Cation Field Strength Research Articles

Structure, chemical durability, and melting properties of aluminosilicate glass

AbstractBorosilicate glasses possess excellent melting properties and high stability against chemical attack by aqueous solutions, enabling this glass family to be used in various fields. In this article, we design a novel glass network in order to achieve a chemically robust glass with a low melting temperature. Therefore, the substitution effect of Na2O by MgO, Al2O3, Li2O, and K2O on the chemical durability and melting properties of sodium aluminosilicate glass (i.e., 80SiO2‒5Al2O3‒15Na2O [mol%]) was examined using a standard hydrolytic resistance test and viscosity measurement. Interestingly, we found that the partial replacement of Na2O by Al2O3, Li2O, and K2O (i.e., 80SiO2‒5Al2O3‒15Na2O → 80SiO2‒6.5Al2O3‒9Li2O‒2.25Na2O‒2.25K2O) makes the glass network with chemical durability and melting properties comparable to those of the commercial borosilicate network, resulting in a low HCl consumption of 0.04 mL/g and working temperature of 1238°C (i.e., temperature at viscosity 104 dPa s). The structural characterizations indicate that the high chemical stability of this glass composition originates from the abundance of SiO4 tetrahedrons with three and four bridging oxygen in the glass network as well as the increase in cationic field strength of mixed alkali ions. These excellent melting properties and superior chemical durability of glass imply the possibility of using the mixed alkali metal oxides aluminosilicate glass together with the commercial borosilicate glass in the markets for numerous practical applications.

Prediction of glass‐forming regions in AlF3‐M(PO3)2‐R2SO4‐based poly‐anionic fluoro‐sulfo‐phosphate glasses

AbstractPhosphate glasses have garnered significant attention as host materials for various laser applications due to their high rare‐earth ion solubility, large stimulated emission cross‐section, and low nonlinear refractive index. Modification of phosphate glass composition is feasible through poly‐anion substitution, leading to poly‐anionic glasses with unique properties. This study explores the glass‐forming regions (GFRs) of AlF3‐R2SO4‐M(PO3)2‐based poly‐anionic fluoro‐sulfo‐phosphate (R/M‐FSP) glasses, a promising class of ionic glasses. Theoretical GFRs are predicted using a thermodynamic approach and then validated through a few experiments. The experimental GFRs range from K/Ba‐FSP > Na/Ba‐FSP > Li/Ba‐FSP > K/Sr‐FSP > Na/Sr‐FSP > Li/Sr‐FSP, with wider areas observed under lower cation field strength. Notably, the K/Ba‐FSP glass system exhibits high anti‐crystallization stability (approximately 140°C) and a low nonlinear refractive index (1.43 × 10–13–1.83 × 10–13 esu), advantageous for high‐power laser operations. Furthermore, a comparative study among K/Ba‐FSP glasses elucidates the general principles of manipulating glass structure and physical properties through compositional variation.

Physical, optical, thermal, structural and mechanical properties of alkaline earth borate glasses

Binary alkaline earth borate glasses were synthesized via the melt quenching technique. The density and molar volume of the resultant glasses were determined experimentally. The glass optical basicity has been found to increase with the glass polarizability. The optical properties of the glasses were comprehensively analyzed, revealing a shift in the cutoff wavelength towards longer wavelengths with increasing glass optical basicity. Additionally, the optical band gap (Eg) was estimated. Structural investigations unveiled an increase in the abundance of BO4 units as the glass optical basicity increased. Furthermore, the glass transition temperature was observed to decrease with decreasing cation field strength. Glass packing density and B2O3 packing factor were calculated to assess structural variations. The longitudinal and shear velocities were determined using the pulse echo technique, providing insights into the elastic moduli of the glasses. The Makishima and Mackenzie approach was employed to predict the elastic moduli, yielding results in good agreement with experimental data. This comprehensive analysis sheds light on the relationship between composition, structure, and mechanical properties of binary alkaline earth borate glasses, offering valuable insights for potential applications.

Sub-Nanometer-Range Structural Effects From Mg2+ Incorporation in Na-Based Borosilicate Glasses Revealed by Heteronuclear NMR and MD Simulations.

Magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) experiments and molecular dynamics (MD) simulations were employed to investigate Na2O-B2O3-SiO2 and MgO-Na2O-B2O3-SiO2 glass structures up to ≈0.3 nm. This encompassed the {Na[p]}, {Mg[p]}, and {B[3], B[4]} speciations and the {Si, B[p], M[p]}-BO and {Si, B[p], M[p]}-NBO interatomic distances to the bridging oxygen (BO) and nonbridging oxygen (NBO) species, where the superscript indicates the coordination number. The MD simulations revealed the dominance of Mg[5] coordinations, as mirrored in average Mg2+ coordination numbers in the 5.2-5.5 range, which are slightly lower than those of the larger Na+ cation but with a narrower coordination distribution stemming from the higher cation field strength (CFS) of the smaller divalent Mg2+ ion. We particularly aimed to elucidate such Na+/Mg2+ CFS effects, which primarily govern the short-range structure but also the borosilicate (BS) glass network order, where both MD simulations and heteronuclear double-resonance 11B/29Si NMR experiments revealed a reduction of B[4]-O-Si linkages relative to B[3]-O-Si upon Mg2+-for-Na+ substitution. These effects were quantified and discussed in relation to previous literature on BS glasses, encompassing the implications for simplified structural models and descriptions thereof.

Effects of rare-earth oxides on grain boundary strength of silicon nitride ceramics

This study investigates the grain boundary (GB) strengths for Si3N4 ceramics doped with 3 wt% RE2O3 (RE = Y, La, or Lu) and 7 wt% MgO, using microcantilever beam specimens having different misorientation angles of the two adjacent grains. The measured strengths are so high that they are comparable to the theoretical strength of the intergranular glassy film (IGF). They are also widely scattered with a Weibull modulus of 3.0. The strength depends on the type of RE2O3 and increases in order of Y<La<Lu. It is suggested that the fracture occurs from the IGF/Si3N4 interfaces rather than within the IGF, and that O anions, which reside within the IGF and do not dissolve into the β-Si3N4 crystal lattice because of the high cationic field strength, reduce the IGF/grain interface strength. The GB strength also little depends on the misorientation angles, which is discussed in relation with the IGF accommodation ability of mismatch.

Impacts of substitution of alkali by zinc on thermo-mechanical properties in borosilicate glasses

To decipher the effects of replacing alkali with zinc on thermo-mechanical properties, a series of borosilicate glasses with the molar compositions of 70.65SiO2·21.09B2O3·1.88Al2O3·1Li2O·(5.38-x)R2O·xZnO (x = 0, 0.34, 0.67, 1, 1.34, 2.69, 4.04, and 5.38) were prepared. Upon adding a slight quantity of ZnO, a local extreme point for glass transition temperature (Tg) appears. This behavior is deciphered to be originated from two opposite factors. On one hand, Tg reduces as a characteristic of the colligative properties for a dilute solution; in addition, Tg rises due to the higher field strength, bond energy and covalent characteristic of zinc cations compared to that of alkali ions. Otherwise, based on the evolution of intermediate-range clusters revealed by infrared, Raman and NMR spectra, we elucidate the atomic-scale structural origin, which leads to the nonlinear evolution of elastic moduli and coefficient of thermal expansion with the molar ratio of [ZnO]/([R2O]+[ZnO]).

Analysis of the Dielectric Properties of Alkali-Free Aluminoborosilicate Glasses by Considering the Contributions of Electronic and Ionic Polarizabilities in the GHz Frequency Range.

Recently, the investigation of the dielectric properties of glasses in the GHz frequency range has attracted great interest for use in printed circuit boards (PCBs) as a reinforcing material in the application of high-speed 5G/6G communications. In particular, glasses with low dielectric properties are a prerequisite for high-frequency applications. In this study, the GHz dielectric properties of alkali-free aluminoborosilicate glasses without and with La2O3 were analyzed using the Clausius-Mossotti equation where both the electronic and ionic polarizabilities contribute to the dielectric constant. The dielectric polarizability (αD) and oxide ion polarizability (αO2-) were calculated from the measured dielectric constant (εGHz) at 1 GHz and the glass density. The dielectric constants (εopt) at the optical frequencies and electronic polarizabilities (αe) of the glasses were calculated from the refractive index measured at 633 nm and the glass density. The εGHz values were found to be significantly higher than the εopt values in both series of glasses, due to the ionic polarizability (αi), which contributes additionally to the εGHz. The lower dielectric constants of the La2O3-incoporated glasses than that of the reference glass without La2O3 may be due to the lower ionic polarizability originated from the incorporation of the high cation field strength of the La3+ ions.

Impact of Lanthanide (Nd3+, Gd3+, and Yb3+) Ionic Field Strength on the Structure and Thermal Expansion of Phosphate Glasses.

Phosphate glasses containing Nd3+, Gd3+, and Yb3+ as lanthanide ions are attractive for applications in laser materials, phototherapy lamps, and solar spectral converters. The composition-structure-property relation in this type of glass system is thus of interest from fundamental and applied perspectives. In this work, the impact of the differing ionic radius of Nd3+, Gd3+, and Yb3+ and consequent field strength on the physical properties of phosphate glasses is investigated, focusing ultimately on thermal expansion effects. The glasses were made by melting with a fixed concentration of the lanthanide ions having 50P2O5-46BaO-4Ln2O3 nominal compositions (mol %) with Ln = Nd, Gd, and Yb. The investigation encompassed measurements by X-ray diffraction (XRD), optical spectroscopy, density, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and dilatometry. XRD supported the amorphous nature of the glasses, whereas absorption and photoluminescence spectra showed the optical features of the Nd3+, Gd3+, and Yb3+ ions in the glasses. Oxygen speciation by XPS indicated an increase in nonbridging oxygens for the larger radii Nd3+ and Gd3+ ions relative to the host, contrasting with Yb3+. Phosphorus XPS analysis further supported the hypothesis that the P 2p binding energies of the glasses increased with the cation field strength of the lanthanides. The Raman spectra were interpreted based on glass depolymerization effects and the impact of Ln3+ ions with high field strength. Particularly, the band position of the symmetric out-of-chain nonbridging oxygen stretch, νs(PO2-), shifted to higher frequencies correlating with the Ln3+ field strength. Dilatometry ultimately revealed a steady decrease in the coefficient of thermal expansion for the glasses, which correlated linearly with Ln3+ field strengths and thus indicated to sustain increased glass rigidities. The various analyses performed thus illuminated the structural foundation of the thermomechanical behavior of the glasses connected with changes in the Ln3+ field strengths.

Structure and chemical durability improvement of alkali silicate glass by zirconium dioxide and erbium oxide addition

Glass structure tailoring of alkali silicate glasses by addition of ZrO2 and Er2O3 is found to enhance the chemical durability of glasses. ZrO2 (x ranged between 5 mol% to 15 mol%) and Er2O3 (y ranged between 0.5 mol% to 1.5 mol%) were used to replace SiO2 and Na2O, respectively, in the glasses with the nominal composition of 10Li2O-(15-y)Na2O-10CaO-(65-x)SiO2-xZrO2-y Er2O3. The samples were prepared by conventional melt quenching technique. The structures of produced glasses were examined by X-ray absorption spectroscopy (XAS) and Raman spectroscopy. XAS spectra demonstrated that the oxidation numbers of Zr and Er ions were +4 and +3, respectively. The chemical environment around both cations was six-fold coordination. In addition, Raman spectra demonstrated that the Zr4+ ions formed the Q4(Zr) structure, which caused the reduction of non-bridging oxygen. In case of the Er3+ ions, the formation of the Si-O-Er bonds was explained from the Raman study. The chemical durability of glass was determined from Na+ ions leaching values. In pH 7 solution, the leached Na+ ions reduced from 25.67% to 21.43% and from 22.50% to 20.49% as a function of concentration of ZrO2 (x = 5 mol% to 15 mol%) and Er2O3 (y = 0.5 mol% to 1.5 mol%), respectively. As the results, the chemical durability of the ZrO2-containing and Er2O3-containing glasses were significantly improved due to charge compensated mechanism and enhancing network rigidity by increasing cation field strength. Moreover, the micro-hardness (580 HV to 837 HV) and density (2.54 g⸳cm-3 to 2.82 g⸳cm-3) also displayed an increased tendency with larger concentration of ZrO2 and Er2O3.

Improved Haacke's quality factor, third order nonlinear susceptibility and specific capacitance realized for PbS thin films through La3+ doping

The present study examines the third order NLO and electrochemical properties of spray deposited lanthanum doped PbS (PbS:La) thin films. FCC crystallization was confirmed by XRD patterns along the plane (2 0 0). PbS crystallites vary in size between 27 and 36 nm with La doping concentration. Surface morphology improved with La doping. La doping increases the band gap from 1.97 to 2.18 eV. Near band edge (NBE) emissions in PL spectra originates from electron-hole recombination. A low resistivity of 0.23 x10−3 Ω-m was realized for PbS film doped with 4 wt% La concentration. Figure of merit of pure PbS improves from 1.32 x 10−3 Ω−1 to 1.607 x 10−2 Ω−1 with La doping. La doping modifies the energy states and band gap of PbS favouring strong nonlinear optical absorption. PbS:La thin films demonstrate self-defocusing due to temperature effects caused by absorption of single photons or free carriers. As a result of the low cationic field strength and high polarizability of La3+ ions, PbS exhibits a higher nonlinear refractive index. The nonlinear susceptibility and refractive index were found to be in the range 3.23–5.33 x 10−6 esu and 2.74 to 3.64 x 10−9 cm2/W, respectively. From the electrochemical studies, increased specific capacitance (256.46 F/g) and decreased charge transfer resistance (12 x 103 Ω) was observed for the 4 wt% La doped film.

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

AbstractWe 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 Mz+ CFS, that is, for higher Mz+⋅⋅⋅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 Mz+⋅⋅⋅O bonds. Our results underscore the advantages of employing BS glasses with high‐CFS cations for enhancing the radiation resistance for nuclear waste storage.

Trace element partitioning coefficients between terrestrial silicate melts and plagioclase feldspar: Improved and simplified parameters

Nernst partition coefficient data are compiled and parameterized against commonly measured and petrologically significant Input Variables, allowing plagioclase/meltD values for 37 trace elements to be calculated. With few exceptions plagioclase/meltDs increase with decreasing temperature, anorthite-content of plagioclase (An), wt% melt MgO and FeO* (all iron as FeO), molar melt Mg/(Mg + Fetotal); and with increasing wt% melt SiO2 and Na2O + K2O. High field strength cations and rare earth elements (REE) with similar ionic radii have nearly fixed ratios of LnD (e.g. LnDLa/LnDCe). These can be linked as a chain to construct a nearest-neighbour plagioclase/meltDREE (NN-DREE) profile from a point of origin at DCe. Correlations between LnDCe and An content in the partitioning data were regressed to connect these variables algebraically. Analysis of these NN-DREE profiles with the Lattice Strain Model (LSM) requires a temperature value, which was pre-defined by fitting simplified temperature-An paths to experimental data binned for melt H2O content. In the LSM, r3+0 is the size of the site into which REE substitute. Three published r3+0 parameterizations were tested. The Dohmen and Blundy (2014) parameterization of r3+0 [Å] (r3+0 = 1.331 − 0.067An) yielded the best fits to the NN-DREE profiles when values of D3+0 and E3+M were optimized. D3+0 is the strain compensated partition coefficient and E3+M is Young’s Modulus of the M-site hosting REE. Starting from the preferred r3+0 parameterization, NN-DREE profiles at many An contents were fit with a LSM by varying D3+0 and E3+M. These multiple fits yielded a tight linear trend of increasing LnD3+0 with decreasing An content [LnD3+0 = (−2.8323An) – 0.0538] applicable to all three temperature-An functions. Previously proposed parameterizations of Young’s Modulus E3+M can reproduce DREE profiles of very calcic plagioclase (>An0.9), but yield profiles that are too steep to fit DREE profiles of more sodic compositions. The LSM fits for dry melts (H2O < 1%) yield a trend of linearly-decreasing LnE3+M with decreasing An content [LnE3+M = (1.2808An) + 3.4897]. The temperature-An functions for wet (1–5% H2O) and very wet (>5% H2O) melts yield similar LnE3+Mvs An trends, but at lower LnE3+M to compensate for lower temperatures. With these parameterizations of temperature, r3+0, D3+0 and E3+M, the NN-DREE Lattice Strain Model reproduces the increasingly flatter and higher DREE profiles of plagioclase crystallizing from basaltic to rhyolitic melts, with An-content as the sole Input Variable needed.

Density functional modeling of the binding energies between aluminosilicate oligomers and different metal cations

Interactions between negatively charged aluminosilicate species and positively charged metal cations are critical to many important engineering processes and applications, including sustainable cements and aluminosilicate glasses. In an effort to probe these interactions, here we have calculated the pair-wise interaction energies (i.e., binding energies) between aluminosilicate dimer/trimer and 17 different metal cations Mn+ (Mn+ = Li+, Na+, K+, Cu+, Cu2+, Co2+, Zn2+, Ni2+, Mg2+, Ca2+, Ti2+, Fe2+, Fe3+, Co3+, Cr3+, Ti4+ and Cr6+) using a density functional theory (DFT) approach. Analysis of the DFT-optimized structural representations for the clusters (dimer/trimer + Mn+) shows that their structural attributes (e.g., interatomic distances) are generally consistent with literature observations on aluminosilicate glasses. The DFT-derived binding energies are seen to vary considerably depending on the type of cations (i.e., charge and ionic radii) and aluminosilicate species (i.e., dimer or trimer). A survey of the literature reveals that the difference in the calculated binding energies between different Mn+ can be used to explain many literature observations associated with the impact of metal cations on materials properties (e.g., glass corrosion, mineral dissolution, and ionic transport). Analysis of all the DFT-derived binding energies reveals that the correlation between these energy values and the ionic potential and field strength of the metal cations are well captured by 2nd order polynomial functions (R2 values of 0.99–1.00 are achieved for regressions). Given that the ionic potential and field strength of a given metal cation can be readily estimated using well-tabulated ionic radii available in the literature, these simple polynomial functions would enable rapid estimation of the binding energies of a much wider range of cations with the aluminosilicate dimer/trimer, providing guidance on the design and optimization of sustainable cements and aluminosilicate glasses and their associated applications. Finally, the limitations associated with using these simple model systems to model complex interactions are also discussed.

The modification and strengthening dual functionality of rare-earth oxide in La2O3-BaO-SiO2 glass for high temperature sealing application

In this paper, the modification and strengthening dual functionality of rare-earth oxide is authenticated by the effect La2O3/BaO on composition-structure-property correlations of new type La2O3-BaO-SiO2 (LBS) glass-ceramics sealing material with high softening point, high coefficient of thermal expansion and excellent high temperature resistivity. As the network modifier, the La2O3 can create more non-bridging oxygen than the BaO, resulting in the increase of Q0 and Q1 units and the decrease of Q2 and Q3 units in the La2O3-BaO-SiO2 glass according to Raman and 29Si Solid-State Nuclear Magnetic Resonance. The strengthening functionality of La2O3 is declared by Static 139La WURST-QCPMG NMR spectra that La3+ ions form La-O bonds with O2- ions in the glass structure and La3+ spectra widens slightly with the increasing of La2O3. Correspondingly, physical properties including Tg, Tc, ρ, and MV of La2O3-BaO-SiO2 glass gradually increase with increasment of effective cation field strength. The main crystal phase of LBS glass-ceramic transforms from Ba2Si3O8 to Ba5Si8O21 and furthur to Ba3Si5O13 phase with high coefficient of thermal expansion and there is not lanthanum-contained phase precipitation. The coefficients of thermal expansion (CTE) of LBS glass-ceramic increases from 12.48 × 10−6/℃ to 13.18 × 10−6/℃ (30–1000 ℃) and the softening temperature are between 1231.1 ℃ and 1305.1 ℃. The direct-current (DC) resistivity of the LBS glass-ceramics is higher 106 Ω·cm at a high temperature of 700 °C, which has good high-temperature electrical insulation. All in all, the high CTE, high Ts and high electrical insulation “Tri-high” properties of rare-earth oxide La2O3-BaO-SiO2 glass-ceramic will be an excellent candidate for solid oxide fuel cell, solid oxide electrolysis cell, oxygen sensors, and so on.

Tuning the fluorescence of Dy3+ via the structure of borophosphate glasses

The optical characteristics of Dy3+-doped phosphate and borophosphate glasses with different divalent network modifiers prepared by melt-quenching are studied. The glass sets (A) with a molar composition of 40MO–60P2O5 and (B) with a molar composition of 40MO–20B2O3–40 P2O5 are investigated, both with M = (Zn2+, Mg2+, Ca2+, Sr2+, or Ba2+) and all doped with 0.1 mol% Dy2O3. Raman and fluorescence spectroscopy are used to analyse the structure and optical characteristics of these glasses. Four typical Dy3+ emission bands in the yellow (572 nm), blue (483 nm) and red (633 and 752 nm) regions of the spectrum are observed in both sets. The fluorescence lifetimes in each glass set are correlated to the network modifier's ionic field strength. The Mg2+ and Zn2+ containing glasses have the longest fluorescence lifetimes. The yellow to blue emission intensity ratio of the respective bands can be used to indicate a symmetric environment around Dy3+ ions and varies with the ionic field strength of the modifier cations: a higher ionic field strength leads to a higher yellow to blue ratio, which in turn indicates a higher asymmetrical local coordination environment of Dy3+ ions in the glassy host network.

Tailoring the efficient laser‐absorption‐melting behavior of Bi2O3‐B2O3‐ZnO‐Nd2O3 glass for the OLED encapsulation

AbstractThe efficient 810 nm laser energy conversion of glass frit had been proven to be the key to the long‐term hermetic encapsulation of Organic Light Emitting Display (OLED). A direct laser energy conversion laser‐assisted Bi2O3‐B2O3‐ZnO‐Nd2O3 sealing glass material without extra laser absorbent such as carbon black, was designed and systematically investigated. The addition of Nd2O3, as glass modifiers with higher cationic field strength, could be conducive to enhancing the polymerization of glass network structure, manifesting that the glass‐transition temperature Tg, onset‐crystallization temperature Tc and thermal stability ΔT (ΔT = Tc‐Tg) increased, while thermal expansion coefficient CTE dropped to 9.72×10−6/°C and advantageously matched with the glass substrate (8±1×10−6/°C). More importantly, the absorption rate of BBZ‐Nd glass was more than 50 % between 800∼810 nm owing to the 4f‐4f electron transition of Nd3+ ions, and yet the reflectivity and transmittance of the wavelength at 800–810 nm were lower. As optimal compositions, the addition of 3.0 wt% Nd2O3 in Bi2O3‐B2O3‐ZnO‐Nd2O3 glass frit with higher absorption coefficients (80 %) led to instantaneous bonding encapsulation between glass substrates without interfacial cracks or pores with the 808 nm wavelength of the laser at 20 W and 2.4 mm/s.

Insights into the mechanism and kinetics of dissolution of aluminoborosilicate glasses in acidic media: Impact of high ionic field strength cations

Achieving thinner and higher performance display/substrate glasses and transparent glass-ceramics with tunable properties requires a precise control of acid-etching process, thus necessitating a comprehensive understanding of glass composition–structure–dissolution behavior relationships in acidic medium. Unfortunately, the literature on this subject has been focused only on a narrow set of glass chemistries. Therefore, consensus on the mechanisms that govern the acidic dissolution of multicomponent silicate glasses over a broad compositional space is still lacking. The present work employs a suite of state-of-the-art spectroscopic techniques, including 1D and 2D NMR, TEM-EELS, ICP-OES, and XPS, to provide an insight into the mechanism and kinetics of corrosion of alkali/alkaline-earth aluminoborosilicate glasses (comprising high field strength cations – HFSCs, i.e., La3+, Ti4+, Zr4+ and Nb5+) in acidic media (HCl; pH = 2). Incorporating the HFSCs into the glasses induces significant structural changes in their network, thus, impacting the forward rate dissolution kinetics. Based on the results, we hypothesize that the glasses dissolve at pH = 2 through an ‘interfacial dissolution – re-precipitation mechanism (IDPM)’ and ‘in-situ recondensation’ coupled pattern, wherein the IDPM results in a Si-rich alteration layer, followed by local recondensation occurring due to limited kinetics near the interfacial solution between the uncorroded glass surface and the outer alteration layer.

Mechanical properties of oxynitride glasses

AbstractOxynitride glasses combine a high refractoriness, with Tg typically &gt;850°C, and remarkable mechanical properties in comparison with their parent oxide glasses. Their Young's modulus and fracture toughness reach 170 GPa and 1.4 MPa m.5, respectively. Most reports show good linear relationships between glass property values and nitrogen content. There is a clear linear dependence of Young's modulus and microhardness on fractional glass compactness (atomic packing density). They also have a better resistance to surface damage induced by indentation or scratch loading. The improvements stem from the increase of the atomic network cross‐linking—because of three‐fold coordinated nitrogen—and of the atomic packing density, despite nitrogen being lighter than oxygen and the Si–N bond being weaker than the Si–O bond. For constant cation composition, viscosity increases by ∼3 orders of magnitude as ∼17 eq.% oxygen is replaced by nitrogen. For rare earth oxynitride glasses with constant N content, viscosity, Young's modulus, Tg, and other properties increase with increasing cation field strength (decreasing ionic radius). Research continues to find lighter, stiffer materials, including glasses, with superior mechanical properties. With higher elastic moduli, hardness, fracture toughness, strength, surface damage resistance, increased high temperature properties, oxynitride glasses offer advantages over their oxide counterparts.

Correlation of the Vickers hardness of RO–Al2O3–SiO2 glasses with predicted liquidus temperatures

AbstractVickers hardnesses of RO–Al2O3–SiO2 glasses were measured over a broad range of compositions, ranging from ternary endpoints to mixed ratios of RO (CaO with MgO, SrO, or BaO), with the systematic variation of Al2O3 and SiO2 levels. The hardnesses of CAS and MAS glasses are similar, ranging from 6.7 to 7.2 GPa, with the replacement of CaO with MgO producing a marginal increase in hardness. The substitution of SrO or BaO for CaO generally produced in a decrease in hardness down to 4.5 GPa with BaO. The sensitivity to alumina and silica levels, however, was much greater ranging from a minimum of 4.5 GPa to a maximum of ∼8.2 GPa. The correlation of the Vickers hardness with melting temperature was observed in the CAS system but generally not in the RO‐blended glasses. Overall, a combined cation field strength of modifier cations determined the hardness above the critical RO blending ratio.

Cation speciation, compactness, and structure‐property correlations in manganese aluminosilicate glasses

AbstractWe report on the elastic properties of xMnO‐Al2O3‐(6‐x)SiO2 manganese aluminosilicate glasses, in which pronounced exchange coupling and antiferromagnetic interaction occurs among the paramagnetic Mn2+ ions. X‐ray absorption reveals a Mn‐O bond length of ∼2.1 Å, and a distance of ∼3 Å between Mn2+ ions in sixfold coordination, further corroborated by electron paramagnetic resonance and dynamic photoluminescence spectroscopy. This indicates the presence of edge‐sharing MnO6 units, in resemblance to edge‐sharing MnO8 in the crystalline Spessartine garnet Mn3Al2[SiO4]3. We argue that these cluster species have a profound effect on material stiffness: the compact structure of manganese aluminosilicate glasses enables a Young's modulus in the 100 GPa range and a Poisson's ratio of about 0.3. This exceeds the compositional trend with cation field strength observed for other aluminosilicate glasses.