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.     

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.     

Field strength effect on structure,hardness, and crack resistance in single modifier aluminoborosilicate glasses

Although the interactions among glass formers and modifiers, for example, connectivity and charge distribution, have been studied extensively in oxide glasses, the impact of a particular modifier species on the mechanical performance of aluminoborosilicate (ABS) glasses is not well understood. This work compares the indentation properties of six ABS glasses, each of which contains a different network modifier (NWM) with varying field strength (FS). Three alkali and three alkaline earth ABS glasses were designed with low NWM content and [NWM] ≈ [Al₂O₃], to test the modifier FS effect at low concentrations and to maximize three-coordinated boron. It has been found that both hardness and crack resistance increase with increasing FS in these ABS systems, which is surprising in the context of historical reports. Using ¹¹B, ²⁷Al, and ²⁹Si solid-state nuclear magnetic resonance, this work provides evidence of how charge distributions differ as a function of NWM species, and how this relates to the observed indentation behaviors.     

Effects of Al:Si and (Al + Na):Si ratios on the properties of the international simple glass,part II: Structure

High-alumina containing high-level waste (HLW) will be vitrified at the Waste Treatment Plant at the Hanford Site. The resulting glasses, high in alumina, will have distinct composition-structure-property (C-S-P) relationships compared to previously studied HLW glasses. These C-S-P relationships determine the processability and product durability of glasses and therefore must be understood. The main purpose of this study is to understand the detailed structural changes caused by Al:Si and (Al + Na):Si substitutions in a simplified nuclear waste model glass (ISG, international simple glass) by combining experimental structural characterizations and molecular dynamics (MD) simulations. The structures of these two series of glasses were characterized by neutron total scattering and ²⁷Al, ²³Na, ²⁹Si, and ¹¹B solid-state nuclear magnetic resonance (NMR) spectroscopy. Additionally, MD simulations were used to generate atomistic structural models of the borosilicate glasses and simulation results were validated by the experimental structural data. Short-range (eg, bond distance, coordination number, etc) and medium-range (eg, oxygen speciation, network connectivity, polyhedral linkages) structural features of the borosilicate glasses were systematically investigated as a function of the degree of substitution. The results show that bond distance and coordination number of the cation-oxygen pairs are relatively insensitive to Al:Si and (Al + Na):Si substitutions with the exception of the B-O pair. Additionally, the Al:Si substitution results in an increase in tri-bridging oxygen species, whereas (Al + Na):Si substitution creates nonbridging oxygen species. Charge compensator preferences were found for Si-[NBO] (Na⁺), ^[3]B-[NBO] (Na⁺), ^[4]B (mostly Ca²⁺), ^[4]Al (nearly equally split Na⁺ and Ca²⁺), and ^[6]Zr (mostly Ca²⁺). The network former-BO-network former linkages preferences were also tabulated; Si-O-Al and Al-O-Al were preferred at the expense of lower Si-O-^[3]B and ^[3]B-O-^[3]B linkages. These results provide insights on the structural origins of property changes such as glass-transition temperature caused by the substitutions, providing a basis for future improvements of theoretical and computer simulation models.     

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.     

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.     

High Na‐ion conducting Na1+x[SnxGe2−x(PO4)3] glass‐ceramic electrolytes: Structural and electrochemical impedance studies

Na‐ion conducting Na_1+x[Sn_xGe_2?x(PO₄)₃] (x = 0, 0.25, 0.5, and 0.75 mol%) glass samples with NASICON‐type phase were synthesized by the melt quenching method and glass‐ceramics were formed by heat treating the precursor glasses at their crystallization temperatures. XRD traces exhibit formation of most stable crystalline phase NaGe₂(PO₄)₃ (ICSD‐164019) with trigonal structure. Structural illustration of sodium germanium phosphate [NaGe₂(PO₄)₃] displays that each germanium is surrounded by 6 oxygen atom showing octahedral symmetry (GeO₆) and phosphorous with 4 oxygen atoms showing tetrahedral symmetry (PO₄). The highest bulk Na⁺ ion conductivities and lowest activation energy for conduction were achieved to be 8.39 × 10^?05 S/cm and 0.52 eV for the optimum substitution levels (x = 0.5 mol%, Na_1.5[Sn_0.5Ge_1.5(PO₄)₃]) of tetrahedral Ge⁴⁺ ions by Sn⁴⁺ on Na–Ge–P network. CV studies of the best conducting Na_1.5[Sn_0.5Ge_1.5(PO₄)₃] glass‐ceramic electrolyte possesses a wide electrochemical window of 6 V. The structural and EIS studies of these glass‐ceramic electrolyte samples were monitored in light of the substitution of Ge by its larger homologue Sn.     

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.     

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.     

Multi-component oxide lens glass with ultra-high mechanical properties inspired by the high-entropy concept

Lenses with high transmittance, high refractive index and excellent scratch resistance are in urgent need for cameras in high-end smartphones, and existing resin lenses exhibits intrinsic upper limits in those properties. Glass, with its naturally high refractive index and mechanical properties, is considered an ideal candidate for high-end lenses, however, due to the lack of targeted design, the intrinsic hardness, modulus and fracture toughness of conventional glass are low and its scratch resistance is inadequate. Here, we combined multi-compositional design and structural modulation of high mechanical lens glass with high-entropy concept, and successfully prepared multi-component 31.6RO-4.1Y₂O₃-23.7TiO₂-7.4ZrO₂-33.2Al₂O₃ (R = Ba, Sr, Ca) glasses with ultra-high hardness (11.06 GPa), modulus (147.6 GPa) and indentation fracture toughness (1.334 MPa m^0.5). The excellently comprehensive properties of the glass are attributed to the synergistic effect of multiple high dissociation energy and high field strength oxides, which leads to the movement of low-coordinated Al^[4] to the higher-coordinated Al^[5]/Al^[6].     

Mixed alkaline‐earth effect on the mechanical and rheological properties of Ca–Mg silicate glasses

In this article, we investigate the mixed alkaline‐earth effect in a silicate glass series with varying the molar ratio of [MgO]/([CaO]+[MgO]). This effect manifests itself as a minimum in Vickers microhardness (H_V), coefficient of thermal expansion (CTE), and isokom temperatures at 10¹²(T_g) and 10² Pa·s, and as a maximum in liquid fragility. To probe the structural origin of the mixed alkaline‐earth effect in CTE and H_v, we conducted the Raman measurements. In contrast to the aluminosilicate glasses, the present glass series exhibit a negative deviation of shift of peak position at ~1100 cm^?1 from a linear additivity, indicating the role of the aluminum speciation in affecting the vibration modes. By fitting the Vogel–Fulcher–Tamann equation to the high‐temperature viscosity data, we found a near‐linear increase of the fractional free volume with the gradual substitution of Ca by Mg, confirming the dynamic structural mismatch model describing the mixed modifier effect. This work gives insight into the mixed modifier effect in glassy systems.     

Structure and disorder in Pb-Na metasilicate (PbO:Na2O:2SiO2) glasses: A view from high-resolution 17O solid-state NMR

Knowledge of the structure of lead (Pb)-bearing silicate glasses, such as degree of polymerization and arrangement among cations, provides improved prospects for understanding their macroscopic properties. Despite the importance, the detailed disorder in Pb-bearing silicate glasses with varying composition (i.e., Pb/alkali content) has not been systematically explored. Here, we reveal the first unambiguous structural information of PbO-Na₂O-SiO₂ glasses with varying PbO content [i.e., X_PbO = PbO/(Na₂O + PbO)], which are the fundamental model system for multicomponent Pb-bearing glasses, using high-resolution ¹⁷O solid-state NMR. ¹⁷O NMR spectra clearly show the resolved multiple oxygen sites, such as Na-O-Si, Si-O-Si, and [Na,Pb]-O-Si. As X_PbO increases, the fraction of [Na,Pb]-O-Si peak increases markedly at the expanse of substantial reduction in the fraction of Na-O-Si/total NBO. This trend indicates the relative predominance of the dissimilar pairs around non-bridging oxygen (NBO) and, therefore, can be explained well with the pronounced chemical ordering among Na⁺ and Pb²⁺. These results confirm that Pb is primarily a network-modifier in the glasses studied here. Atomic environments around both NBO and BO are affected by the change in Na/Pb ratio, while topological disorder due to cation mixing around NBO is much more prominent in Pb endmember. The structural details of short-range configurations around oxygen in alkali Pb-silicate glasses provide atomistic insights for understanding the properties of Pb-bearing multicomponent silicate glasses.     

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.     

Toward hard and highly crack resistant magnesium aluminosilicate glasses and transparent glass-ceramics

High hardness and high crack resistance are usually mutually exclusive in glass materials. Through the aerodynamic levitation and laser melting technique, we prepared a series of magnesium aluminosilicate glasses with a constant MgO content, and found a striking enhancement of both hardness and crack resistance with increasing Al₂O₃. The crack resistance of the magnesium aluminosilicate glass is about five times higher than that of the binary alumina-silica glass for the similar [Al]/([Al] + [Si]) molar ratio (around 0.6). For the selected magnesium aluminosilicate glass with R = 0.32, when subjected to isothermal treatment at 1283K, we observed a further drastic enhancement of both hardness and crack resistance by extending the heating time. Based on the structural analyses, we propose an atomic-scale model to explain the mechanism of synergetic enhancement in hardness and crack resistance for the magnesium aluminosilicate glasses and glass-ceramics.     

Field strength effect on elastoplastic behavior of aluminoborosilicate glass: I. Elastic moduli and indentation size effect

The modifier field strength (FS) is believed to play an important role in determining the elastic–plastic responses of aluminoborosilicate (ABS) glasses, but its effect is not well understood. Three novel alkali and three alkaline earth (AE) ABS compositions were created for this study which is the first part of two studies that explored the elastoplastic responses of these glasses. Six compositions were designed using different network modifiers (NWMs) to cover a range of cation FS. The glasses were also designed such that the concentrations of NWM and Al₂O₃ were similar, which maximized the three-coordinated boron fraction in the network. It is well known that modifier FS can affect the coordination number (CN) of Al and B in an ABS glass structure, for example, a higher FS modifier can promote B³ → B⁴ and higher [Al^5,6], but the degree of this depends on network former (NWF) ratios. Previous work used solid-state NMR spectroscopic analysis on the current glasses to find that there was variation between [B⁴] and [Al⁴] between the two glass series (alkali vs. AE) but that was attributed to synthesis factors and no trend with FS was associated with the varying NWF CN. Further, ²⁹Si ssNMR showed no evidence of NBOs which made sense based on composition. The conclusion, therefore, was that there was a far greater correlation with modifier FS for the increased mechanical and physical properties rather than the CN of Al and B. Part I of the current work focused on the elastic moduli, Poisson's ratio, the indentation size effect (ISE), and the bow-in parameter. This part laid out the foundation to investigate the intersection of these elastoplastic properties with hardness and crack resistance as a function of NWM FS. Results showed that: (i) the Young's, bulk, and shear moduli increased with modifier FS, whereas Poisson's ratio did not trend with FS; (ii) the alkali glasses had a significantly higher magnitudes of ISE compared to the AE glasses; and (iii) the bow-in parameter was load dependent and decreased with modifier FS at the highest indentation load.     

Structural and emission properties of Eu3+‐doped alkaline earth zinc‐phosphate glasses for white LED applications

Quaternary alkaline earth zinc‐phosphate glasses in molar composition (40 ? x)ZnO – 35P₂O₅ – 20RO – 5TiO₂ – xEu₂O₃ (where x=1 and R=Mg, Ca, Sr, and Ba) were prepared by melt quenching technique. These glasses were studied with respect to their thermal, structural, and photoluminescent properties. The maximum value of the glass transition temperature (T_g) was observed for BaO network modifier mixed glass and minimum was observed for MgO network modifier glass. All the glasses were found to be amorphous in nature. The FT‐IR suggested the glasses to be in pyrophosphate structure, which matches with the theoretical estimation of O/P atomic ratio and the maximum depolymerization was observed for glass mixed with BaO network modifier. The intense emission peak was observed at 613 nm (⁵D₀→⁷F₂) under excitation of 392 nm, which matches well with excitation of commercial n‐UV LED chips. The highest emission intensity and quantum efficiency was observed for the glass mixed with BaO network modifier. Based on these results, another set of glass samples was prepared with molar composition (40 ? x)ZnO – 35P₂O₅ – 20BaO – 5TiO₂ – xEu₂O₃ (x=3, 5, 7, and 9) to investigate the optimized emission intensity in these glasses. The glasses exhibited crystalline features along with amorphous nature and a drastic variation in asymmetric ratio at higher concentration (7 and 9 mol%) of Eu₂O₃. The color of emission also shifted from red to reddish orange with increase in the concentration of Eu₂O₃. These glasses are potential candidates to use as a red photoluminsecent component in the field of solid‐state lighting devices.     

Crystallization Kinetics of Superionic Conductive Al(B,La)‐ Incorporated LiTi2(PO4)3 Glass‐Ceramics

For the purpose of developing high‐performance glass‐ceramic superionic conductor, the controllable precipitation of LiTi₂(PO₄)₃‐like superionic conducting phase in the Li₂O–TiO₂–P₂O₅ glass system was studied. Al with B or La co‐incorporated LiTi₂(PO₄)₃‐based glass‐ceramics were prepared by the crystallization of the corresponding original glasses. Compared with the sole Al‐incorporated LiTi₂(PO₄)₃‐based glass‐ceramics, the ionic conductivity shows an increase for the boron co‐incorporated one and a decrease for the lanthanum co‐incorporated one. Through the further in‐depth analysis based on the methods of DSC and X‐ray diffractive technique, this opposite change in ion conductivity was ascribed to the alterations of crystallization mechanism together with quantity of crystal phases within the glass‐ceramics.. The boron addition promoted the precipitation of LiTi₂(PO₄)₃ phase and restrained the precipitation of second phase. The highest ionic conductivity 1.3 × 10^?3 S/cm at 25°C was obtained through the heat treatment of B and Al co‐incorporated glassy samples at 900°C for 12 h. These inorganic solid electrolytes have a potential application in lithium batteries or other electrochemical ionic devices.     

Mixed modifier effect in lithium‐calcium borosilicate glasses

The mixed modifier effect (MME) in the lithium‐calcium borosilicate glasses, which have a composition of 0.4[(1?x)Li₂O–xCaO]–0.6[(1?y)B₂O₃–ySiO₂] with x in the range of 0~1 and y in the range of 0.33~0.83, is investigated. The MME manifests itself as a positive deviation from linearity in the activation energy of electrical conductivity (Ea^σ) and as a negative deviation from linearity in the fraction of four‐coordinated boron (N₄), glass transition temperature (T_g), dilatometric softening temperature (T_d), Vickers microhardness (H_v), dielectric constant (ε), and dielectric loss (tanδ). Moreover, the deviation, which exhibits a maximum at [CaO]/([CaO]+[Li₂O])=0.5, is enhanced with increasing [SiO₂]/[B₂O₃] ratio in the glass network. The observed MME in T_g, T_d, and H_v are attributed to the bond weakening in the network; however, the MME in ε, tanδ, and Ea^σ are caused by the obstruction of modifier transport in the glass network.     

Reduction‐Induced Inward Diffusion and Crystal Growth on the Surfaces of Iron‐Bearing Silicate Glasses

We investigate the sodium inward diffusion (i.e., sodium diffusion from surface toward interior) in iron containing alkaline‐earth silicate glasses under reducing conditions around T_g and the induced surface crystallization. The surface crystallization is caused by formation of a silicate‐gel layer first and then the growth of silica crystals on the glass surface. The type of alkaline‐earth cations has a strong impact on both the glass transition and the surface crystallization. In the Mg‐containing glass, a quartz layer forms on the glass surface. This could be attributed to the fact that Mg²⁺ ions have stronger bonds to oxygen and lower coordination number (4–5) than Ca²⁺, Sr²⁺, and Ba²⁺ ions. In contrast, a cristobalite layer forms in Ca‐, Sr‐, and Ba‐containing glasses.