Structure-property relations in crack-resistant alkaline-earth aluminoborosilicate glasses studied by solid state NMR

The effect of the average ionic potential ξ = Ze/r of the network modifier cations on crack initiation resistance (CR) and Young's modulus E has been measured for a series of alkaline-earth aluminoborosilicate glasses with the compositions 60SiO₂–10Al₂O₃–10B₂O₃–(20−x)M₍₂₎O–xM’O (0 ≤ x ≤ 20; M, M’ = Mg, Ca, Sr, Ba, Na). Systematic trends indicating an increase of CR with increasing ionic potential, ξ, have been correlated with structural properties deduced from the NMR interaction parameters in ²⁹Si, ²⁷Al, ²³Na, and ¹¹B solid state NMR. ²⁷Al NMR spectra indicate that the aluminum atoms in these glasses are essentially all four-coordinated, however, the average quadrupolar coupling constant <C_Q> extracted from lineshape analysis increases linearly with increasing average ion potential computed from the cation composition. A similar linear correlation is observed for the average ²⁹Si chemical shift, whereas the fraction of four-coordinate boron decreases linearly with increasing ξ. Altogether the results indicate that in pure alkaline-earth boroaluminosilicate glasses the crack resistance/E-modulus trade-off can be tailored by the alkaline-earth oxide inventory. In contrast, the situation looks more complicated in glasses containing both Na₂O and the alkaline-earth oxides MgO, CaO, SrO, and BaO. For 60SiO₂–10Al₂O₃–10B₂O₃–10MgO–10Na₂O glass, the NMR parameters, interpreted in the context of their correlations with ionic potentials, are consistent with a partial network former role of the MgO component, enhancing crack resistance. Altogether the presence of MgO in aluminoborosilicate glasses helps overcome the trade-off issue between high crack resistance and high elasticity modulus present in borosilicate glasses, thereby offering additional opportunities for the design of glasses that are both very rigid and very crack resistant.     

Cation field-strength effects on ion irradiation-induced mechanical property changes of borosilicate glass structures

We examine the impact of the glass network-modifier cation field strength (CFS) on ion irradiation-induced mechanical property changes in borosilicate (BS) glasses for the ternary M₂O–B₂O₃–SiO₂ systems with M = {Na, K, Rb} and the quaternary [0.5M₍₂₎O–0.5Na₂O]–B₂O₃–SiO₂ systems with M = {Li, Na, K, Rb Mg, Ca, Sr, Ba}. ¹¹B nuclear magnetic resonance (NMR) experiments on the as-prepared BS glasses yielded the fractional population of four-coordinated B species (B^[4]) out of all {B^[3], B^[4]} groups in the glass network, along with the fraction of B^[4]–O–Si linkages out of all B^[4]–O–Si/B bonds. Both parameters correlated linearly with the (average) CFS of the M⁺ and/or {M⁽²⁾⁺, Na⁺} cations. Both the nanoindentation-derived hardness and Young's modulus values of the glasses reduced upon their irradiation by Si²⁺ ions, with the property deterioration decreasing linearly with increasing M^z+ CFS, that is, for higher M^z+⋅⋅⋅O interaction strength. The irradiation damage of the glass network also increased linearly with the fraction of B^[4]–O–Si linkages, which are the second weakest in the structure after the M^z+⋅⋅⋅O bonds. Our results underscore the advantages of employing BS glasses with high-CFS cations for enhancing the radiation resistance for nuclear waste storage.     

Vanadium in Borosilicate Glass

Understanding the role of V₂O₅ within borosilicate glass matrices is important for the development of novel matrices toward immobilization of sulfate containing high‐level nuclear wastes. Present investigation shows, within sodium barium borosilicate glass matrix V₂O₅ can be homogeneously added up to 5 mol% and beyond which it separates out into three phases, for example, (i) silica (ii) Barium (Ba) – Vanadium (V) oxide, and (iii) glass matrix. ²⁹Si MAS NMR (Nuclear Magnetic Resonance) studies of the samples show that below 5 mol% V₂O₅ addition, silicate network is dominantly constituted of Q² and Q³ structural units, whereas above this, the network gets more polymerized through formation of Q³ and Q⁴ units. In case of borate network, ¹¹B MAS NMR investigations revealed that the concentration of BO₄ [(0B, 4Si)] unit increases gradually up to 5 mol% and then it decreases at the cost of BO₄ [(1B, 3Si)], BO₃ (symmetric) and BO₃ (asymmetric) units. Micro‐Raman analyses of the samples showed that with additions of V₂O₅ in diluted concentrations, amorphous silicate network remained unaltered, whereas some amplification in signals corresponding to ring‐type metaborate and VO₅ units exists. It is therefore apparent from both MAS‐NMR and micro‐Raman studies that with V₂O₅ additions within the solubility limit (≤5 mol%), borate network gets depolymerized leading to decrease in hardness from an average value of 5.0–4.2 GPa.     

Energetics and Structure of Polymer‐Derived Si–(B–)O–C Glasses: Effect of the Boron Content and Pyrolysis Temperature

The structure and properties of polymer‐derived Si–(B–)O–C glasses have been shown to be significantly influenced by the boron content and pyrolysis temperature. This work determined the impact of these two parameters on the thermodynamic stability of these glasses. High‐temperature oxide melt solution calorimetry was performed on a series of amorphous samples, with varying boron contents (0–7.7 at.%), obtained by pyrolysis of precursors made by a sol–gel technique. Thermodynamic analysis of the calorimetric results demonstrated that at a constant pyrolysis temperature, adding boron makes the materials energetically less stable. While the B‐containing glasses pyrolyzed at 1000°C were energetically less stable than the competitive crystalline components, increasing the pyrolysis temperature to 1200°C led to their enthalpic stability. ²⁹Si and ¹¹B MAS nuclear magnetic resonance (NMR) spectroscopy measurements on selected samples confirmed a decrease in the concentrations of mixed Si‐centered SO_iC_4?i and B‐centered BO_jC_3?j bonds at the expense of formation of SiO₄ and B(OSi)₃ species (indicating a tendency toward phase separation) when the boron content and pyrolysis temperature increased. In light of the findings from calorimetry and NMR spectroscopy, we propose a structure–energetic relationship in Si–(B–)O–C glasses.     

Structural dependence of crystallization in phosphorus-containing sodium aluminoborosilicate glasses

The article reports on the structural dependence of crystallization in Na₂O–Al₂O₃–B₂O₃–P₂O₅–SiO₂-based glasses over a broad compositional space. The structure of melt-quenched glasses has been investigated using ¹¹B, ²⁷Al, ²⁹Si, and ³¹P magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, while the crystallization behavior has been followed using X-ray diffraction and scanning electron microscopy combined with energy dispersive spectroscopy. In general, the integration of phosphate into the sodium aluminoborosilicate network is mainly accomplished via the formation of Al–O–P and B–O–P linkages with the possibility of formation of Si–O–P linkages playing only a minor role. In terms of crystallization, at low concentrations (≤5 mol.%), P₂O₅ promotes the crystallization of nepheline (NaAlSiO₄), while at higher concentrations (≥10 mol.%), it tends to suppress (completely or incompletely depending on the glass chemistry) the crystallization in glasses. When correlating the structure of glasses with their crystallization behavior, the MAS NMR results highlight the importance of the substitution/replacement of Si–O–Al linkages by Al–O–P, Si–O–B, and B–O–P linkages in the suppression of nepheline crystallization in glasses. The results have been discussed in the context of (1) the problem of nepheline crystallization in Hanford high-level waste glasses and (2) designing vitreous waste forms for the immobilization of phosphate-rich dehalogenated Echem salt waste.     

Effect of Mg2+ and fluorine on the network and highly efficient photoluminescence of Eu3+ ion in MgF2–BaO–B2O3 glasses

The glass structure and photoluminescence of new oxyfluoride glasses with the composition of xMgF₂–(66.7−2x/3)BaO–(33.3−x/3)B₂O₃ (x = 10-50 mol%) were investigated in this work. The structure of the glasses was investigated by magic-angle spinning NMR, XAS, and Raman scattering spectroscopies. It was revealed that the glasses are mainly composed of BO₃ units with a disconnected borate network consisting mainly of ortho- and pyro-borate units, and ortho-borate increases with the addition of MgF₂. The fluorine atoms are surrounded by Mg²⁺ and Ba²⁺ ions. The photoluminescence of Eu³⁺-doped samples were investigated. It was indicated that asymmetry of the Eu³⁺ site increased with the addition of MgF₂. The photoluminescence quantum yield (η) of the glasses are very high and increased with MgF₂ addition; red photoluminescence is observed with η = 82% for 10MgF₂ and η = 98% for 50MgF₂ for excitation at 393 nm.     

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.     

Searching for correlations between vibrational spectral features and structural parameters of silicate glass network

Infrared (IR) and Raman spectroscopic features of silicate glasses are often interpreted based on the analogy with those of smaller molecules, molecular clusters, or crystalline counterparts; this study tests the accuracy and validity of these widely cited peak assignment schemes by comparing vibrational spectral features with bond parameters of the glass network created by molecular dynamics (MD) simulations. A series of sodium silicate glasses with compositions of [Na₂O]_x[Al₂O₃]₂[SiO₂]_98−x with x = 7, 12, 17, and 22 were synthesized and analyzed with IR and Raman. A silica glass substrate and a crystalline quartz were also analyzed for comparison. Glass structures with the same compositions were generated with MD simulations using three types of potentials: fixed partial charge pairwise (Teter), partial diffuse charge potential (MGFF), and bond order-based charge transfer potential (ReaxFF). The comparison of simulated and experimental IR spectra showed that, among these three potentials tested, ReaxFF reproduces the concentration dependence of spectral features closest to the experimentally observed trend. Thus, the bond length and angle distributions as well as Si–Qⁿ species and ring size distributions of silica and sodium silicate glasses were obtained from ReaxFF-MD simulations and further compared with the peak assignment or deconvolution schemes—which have been widely used since 1970s and 1980s—(a) correlation between the IR peak position in the Si–O stretch region (1050-1120 cm⁻¹) and the Si–O–Si bond angle; (b) deconvolution of the Raman bands in the Si–O stretch region with the Qⁿ speciation; and (c) assignment of the Raman bands in the 420-600 cm⁻¹ region to the bending modes of (SiO)_n rings with different sizes (typically, n = 3-6). The comparisons showed that none of these widely used methods is congruent with the bond parameters or structures of silicate glass networks produced via ReaxFF-MD simulations. This finding invokes that the adequacy of these spectral interpretation methods must be questioned. Alternative interpretations are proposed, which are to be tested independently in future studies.     

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.     

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.     

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 the Glass Structure on Emission of Rare‐Earth‐Doped Borate Glasses

A series of glasses composed of xB₂O₃–8Al₂O₃‐(90?x)Na₂O–R₂O₃ (x = 65, 70, 75, 80, 85; R = Dy³⁺, Tb³⁺, Sm³⁺) were prepared through melt‐quenching. Structural evolution was induced by varying the glass composition. Increasing the glass network former B₂O₃ enhanced the luminescence of rare‐earth ions, as observed in the emission spectra. The mechanism of the glass structural evolution was investigated by the NMR spectra analysis. The dispersant effect of the glass structure was believed to promote the better distribution of the rare‐earth ions in the matrix and reduced the concentration quenching between them. The relationship between the glass structure and its optical properties was established.     

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.     

Synthesis,physical, optical,structural and radiation shielding characterization of borate glasses: A focus on the role of SrO/Al2O3 substitution

In a bid to expand the amount of information available on glass systems and their potential applications for radiation shielding design, glass samples with the compositions (30-x)SrO-xAl₂O₃–68B₂O₃–2V₂O₅(x = 5, 7.5, 10, 12.5&15 mol %) coded as SABV0 - 4 were prepared by the melt-quenching technique and analyzed for their optical, structural, physical, and radiation shielding features. The glassy (amorphous) nature of the SABV glass samples was affirmed by broad peaks of X-ray diffraction spectra. Calculated values of density and molar volume shown opposite behavior and the variation of these values were discussed as structural modifications in the glass matrix. From recorded optical absorption spectra optical band gap energy (Eg)-indirect transition, Urbach energy and optical basicity were estimated. FTIR spectra were recorded for all the samples in the range 400 cm^?1 to 4000 cm^?1. The FTIR absorbance spectra unveiled the SABV network structure mainly incorporating of BO₃ and BO₄ units. Raman spectroscopy is achieved to detect the structural changes and at higher wavenumber, B–O stretching modes in [BO₃] observed with one or two NBO's. The results of ESR spectra of glasses have indicated the highly covalent environment of vanadium ions. Analysis of the photon shielding parameters of the glasses which were obtained primarily from FLUKA Monte Carlo simulations and XCOM computations revealed photon energy and glass chemical composition dependence. The mass attenuation coefficient and effective atomic number ranged from 0.2668 to 0.3385 cm²g^-1 and 12.98–15.93 accordingly as the weight fraction of Sr increased from 16.06 to 26.72% in the glasses. Generally, photon shielding ability of the SABV glasses follows the trend: SABV0 > SABV1 > SABV2 > SABV3 > SABV4. The thermal neutron total cross section follows the same trend with values fluctuating between 71.9553 and 80.6268 cm^?1. However, SABV1 showed superior fast neutron moderating capacity among the glasses. The present SABV glasses showed outstanding photon shielding ability compared to common shields. The prepared glasses are thus suitable candidates for radiation protection applications.     

First Identification of Rare‐Earth Oxide Nucleation in Chalcogenide Glasses and Implications for Fabrication of Mid‐Infrared Active Fibers

Gallium (Ga) helps solubilize rare‐earth ions in chalcogenide glasses, but has been found to form the dominant crystallizing selenide phase in bulk glass in our previous work. Here, the crystallization behavior is compared of as‐annealed 0–3000 ppmw Dy³⁺‐doped Ge–As–Ga–Se glasses with different Ga levels: Ge_16.5As_(19?x)Ga_xSe_64.5 (at.%), for x = 3 and 10, named Ga₃ and Ga₁₀ glass series, respectively. X‐ray diffraction and high‐resolution transmission electron microscopy are employed to examine crystals in the bulk of the as‐prepared glasses, and the crystalline phase is proved to be the same: Ge‐modified, face centered cubic α‐Ga₂Se₃. Light scattering of polished glass samples is monitored using Fourier transform spectroscopy. When Ga is decreased from 10 to 3 at.%, the bulk crystallization is dramatically reduced and the optical scattering loss decreases. Surface defects, with a rough topology observed for both series of as‐prepared chalcogenide glasses, are demonstrated to comprise Dy, Si, and [O]. For the first time, evidence for the proposed nucleation agent Dy₂O₃ is found inside the bulk of as‐prepared glass. This is an important result because rare‐earth ions bound in a high phonon–energy oxide local environment are, as a consequence, inactive mid‐infrared fluorophores because they undergo preferential nonradiative decay of excited states.     

Effects of Difference in Ionic Radii on Chemical Ordering in Mixed‐Cation Silicate Glasses: Insights from Solid‐State 17O and 7Li NMR of Li–Ba Silicate Glasses

Understanding of the extent of cation disorder and its effect on the properties in glasses and melts is among the fundamental puzzles in glass sciences, materials sciences, physical chemistry, and geochemistry. Particularly, the nature of chemical ordering in mixed‐cation silicate glasses is not fully understood. The Li–Ba silicate glass with significant difference in the ionic radii of network‐modifying cations (~0.59 Å) is an ideal system for revealing unknown details of the effect of network modifiers on the extent of mixing and their contribution to the cation mobility. These glasses also find potential application as energy and battery materials. Here, we report the detailed atomic environments and the extent of cation mixing in Li–Ba silicate glasses with varying X_BaO [BaO/(Li₂O + BaO)] using high‐resolution solid‐state nuclear magnetic resonance (NMR) spectroscopy. The first ¹⁷O MAS and 3QMAS NMR spectra for Li–Ba silicate glasses reveal the well‐resolved peaks due to bridging oxygen (Si–O–Si) and those of the nonbridging oxygens including Li–O–Si and mixed {Li, Ba}–O–Si. The fraction of Li–O–Si decreases with an increase in X_BaO and is less than that predicted by a random Li–Ba distribution. The result demonstrates a nonrandom distribution of Li⁺ and Ba⁺ around NBOs characterized by a prevalence of the dissimilar Li–Ba pair. Considering the previously reported experimental results on chemical ordering in other mixed‐cation silicate glasses, the current results reveal a hierarchy in the degree of chemical order that increases with an increase in difference in ionic radius of the cation in the glasses [e.g., K–Mg (~0.66 Å) ≈Ba–Mg (~0.63 Å) ≈Li–Ba (~0.59 Å) > Na–Ba (~0.33 Å) > Na–Ca (~0.02 Å)]. The ⁷Li MAS NMR spectra of the Li–Ba silicate glasses show that the peak maximum increases with increasing X_BaO, suggesting that the average Li coordination number and thus Li–O distance decrease slightly with increasing X_BaO, potentially leading to an increased activation energy barrier for Li diffusion. Current experimental results confirm that the degree of chemical ordering due to a large difference in ionic radii controls the transport properties of the mixed‐cation silicate glasses.     

Factors Controlling Properties of Ca‐Mg,Ca‐Er,Ca‐Nd,or Ca‐Y‐Modified Aluminosilicate Glasses Containing Nitrogen and Fluorine

Glasses with composition (in eq.%) (30 ? x)Ca:xM:55Si:15Al:80O:15N:5F have been prepared with different levels of substitution of Ca²⁺ cations by Mg²⁺, Y³⁺, Er³⁺, or Nd³⁺. The properties of these glasses are examined in detail and changes observed in molar volume (MV), free volume, fractional glass compactness, Young's modulus, microhardness, glass transition temperature, and thermal expansion as a function of M content are presented. Using linear regression analysis, evidence is presented which clearly shows that these glass properties are either solely dependent on the effective cation field strength, if modifier cation valency is the same (e.g., Mg substitution for Ca), or dependent on the effective cation field strength and the number of (Si, Al) (O, N, F) tetrahedra associated with each modifier when Ca is replaced by the trivalent modifiers. Combining these correlations with those observed previously relating glass properties to N and F substitution for O, it becomes apparent that glass properties for Ca–M–Si–Al–O–N–F glasses can be described by correlations which involve independent, but additive contributions by N and F substitution levels, effective cation field strength, and the number of tetrahedra associated with each modifier ion.     

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.     

Effects of magnesium on the structure of aluminoborosilicate glasses: NMR assessment of interatomic potentials models for molecular dynamics

Classical molecular dynamics simulations have been used to investigate the structural role of Mg and its effect when it is incorporated in sodium aluminoborosilicate glasses. The simulations have been performed using three interatomic potentials; one is based on the rigid ionic model parameterized by Wang et al. (2018) and two slightly different parameterization of the core–shell model provided by Stevensson et al. (2018) and Pedone et al. (2020) The accuracies of these models have been assessed by detailed structural analysis and comparing the simulated nuclear magnetic resonance (NMR) spectra for spin active nuclei (²⁹Si, ²⁷Al, ¹¹B, ¹⁷O, ²⁵Mg, and ²³Na) with the experimental counterparts collected in a previous work. Our simulations reveal that the core–shell parameterizations provide better structural models. In fact, they better reproduce the NMR spectra of all the investigated nuclei and give better agreement with known experimental data. Magnesium is found to be five coordinated on average with distances with oxygen in between a network modifier (like Na) and an intermediate network formed (like Al). It prefers to lay closer to three-coordinated B atoms, forming B–NBO bonds, with respect to Si and especially Al. This can explain the formation of AlO₅ and AlO₆ units in the investigated Na-free glass, together with a Si clusterization.