ ions can be effectively reduced to stable Ce³⁺ ions by the full replacement of BaO by Al₂O₃, and both the PL andRL intensity of the designed borosilicate scintillating glass are enhanced by a factor of 6.7 and 5.2, respectively. The integral RL intensity of the synthesized Ce³⁺‐activated borosilicate scintillating glass is ~17.2%BGO, with a light output of about 1180 ph/MeV. The strategy of substituting BaO by Al₂O₃ will trigger more scientific and technological considerations in designing novel fast scintillating glasses.     

Structural and thermal influence of niobia in aluminoborosilicate glasses

The addition of small amounts of niobia (Nb₂O₅) in borosilicate glasses was explored. By analysis on thermal and structural changes, we found evidences that niobium integrates the glass structure in octahedral NbO₆ coordination. Adding up to 8.0 mol% of Nb₂O₅, the oxide partially ruptured the glass structure, interfering in the BO₃/BO₄ ratio, but the predominant network configuration was maintained. Thermally, there was an increase in the processing interval and the glasses became more resistant against crystallization, with the presence of niobia. Also, the oxide contributed to a notable decrease in the viscosity of the melts. The improvement of such properties were obtained by the controlled dispersion of the oxide in the glass network structure, avoiding large areas of phase-to-phase separation to preserve the desired ability of these glasses to incorporate a wide range of elements.     

Effect of Al2O3 content on BaO–Al2O3–B2O3–SiO2 glass sealant for solid oxide fuel cell

The glass structure, wetting behavior and crystallization of BaO–Al₂O₃–B₂O₃–SiO₂ system glass containing 2–10 mol% Al₂O₃ were investigated. The introduction of Al₂O₃ caused the conversion of [BO₃] units and [BO₄] units to each other and it played as glass network former when the content was up to 10 mol%, accompanied by [BO₄] → [BO₃]. The stability of the glass improved first and then decreased as Al₂O₃ increased from 2 to 10 mol%, the glass with 5 mol% Al₂O₃ being the most stable one. The wetting behavior of the glasses indicates that excess Al₂O₃ leads to high sealing temperature. The glass containing 5 mol% Al₂O₃ characterized by a lower sealing temperature is suitable for SOFC sealing. Al₂O₃ improves the crystallization temperature of the glass. The crystal phases in the reheated glasses are mainly composed of Ba₂Si₃O₈, BaSiO₃, BaB₂O₄ and BaAl₂Si₂O₈. Al₂O₃ helps the crystallization of BaSiO₃ and BaAl₂Si₂O₈.     

Effect of substituting CaO with BaO on the viscosity and structure of CaO‐BaO‐SiO2‐MgO‐Al2O3 slags

In this study, the effect of CaO and BaO substitution on the viscosity and structure of CaO‐BaO‐SiO₂‐MgO‐Al₂O₃ slags was investigated. The results showed that the viscosity increased with an increase in the BaO substitution concentration, which was correlated to an increase in the degree of polymerization (DOP) of the slag structural units as the activation energy increased from 207.9 to 263.8 kJ/mol for viscous flow. Deconvolution and area integration of the Raman spectrum of the slag revealed that the ratio of Q³/Q² (Qⁱ, i is the number of O⁰ in a [SiO₄]‐tetrahedral unit) increased and NBO/Si (nonbridging oxygen per unit silicon atom) decreased with higher BaO content. It was also observed from the ²⁷Al magic angles pinning nuclear magnetic resonance (²⁷Al MAS‐NMR) spectrum that the relative proportion of Al^IV increased, while that of Al^V decreased because of the decrease in the percentage of nonbridging oxygen (O^?), indicating the polymerization of the slag. O_1s X‐ray photoelectron spectroscopy (XPS) was also carried out to semi‐quantitatively analyze the various types of oxygen anions present in the slag. The XPS results correlated well with the results obtained from the analysis of the Raman and ²⁷Al MAS‐NMR spectra of the slags and its viscous behavior.     

Structural and Luminescence Studies on Barium Sodium Borosilicate Glasses Containing Uranium Oxides

Barium sodium borosilicate glasses containing different amounts of uranium oxides were prepared by conventional melt quench method and investigated for their structural aspects by ²⁹Si and ¹¹B MAS NMR technique combined with steady‐state luminescence and lifetime measurements. Based on MAS NMR studies, it is confirmed that uranium ions act as network modifier up to 15 wt% and beyond which a separate uranium containing phase is formed. From the luminescence studies, it is inferred that uranyl species is in a highly distorted environment. For more than 15 wt% uranium oxide incorporation, weaker U–O–U linkages are formed at the expense stronger U–O–Si/B linkages, as suggested by the excited state lifetime value of the uranyl species as well as red shift in emission peak maximum. For glass samples containing more than 25 wt% uranium oxides, crystalline barium uranium silicate gets phase separated from glass matrix as confirmed by XRD studies.     

Corrosion of Borosilicate Glasses Subjected to Aggressive Test Conditions: Structural Investigations

Sodium borosilicate (NBS) and barium sodium borosilicate (BBS) glasses, used for immobilization of high‐level nuclear waste with compositions (SiO₂)_0.477(B₂O₃)_0.239(Na₂O)_0.170(TiO₂)_0.023(CaO)_0.068(Al₂O₃)_0.023 and (SiO₂)_0.482(B₂O₃)_0.244(Na₂O)_0.220(BaO)_0.054 were subjected leaching experiments under hydrothermal conditions in an autoclave at 200°C for different time durations. Morphological and structural transformations associated with leaching, have been monitored with techniques like XRD, SEM, solid‐state nuclear magnetic resonance. XRD and SEM along with NMR studies have confirmed that, upon leaching, formation of an aluminosilicate phase, Zeolite‐P (Na₆Al₆Si₁₀O₃₂·12H₂O), occurs with NBS glass. BBS glass upon subjecting to the same conditions leads to formation of multiple amorphous phases having Q⁴ (silica rich phase) and Q³ structural units of Silicon along with structurally modified residual glass. Upon leaching BO₃ structural units preferentially get released from BBS glass. Comparison of results with international simple glass confirmed that, for the latter, mass loss rates are one order of magnitude lower.     

Structure of cesium–borosilicate glasses according to NMR spectroscopy

The local structure of cesium-borosilicate glasses with various Cs₂O and B₂O₃ proportions and constant SiO₂ content (50 mol %) is studied with ¹¹B, ²⁹Si, and ¹³³Cs MAS NMR spectroscopy. The portions of three- and four-fold Si atoms are determined, as well as the concentrations of various silicate Q ⁿ units. Our experimental data are compared with the predictions of Dell’s model and thermodynamic modeling for sodium–borosilicate analogs of the glasses studied.     

Structural characterization of TiO2–P2O5–CaO glasses by spectroscopy

The structure of glasses with composition x TiO₂·(65 ? x) P₂O₅·35 CaO (x = 0–30 mol%) has been studied and their glass transition temperature, Raman and NMR spectra have been analysed.For TiO₂-free glass two phosphate species have been identified as Q² and Q³. Increasing TiO₂ content in glass compositions results in the disappearance of the Q³ and Q² species and in the formation of, mainly, pyrophosphate structure, Q¹.In calcium titanophosphate glass with higher TiO₂ content the structure consists of a distorted Ti octahedral linked to pyrophosphate unit through P–O–Ti bonds. In these glass series the structural cohesion increases with TiO₂, although a depolymerization in the original P–O–P network occurs.The study of these glasses and the understanding of their structural characteristics can give a valuable contribution for the clarification of their degradation behaviour namely in biological environments.     

Improved Prediction of Young's Modulus of Fluorine‐Containing Glasses Using MAS‐NMR Structural Data

The model developed by Makishima and Mackenzie (M–M) may yield reasonable estimates for the E‐modulus of a range of glasses. In the M–M model the bonding enthalpy and packing densities present in the compounds that form the glass are taken as input for the calculation. This study shows that a more accurate estimate can be obtained by incorporating in the model structural information from MAS‐NMR data. Specifically, we have determined by means of the impulse excitation technique (IET) the E‐modulus for ionomer glasses with composition 4.5SiO₂–3Al₂O₃–1.5P₂O₅–3MO–2MF₂, where M denotes the alkaline earth metal (M = Mg, Ca, Sr, or Ba). The MAS‐NMR structural analysis shows that substitution of calcium by barium or strontium results in a disrupted network, whereas magnesium leads to a more packed network. In this study we will show how a higher coordination state of the aluminum as determined by ²⁷Al MAS‐NMR can be taken into account in the model. This leads to rather small corrections of the estimates for these particular glasses. In contrast, the ¹⁹F MAS‐NMR study shows the presence of Al–F–M(n) or Al–F and Si–F–M(n) types of environment in the glass network. Al–F and Si–F bonds are not accounted for in the E‐modulus estimate by the M–M model. We will show how by incorporating the new bonding of F with Al and Si a significantly improved estimate of the E‐modulus is obtained compared with the original model.     

Thermal stability of [B]ZSM-5 molecular sieve

The thermal stability of [BJZSM-5 (boronsilicalite) has been examined by IR, XRD,¹¹B MAS NMR and XPS techniques. [B]ZSM-5 and amorphous borosilicate were converted to α-cristobalite at high temperatures (=750C). However, Na-free amorphous borosilicate was not converted to a-cristobalite at 750C. Therefore, the presence of Na ions in [BJZSM-5 would determine whether this transition occurred or not. When the phase transition to α-cristobalite occurred, most of B atoms tetrahedrally coordinated were released from the ZSM-5 structure and migrated to the exterior surface as a boron compound having trigonal BO₃ units and oxidation states of 3.     

Effect of Ta2O5 addition on the structure,crystallization mechanism,and properties of CaO–B2O3–SiO2 glasses for LTCC applications

CaO–B₂O₃–SiO₂–Ta₂O₅ (CBST) glass-ceramics, with different Ta₂O₅ content, (up to 6 mol%), have been prepared by using glass melt quenching followed by heat treatment between 800 and 880 °C. The Fourier Transform Infrared (FTIR) results showed that the stronger the attraction of Ta⁵⁺ to the oxygens in the BO₃^3? and SiO₃^2? structures, the more easily the B–O and Si–O bonds will be destroyed. The underlying reason is most probably the high field strength of Ta⁵⁺, which results in a weakening of the vibration intensities of the [BO₃] and [SiO₄] units. Moreover, the Differential Scanning Calorimetry (DSC) results showed that the softening point (T_g), crystallization starting temperature (T_c1), and exothermic crystallization peak temperature (T_p1), of the CaSiO₃ phase, shifted to higher values with the addition of Ta₂O₅. Also, the crystallization activation energy (E_a) and the glass stability factor (ΔT) of the CaSiO₃ phase increased, which indicated that the CaSiO₃ phase of the glass became inhibited by the addition of Ta₂O_5. It was, thus, obvious that there was a need of glass characterization. The results of the crystallization kinetics showed that the critical cooling rate decreased with the addition of Ta₂O₅, which indicated that the viscosity of the system had increased. The CBST glass-ceramics, containing 1 mol% Ta₂O_5, that were sintered at 875 °C for 15 min showed excellent dielectric properties: ε_r = 6.22 and tanδ = 1.19 × 10^?3 (1 MHz). To sum up, CaO–B₂O₃–SiO₂–Ta₂O₅ glass-ceramics are potential low temperature co-fired ceramic substrate materials.     

Influence of Al2O3/SiO2 ratio in multicomponent LNAS glasses and glass-ceramics on the crystallization behavior,microstructure and mechanical performance

Transparent glass-ceramics containing eucryptite and nepheline crystalline phases were prepared from alkali (Li, Na) aluminosilicate glasses with various mole substitutions of Al₂O₃ for SiO₂. The relationships between glass network structure and crystallization behavior of Li₂O–Na₂O–Al₂O₃–SiO₂ (LNAS) glasses were investigated. It was found that the crystallization of the eucryptite and nepheline in LNAS glasses significantly depended on the concentration of Al₂O₃. LNAS glasses with the addition of Al₂O₃ from 16 to 18 mol% exhibited increasing Q⁴ (mAl) structural units confirmed by NMR and Raman spectroscopy, which promoted the formation of eucryptite and nepheline crystalline phases. With the Al₂O₃ content increasing to 19–20 mol%, the formation of highly disordered (Li, Na)₃PO₄ phase which can serve as nucleation sites was inhibited and the crystallization mechanism of glass became surface crystallization. Glass-ceramics containing 18 mol% Al₂O₃ showed high transparency ～84% at 550 nm. Moreover, the microhardness, elastic modulus and fracture toughness are 8.56 GPa, 95.7 GPa and 0.78 MPa m^1/2 respectively. The transparent glass-ceramics with good mechanical properties show high potential in the applications of protective cover of displays.