Transition in deformation mechanism of aluminosilicate glass at high pressure and room temperature

Deformation experiments for 20(MgO or Na₂O)-20Al₂O₃-60SiO₂ glasses were performed in simple shear geometry at 1.5-5 GPa and room temperature. An abrupt change in the thinning rate and the turning of the birefringence azimuth at a shear strain of γ = 1-2 indicate a transition of deformation mechanism from uniaxial compression aided by densification to shear flow in the glasses. The high-dense magnesium aluminosilicate glass showed strain softening controlled by the rearrangement of the tetrahedral network. On the other hand, low-dense sodium aluminosilicate glass deformed by packing-induced flow associated with densification and via the rearrangement of the tetrahedral network at lower and higher strains, respectively. The transition of the deformation mechanism was triggered by the limitations of the densification of the tetrahedral network. The difference of deformation mechanism brought about higher strain in magnesium aluminosilicate glass than sodium aluminosilicate glass at the same stress condition. Easiness of remarkable deformation, which relaxed residual stress, and high deformability contributed to the high ductility of the MgO-aluminosilicate glass.     

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.     

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.     

Mg and Al mixed effects on thermal properties in aluminosilicate glasses

By using the aerodynamic levitation and laser melting technique to well extend the glass-forming region into the Mg-rich and peraluminous regime, a series of magnesium aluminosilicate glasses were prepared to investigate the Mg and Al mixed effects on thermal properties, including glass transition temperature (T_g), crystallization behavior, and thermal stability. With the gradual substitution of Mg by Al, T_g exhibits two types of near-linear rises with different slopes in two compositional regions separated by r = 0.57, where r is equal to the molar ratio of [Al₂O₃]/([Al₂O₃] + [MgO]). Moreover, when it comes to other properties, that is, crystallization behavior and thermal stability, this critical point precisely appears at the same r = 0.57. Compared to the slower increase of T_g in Mg-rich region, the steeper rise of T_g in the peraluminous region is mainly ascribed to the step-by-step formation of oxygen triclusters driven by Pauling's second rule. Moreover, the occurrence of the critical point for T_g rise at r = 0.57 rather than the theoretical 0.5 can be seen as a proof of the role of Mg cations partly as a network former.     

Competitive effects of free volume,rigidity, and self-adaptivity on indentation response of silicoaluminoborate glasses

Lithium aluminoborate glasses have recently been found to feature high resistance to crack initiation during indentation, but suffer from relatively low hardness and chemical durability. To further understand the mechanical properties of this glass family and their correlation with the network structure, we here study the effect of adding SiO₂ to a 25Li₂O–20Al₂O₃–55B₂O₃ glass on the structure and mechanical properties. Addition of silica increases the average network rigidity, but meanwhile its open tetrahedral structure decreases the atomic packing density. Consequently, we only observe a minor increase in hardness and glass transition temperature, and a decrease in Poisson's ratio. The addition of SiO₂, and thus removal of Al₂O₃ and/or B₂O₃, also makes the network less structurally adaptive to applied stress, since Al and B easily increase their coordination number under pressure, while this is not the case for Si under modest pressures. As such, although the silica-containing networks have more free volume, they cannot densify more during indentation, which in turn leads to an overall decrease in crack resistance upon SiO₂ addition. Our work shows that, although pure silica glass has very high glass transition temperature and relatively high hardness, its addition in oxide glasses does not necessarily lead to significant increase in these properties due to the complex structural interactions in mixed network former glasses and the competitive effects of free volume and network rigidity.     

Topological hardening through oxygen triclusters in calcium aluminosilicate glasses

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

The state of magnesium in silicate glasses and melts

The properties of silicate glasses and melts containing magnesium are analyzed in comparison with the properties of glasses and melts in which magnesium is replaced by aluminum. In particular, the properties of the glass and the melt of the diopside composition CaMgSi₂O₆ are analyzed in comparison with the properties of the glass and the melt of the anorthite composition CaAl₂Si₂O₈. It is demonstrated that the properties of aluminosilicate and magnesium silicate glasses and melts differ not so strongly as should be expected upon replacement of modifier ions by network-former ions. By using the parameters γ _n characterizing the cation field strength, it is shown that Mg²⁺ cations can fulfill both the function of network formers like Al³⁺ cations and the function of modifiers like Ca²⁺ cations. The degree of depolymerization of the glass and the melt of the composition CaMgSi₂O₆ is estimated to be 0.4–0.5 from the dependences of the change in the relative density (d − d ₀)/d at different pressures on the degree of depolymerization NBO/T (the ratio of the number of nonbridging oxygen atoms to the number of network-former cations) for silicate glasses and the dependence of the isothermal bulk modulus K _t on the quantity NBO/T for silicate melts.     

Structure and composition of surface depletion layers in poled aluminosilicate glasses

Thermal poling processes can be used to form modified surface layers on glass that, under ion-blocking electrode conditions, are depleted of virtually all network-modifying cations relative to the network-forming species. During this process, many outstanding questions remain as to the structure of these layers and how it may vary between glasses of different “parent” composition, with important implications for resultant surface properties and industrial applications of this technology. This phenomenon of depleting modifiers is particularly difficult to rationalize in aluminosilicate glass compositions, where—in the parent glass—aluminum ions are predominantly present as cation-charge-compensated [AlO4]⁻ tetrahedra prior to poling. Here, we present results of a detailed investigation into the surface depletion layers formed across a wide range of ternary sodium aluminosilicate (NAS) glasses, applying a host of surface-sensitive spectroscopy methods to directly interrogate the resulting composition and structure within the Na-depleted, anode-side surface layers. The desired depletion layers were successfully formed on all of the NAS glasses attempted, all showing (a) near-complete depletion of alkali within 300-500 nm-thick layers on the anode-side surfaces, (b) thin zones of Al depletion with the Na-depleted layer, and (c) the absence of injected H⁺ ions that could serve as an alternative charge-compensation mechanism. These data essentially confirmed a true binary Al₂O₃–SiO₂ composition inside the depletion layers. However, no significant structural dependence was found as a function of parent glass, where initial compositions ranged from peralkaline to charge-balanced. Importantly, TEM imaging showed the depletion layers to be fully amorphous and homogeneous (not phase-separated) at the nanoscale, despite final compositions in the range of 5-33 mol% Al₂O₃—a composition space notoriously prone to phase-separation if prepared by conventional melting. Within the depletion layers, ELNES and TEY-XANES evidence is shown for retention of Al in a 4-coordinated state, along with XPS data indicating elimination of non-bridging oxygen. Taken as a whole, our results indicate a highly-connected aluminosilicate network, most likely with a relatively high concentration of 3-coordinated oxygen—or O “triclusters”—as a plausible means of charge-compensating 4-coordinated Al in the absence of Na⁺ or H⁺. The combined results of this work provide convincing new evidence for unique glass structures within the depletion layers not achievable through analogous melt pathways, with important implications for surface properties.     

Modeling of thermo-viscoelastic material behavior of glass over a wide temperature range in glass compression molding

In glass compression molding, most current modeling approaches of temperature-dependent viscoelastic behavior of glass materials are restricted to thermo-rheologically simple assumption. This research conducts a detailed study and demonstrates that this assumption, however, is not adequate for glass molding simulations over a wide range of molding temperatures. In this paper, we introduce a new method that eliminates the prerequisite of relaxation functions and shift factors for modeling of the thermo-viscoelastic material behavior. More specifically, the temperature effect is directly incorporated into each parameter of the mechanical model. The mechanical model parameters are derived from creep displacements using uniaxial compression experiments. Validations of the proposed method are conducted for three different glass categories, including borosilicate, aluminosilicate, and chalcogenide glasses. Excellent agreement between the creep experiments and simulation results is found in all glasses over long pressing time up to 900 seconds and a large temperature range that corresponds to the glass viscosity of log (η) = 9.5 – 6.8 Pas. The method eventually promises an enhancement of the glass molding simulation.     

Slow-crack-growth and indentation damage in calcium magnesium aluminosilicate (CMAS) glass from desert sand

Desert sand from a Middle East country was melted into calcium magnesium aluminosilicate (CMAS) glass. Its chemical composition was analyzed to be 25.2CaO-2.6MgO-8.2Al₂O₃-59.8SiO₂-1.6Fe₂O₃-1.5K₂O weight % using inductively coupled plasma-atomic emission spectrometry. The CMAS glass powder was hot pressed into billets. Slow-crack-growth (SCG) and indentation deformation/fracture of the CMAS glass was investigated. The SCG susceptibility parameter (n) was found to be 25 ± 3 which is within a range of n = 15–35 that has been observed in many silicate glasses and glass ceramics. A similarity in indentation hardness and toughness was found between the CMAS glass and the low-silica content (50–70%) glasses. However, an exception was that significant lateral cracking was typified in the CMAS glass, as quantified via stress analysis in the vicinity of an indent.     

Microscopic Origins of Compositional Trends in Aluminosilicate Glass Properties

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

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

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

Mixed modifier effects on structural,mechanical, chemical,and mechanochemical properties of sodium calcium aluminosilicate glass

Glass properties are governed by the interplay between network formers and network modifiers; for a given composition of network formers, the ratio of different cationic modifiers compensating the anionic species in the network has a profound effect, which is often nonlinear, called a mixed modifier effect (MME). We have investigated the MME of sodium (Na) and calcium (Ca) in an aluminosilicate (NCAS) glass series following the formula [Na₂O]_30−x [CaO]_x [Al₂O₃]₁₀ [SiO₂]₆₀, where x = 0, 7.5, 15, 22.5, and 30. A nonadditive trend was observed in hardness and indentation toughness, with aqueous corrosion resistance exhibiting a shift from incongruent to congruent corrosion, whereas the network structure determined by molecular dynamics simulations revealed no significant trend with composition. Additionally, the NCAS glass containing both [Na₂O] and [CaO] within an intermediate range exhibited superior resistance to wear at high humidity, a clear MME phenomenon previously only observed in soda–lime silica.     

Mixed modifier effect in Na2O·K2O·CaO aluminosilicate glasses: Pairwise and ternary interactions

The mixed modifier effect (MME) is one of the most challenging puzzles in the field of oxide glasses, as there exists no universal quantitative theoretical model for accurately describing and predicting the nonlinear deviation of property values. In this paper, pairwise and ternary interactions are examined experimentally to understand the MME in a series of aluminosilicate glasses. By keeping the glass network former concentration constant and adjusting the molar ratios of three network modifiers (Na₂O, K₂O, and CaO), the MMEs in glass transition temperature (T_g), Vickers hardness (H_v), and activation energy (E_a) for aqueous dissolution for each modifier cation are investigated. We examine whether a pairwise interaction model is sufficient, or if ternary interactions also need to be included to predict the MME in these aluminosilicate glass systems. This work reveals that the pairwise model can be used to predict the MME for T_g in complex multiple-modifier glass systems using only two-body interaction factors. However, ternary mixed-modifier interactions are present in other properties such as H_v and E_a.     

Residual stress versus microstructural effects on the strength and toughness of phase-separated PbO–B2O3–Al2O3 glasses

A few authors have reasonably proposed that liquid–liquid phase-separated (LLPS) glasses could show improved fracture strength, S_f, and toughness, K_Ic, as the second phase could provide a barrier to crack propagation via deflection, bowing, trapping, or bridging. Due to the associated tensile or compressive residual stresses, the second phase could also act as a toughening or a weakening mechanism. In this work, we investigated five glasses of the PbO–B₂O₃–Al₂O₃ system spanning across the miscibility gap: Four of them undergo LLPS—three are binodal (two B₂O₃-rich and one PbO-rich) and one is spinodal—and one does not show LLPS (composition outside the miscibility gap). Their compositions were designed in such a way that the amorphous particles are under compressive residual stresses in some and under tensile residual stresses in others. The following mechanical properties were determined: the Vickers hardness, ball on three balls (B3B) strength, and toughness, K_Ic-SEVNB (single-edge V-notch beam [SEVNB]). The microstructures and compositions were analyzed using scanning electron microscopy with energy-dispersive X-ray spectrometry. The spinodal glass showed, by far, the best mechanical properties. Its K_Ic-SEVNB = 1.6 ± 0.1 MPa m^1/2, which embodies an increase of almost 50% over the B₂O₃-rich binodal composition, and 90% considering the PbO-rich binodal composition. Moreover, its fracture strength, S_f = 166 ± 7 MPa, is one of the highest ones ever reported for an LLPS glass. Fracture analyses evidenced that the spinodal composition exhibited the lowest net stress at the fracture point. Moreover, calculations indicate that the internal residual stress level is the lowest in the spinodal glass. The overall results indicate that the microstructural effect of the spinodal glass is the most significant factor for its superior mechanical properties. This work corroborates the idea that LLPS provides a feasible and stimulating solution to improve the mechanical properties of glasses.     

Structural and Textural Modifications of Ternary Phosphate Glasses by Thermal Treatment

Phosphate-based glasses of composition xNa₂O−(45+(10−x))CaO−45P₂O₅ with different Na₂O, CaO (x = 1, 5, 10, 15, and 20 mol%), and invariable P₂O₅ (45 mol%) contents were prepared using the rapid melt quench technique. The obtained thermal data from differential thermal analysis revealed a decline in glass transition (T_g) and crystallization (T_c) temperatures of glasses against the compositional changes. The inclusion of Na₂O at the cost of CaO in the glass network led to a reduction in its thermal stability. The thermal treatment carried out on glasses helped to derive their glass-ceramic counterparts. The amorphous and crystalline features of samples were characterized using X-ray diffraction patterns. The crystalline species that emerged out of the calcium phosphate phases confirmed the dominance of Q¹ and Q² structural distributions in the investigated glass-ceramics. The obtained scanning electron micrographs and atomic force microscopic images confirmed the surface crystallization and textural modification of the samples after thermal treatment. The N₂-adsorption–desorption studies explored the reduction of porous structures due to thermal treatment on the melt-driven glass surface. The measured elastic moduli and Vicker's hardness values of the glasses showed an increase after thermal treatment, which were reduced against the inclusion of alkali content in both glass and glass-ceramics.     

Comparative 27Al NMR and LAXS studies on rapidly quenched aluminosilicate glasses

Aluminium site occupancies deduced from ²⁷Al NMR measurements of several aluminosilicate glasses of composition 35–60 mol% Al₂O₃ were used to calculate the mean coordination number, assuming two polyhedral models. In the models the 30 ppm Al NMR resonance was assigned to fivefold coordinated Al or to distorted tetrahedral units, respectively. Comparison of these mean coordination numbers with those derived from pair distribution functions (PDF) from X-ray scattering data of these glasses support the model in which the 30 ppm Al NMR peak is assigned to distorted tetrahedral units. This conclusion is also supported by simulations of the PDF line profiles using the NMR site occupancies and mean polyhedral bond lengths.     

New Aluminosilicate Glasses as High-Power Laser Materials

In the past few years, aluminosilicate glasses of an extremely broad compositional range have been prepared and analyzed to scan this glass type for its potential use as high-power laser material. The tested network modifier ions included Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺, Pb²⁺, Y³⁺, and La³⁺. Preliminary investigations have been conducted with Sm³⁺- and Eu³⁺-doped glasses; selected glass compositions have also been prepared with Yb³⁺ doping for laser testing. It has been found that low refractive indices/low average molecular weights/low densities of the glasses in most cases support relatively long fluorescence lifetimes of the doped ions. It was further concluded that the phonon energy of the molecular network of the glasses does not affect the fluorescence properties of the doped samples. The mechanical properties such as Young's modulus, Vickers hardness, and fracture toughness generally increase with increasing field strength of the network modifier ion for constant stoichiometric ratios of the glass components. The lowest potential thermal stress values were found for zinc and magnesium aluminosilicate glasses, which also have relatively high field strengths. Taking all these facts into account, a ternary lithium aluminosilicate and a mixed lithium magnesium aluminosilicate glass doped with Yb³⁺ have been prepared in high optical quality and tested with respect to their laser performance. The fluorescence lifetime values are somewhat lower than in well-established Yb³⁺-doped laser materials, such as fluoride phosphate glass or single crystalline calcium fluoride. Nevertheless, the aluminosilicate glasses show exceptionally high absorption and emission cross sections, smooth and very broad amplification profiles, as well as much better thermomechanical properties. Quantum efficiencies close to unity could be reached by consequently removing dissolved OH from the glass melt.     

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.     

Predictable tendency of Bi NIR emission in Bi‐doped magnesium aluminosilicate laser glasses

Because of superbroad luminescence in the range of near infrared (NIR), Bi‐doped glasses and fibers have received more attentions recently for the applications in super broadband optical fiber amplifiers or new wavelength lasers. As the luminescence comes from the transitions between naked 6p orbitals of bismuth, it is very susceptible to slight changes of local field around Bi. Therefore, it is always very challenging to predict NIR emission of bismuth in advance. Here, we found bismuth NIR emission shows predictable tendency in ternary glass system of MgO–Al₂O₃–SiO₂. The emission peak shifts red along the content of magnesium upon the excitation of 484 nm, which follows a single exponential growth equation. In the meantime, the full width at half maximum (FWHM) is broadened while the lifetime keeps decreasing. Glass structure analysis on basis of FTIR, ²⁷Al NMR, ²⁹Si NMR spectra reveals that these changes correlate to integrity of glass network, the increased disorder of local field around bismuth and the enhanced interaction between bismuth and host, which are perhaps due to the linear increase of nonbridging oxygen, and the enhanced Si–O asymmetric stretching vibrations along with magnesium, respectively. Electron probe microanalysis shows good homogeneity of Si, Al, Mg, Bi, and O distribution within the samples, and yoyo experiments of heating and cooling between 30°C and 300°C reveal the good resistance of such doped glasses to thermal degradation. This makes the glasses promising in applications of fiber devices even under extreme condition such as at higher temperature. The finding in this work should be helpful for the design of Bi‐doped laser glasses in future.