Calcium Aluminosilicate Glasses Research Articles

Mechanisms and energetics of calcium aluminosilicate glass dissolution through ab initio molecular dynamics-metadynamics simulations

The dissolution of silicate glasses has implications in diverse fields ranging from the immobilization of radioactive waste to the development of sustainable alternatives to Portland cement. Here, we used ab initio molecular dynamics simulations biased with well-tempered metadynamics to study Si-O-T bridge dissociation in calcium aluminosilicate glasses, crucial for understanding their dissolution. In a departure from the conventional Michalske-Freiman model, our findings reveal a nucleophilic substitution reaction mechanism characterized by a short-lived, 5-fold coordinated Si intermediate or transition state, depending on the Si bridge coordination, with a near-trigonal bipyramidal geometry. We find that the reorganization required for reaching this state causes the activation energy barriers to be dependent on the Si bridge coordination, with Si Q3 species serving as the rate-limiting step in the dissolution reaction. Our findings not only challenge long-standing theoretical models but also pave the way for more accurate and comprehensive frameworks for understanding the dissolution of silicate glasses in various applications.

Radiation shielding properties of 35-XBaO-15CaO-5Al2O3-10B2O3-35SiO2-XBNNT (X=5, 10, 15, 20) glass reinforced with boron nitride nanotubes

Glass composite materials are the most widely used radiation shielding materials. Barium aluminosilicate glass have versatile properties which make them very useful for applications in industries. In the present study, the mass attenuation coefficient, effective atomic numbers as well as effective electron densities of barium calcium aluminosilicate glass (BCAS) were studied by adding boron nitride nanotubes in various concentrations. Analysis were conducted using phy-x/PSD simulation codes. It as was found that MAC and δa decrease with increasing photon energy in consistent with previous works. It was also found that attenuation parameters such as MAC, LAC, HVL and Zeff were all influenced by change in density of BCAS/BNNT glass. The present study found BCAS/BNNT1 glass as best for gamma radiation protection.

The first demonstration of wavelength-tunable Yb3+-doped low silica calcium aluminosilicate (LSCAS) glass lasers

We report on the first demonstration of diode-pumped wavelength-tunable Yb3+-doped low silica calcium aluminosilicate (LSCAS) glass lasers. Using a 976 nm diode laser as pump source, a Yb:LSCAS laser has been successfully achieved with a maximum output power of about 0.28 W. Using an MgF2 thin plate as birefringence filter, we have found that the lasing wavelength can be tuned with a range of about 60 nm. We have also analyzed the intracavity round-trip loss of the current laser cavity, and related it to the optical quality of the used Yb glass. This sheds light on the path of the development of upcoming Yb3+ glass lasers in the future since it has many advantages, and after improving the optical quality, the wide and smooth emission spectrum of Yb:LSCAS will be very conducive to obtaining femtosecond pulse lasers.

High pressure-driven effects on the structural and spectroscopic attributes of Eu3+-doped amorphous silicates

The present study focuses on synthesizing and investigating the structure of Eu3+-doped sodium calcium silicate and calcium alumino silicate glasses under extreme high-pressure conditions. For a thorough understanding of glassy systems in extreme conditions, we conducted in-situ micro-luminescence experiments using a diamond anvil cell, reaching pressures up to 16 GPa. Hydrostatic pressure demonstrated a notable impact on luminescence, attributed to the nephelauxetic effect causing the contraction of central-ion-ligand distances. The band transitions of Eu3+ from the 5D0 to 7F1,2 states revealed pronounced pressure-induced splitting, highlighting the pressure influence on crystal-field properties. The energy shifts for the 5D0 → 7F1 transitions were determined to be 0.14 nmGPa−1 and 0.20 nmGPa−1 for sodium calcium silicate and calcium alumino silicate, respectively. These distinct slope differences indicated a lower structural adaptability of the former glass, resulting in reduced deformability under high-pressure conditions. Furthermore, as pressure increased, the asymmetry ratio of the 5D0 → 7F2/1 transitions decreased, though it consistently maintains levels higher than unity, reflecting the highly asymmetric environment surrounding Eu3+ ions. The estimated elastic limit for both samples was approximately 7 GPa. To assess pressure-induced changes in the local environment, Judd-Ofelt intensity parameters were employed for the calcium alumino silicate glass. The trends observed throughout compression revealed that Ω2 > Ω4 up to 6.8 GPa, while Ω2 < Ω4 for higher pressures, indicating higher covalency between Eu3+ ions and ligands in the elastic domain compared to the plastic domain. The observed increase in Si and Al coordination in the plastic domain was found to play a role in these parameters.

Atomistic simulations of calcium aluminosilicate interfaced with liquid water.

The dissolution behavior of calcium aluminosilicate based glass fibers, such as stone wool fibers, is an important consideration in mineral wool applications for both the longevity of the mineral wool products in humid environments and limiting the health impacts of released and inhaled fibers from the mineral wool product. Balancing these factors requires a molecular-level understanding of calcium aluminosilicate glass dissolution mechanisms, details that are challenging to resolve with experiment alone. Molecular dynamics simulations are a powerful tool capable of providing complementary atomistic insights regarding dissolution; however, they require force fields capable of describing not-only the calcium aluminosilicate surface structure but also the interactions relevant to dissolution phenomena. Here, a new force field capable of describing amorphous calcium aluminosilicate surfaces interfaced with liquid water is developed by fitting parameters to experimental and first principles simulation data of the relevant oxide-water interfaces, including abinitio molecular dynamics simulations performed for this work for the wüstite and periclase interfaces. Simulations of a calcium aluminosilicate surface interfaced with liquid water were used to test this new force field, suggesting moderate ingress of water into the porous glass interface. This design of the force field opens a new avenue for the further study of calcium and network-modifier dissolution phenomena in calcium aluminosilicate glasses and stone wool fibers at liquid water interfaces.

Prediction of the surface chemistry of calcium aluminosilicate glasses

We have used a combination of density functional theory, the implicit solvent model COSMO-RS and molecular dynamics simulations to predict the pKa of surface groups on calcium aluminosilicate glasses. We found that the average of pKa for deprotonation and protonation for silanols agrees well with the point of zero charge for pure silica materials. Similarly, the average of pKa for deprotonation and protonation for aluminols agrees well with the point of zero charge for pure alumina. We identified trends in the pKa related to the hydrogen bonding of the surface groups, as well as the influence of tri-briding oxygen defects.

Insights from molecular dynamics into the chemistry-structure relationships of calcium aluminosilicate glasses

Calcium aluminosilicate (CAS) glasses are ubiquitous in nature and play an important role in diverse technological applications ranging from structural glasses to sustainable cementitious materials. Understanding the relationship between the chemical composition and the structure of CAS glasses is an essential step towards optimizing their properties for different uses in the future. Here, we use extensive molecular dynamics (MD) simulations to characterize the multiscale structure of CAS glasses over the full compositional range. Analysis of the short and medium range order of the glasses reveals that Lowenstein's rule is widely violated, that silica is more susceptible than alumina to the depolymerizing effects of calcium, and that high-silica glasses favor calcium in lower oxygen coordination states, while the opposite is true for high-alumina ones. We also find the presence of highly coordinated aluminum and tricluster oxygens in high-alumina glasses, which form as a charge compensation mechanism. We find that current theoretical models used to predict oxygen species, oxygen bridge types, or tetrahedral coordination, while overall qualitatively reasonable, simplify the complex interplay between the different oxides which results in inaccurate predictions, particularly for glasses in intermediate compositional regions. Our analysis of the cluster, chain, and ring topological structures in the aluminosilicate network reveals a sharp transition from a connected to a disconnected graph which depends not only on the calcium content of the glass, but also on the ratio of silica to alumina. Glasses in the compositional region corresponding to such transition display the largest ring and longest chain structures of any glass studied.

Downconversion luminescence in Ce3+, Yb2+, and Yb3+ co-doped low silica calcium aluminosilicate glasses: Potential for spectral conversion in solar cell technology

Yb–Ce co-doped LSCAS glasses melted under a vacuum atmosphere are free of OH− radicals presenting downconversion luminescence of interest for solar cell application. Absorption spectra showed an ultraviolet–visible broad band related to the 2F5/2, 2F7/2 → 5d transitions of the Ce3+. Time-resolved luminescence evidenced energy transfer from Ce3+ to Yb3+, and the contour maps spectra showed a decrease in Ce3+ emission with the increase of Yb concentration. Thermal lens results evidenced an increase in heat generation, suggesting the occurrence of nonradiative transitions due to the formation of Yb2+ or Ce4+ ions. The observed emissions are attributed to energy transfer from Ce3+ or Yb2+ to two Yb3+ ions by quantum cutting mechanism, emission from Ce3+ at 520 nm, and predominantly, a phonon-assisted energy transfer from Ce3+ or Yb2+ to one Yb3+ ion.

Role of Zn in aluminosilicate glasses used as supplementary cementitious materials

The cement industry relies on the use of supplementary cementitious materials (SCM) to lower the related CO2 emission. SCM are often amorphous materials containing minor elements, which is why it is important to study the impact of these materials on cement reactivity. Two calcium aluminosilicate glass series as model substances of SCM were synthesized and investigated. In both series Ca was partially replaced by Zn, Sr and Mg in different ratios. Moreover, four cement blends made with CEM I 52.5 R and aqueous solutions of Mg(NO3)2·6H2O, Zn(NO3)2·6H2O and Sr(NO3)2 were investigated. Zn retards the reactivity of both glasses and cements system. This retardation effect is suggested to be related both to the formation of the calcium hydroxozincate hydrate, which affects the portlandite formation and, thus, the pH of the system, and to the formation of surface complexes which retards the dissolution and so the reactivity of the glasses.

Mechanisms of microstructural deformation governing Vickers hardness in phase‐separated calcium aluminosilicate glasses

AbstractThe impact of microstructure on hardness in phase‐separated calcium aluminosilicate glasses is investigated. Changes in hardness are governed by microstructure deformations that occur during indentation. Phase separation leads to decreased hardness due to the incongruent yielding of the droplet and matrix phases. Moreover, the deformation of microstructures possessing dilute, spherical droplets did not have a significant impact on hardness. Microstructures characterized by concentrated, acicular droplets were found to deform through a process of droplet coalescence. This process absorbs additional energy during yielding and results in glasses that deform through droplet coalescence possessing improved hardness.

The changes in the reaction kinetics and phase assemblage of sodium silicate-activated CaO-MgO-Al2O3-SiO2 glasses induced by the Al replacement by Mg

Although intensive research was done on the impact of slag chemistry on the reaction kinetics of alkali-activated materials, its role remains unclear due to the slag's uncontrolled oxides variations. This research investigated the role of the Al replacement by Mg on the reaction kinetics and phase assemblage of sodium silicate-activated calcium‑magnesium-aluminosilicate (CMAS) glasses by a novel approach. The calcium-aluminosilicate (CAS) glass reacted faster than the CMAS ones. Also, increasing the replacement level in the CMAS glasses slightly accelerated the reaction but considerably increased the total heat. Katoite and strätlingite precipitated at high Al2O3 wt% of 20 and 25, respectively. A decrease in the total volume of the hydrates was predicted by thermodynamic modelling and further supported by gas adsorption measurements. The paper's outcomes aid in providing a fundamental understating of the effect of Al and Mg which could help with customising the mix design for enhanced performance of alkali-activated binders.

Broadband downconversion in Eu2+,3+/Yb3+ doped calcium aluminosilicate glasses for solar cells applications

Novel Eu2+,3+/Yb3+ co-doping calcium aluminosilicate glasses prepared under a vacuum atmosphere were developed and characterized from the spectroscopic point of view, as a potential spectral converter for application in solar cells. The emission of near-infrared photons by downconversion due to cooperative energy transfer (ET) from Eu2+ and Eu3+ to Yb3+ in these glasses was reported. Absorption, excitation, emission, and fluorescence decay measurements were performed to examine the ET processes. The occurrence of cooperative energy transfer from Eu2+ and/or Eu3+ to Yb3+ ions was discussed in detail. The obtained samples have high efficiency and broad absorption in the ultraviolet and visible regions. Under 325 nm excitation, the samples achieve intense near-infrared emission, which increases with Yb2O3 concentration (0 &amp;lt; Yb2O3 &amp;lt; 1.38 mol. %). The energy transfer efficiency from Eu2+,3+ to Yb3+ was evaluated, and a maximum efficiency of ∼85% was obtained (Yb2O3 = 1.38 mol. %).

The Effect of Glass Structure on the Luminescence Spectra of Sm3+-Doped Aluminosilicate Glasses.

Peralkaline Sm3+-doped aluminosilicate glasses with different network modifier ions (Mg2+, Ca2+, Sr2+, Ba2+, Zn2+) were investigated to clarify the effect of glass composition and glass structure on the optical properties of the doped Sm3+ ions. For this purpose, the Sm3+ luminescence emission spectra were correlated with the molecular structure of the glasses derived by molecular dynamics (MD) simulations. The different network modifier ions have a clear and systematic effect on the peak area ratio of the Sm3+ emission peaks which correlates with the average rare earth site symmetry in the glasses. The highest site symmetry is found for the calcium aluminosilicate glass. Glasses with network modifier ions of lower and higher ionic radii show a notably lower average site symmetry. The symmetry could be correlated to the rare earth coordination number with oxygen atoms derived by MD simulations. A coordination number of 6 seems to offer the highest average site symmetry. Higher rare earth coordination probabilities with non-bridging oxygen result in an increased splitting of the emission peaks and a notable broadening of the peaks. The zinc containing glass seems to play a special role. The Zn2+ ions notably modify the glass structure and especially the rare earth coordination in comparison to the other network modifier ions in the other investigated glasses. The knowledge on how glass structure affects the optical properties of doped rare earth ions can be used to tailor the rare earth absorption and emission spectra for specific applications.

Influences of Mn2+ ions, and Mn2+–Yb3+ dimer on the optical band gaps and bandwidth flatness of near-infrared emissions of Ho3+/Tm3+, Ho3+/Tm3+/Yb3+ co-doped calcium aluminosilicate glasses

We investigate and report the influences of Mn2+−Yb3+ dimer on the optical band gaps and bandwidth flatness of near-infrared (NIR) emission spectra of Ho3+/Tm3+, and Ho3+/Tm3+/Yb3+ co-doped CaO–Al2O3–SiO2 (CAS) calcium aluminosilicate glasses. Differential thermal analysis (DTA) and Energy dispersive X-ray spectroscopy (EDS) analyzes were performed to determine temperature values for heat treatment and elemental composition existing in the glass materials, respectively. NIR emission spectra of Ho3+/Tm3+/Yb3+ co-doped CAS glasses with a bandwidth of ∼450 nm using a 980 nm laser diode (LD) as the excitation resource was identified. Influences of Mn2+ ions and Mn2+–Yb3+ dimer on the direct/indirect optical band gaps, and bandwidth flatness of NIR emission of Ho3+/Tm3+/Yb3+ co-doped were investigated. At the same time, we determined the optimal Mn2+:Yb3+concentration ratio for the best flatness of the bandwidth NIR emission of Ho3+/Tm3+/Yb3+ co-doped CAS glasses.

Quantification of the resonant energy transfer processes in Er3+/Yb3+ co-doped Ca3Al2Si3O12 glasses

The resonant cross relaxation processes between Yb3+ and Er3+ ions in calcium alumino-silicate glasses have been quantified under selective Er3+ excitation. The infrared emission spectra, measured under steady state conditions (CW excitation to the 4I9/2 erbium level), have allowed to obtain an experimental relationship linking the transfer (Yb3+ → Er3+) and back transfer (Er3+ → Yb3+) parameters. These measurements combined with the dynamics of the main emitting levels, measured under pulsed excitation to the 2H11/2 erbium level, have allowed the fully quantification of the energy transfer parameters. The obtained values, C25=5.5×10−18cm3s−1 (Yb3+ → Er3+), C52=1.5×10−18cm3s−1 (Er3+ → Yb3+) and C27=7.6×10−18cm3s−1 (up-conversion mechanism, estimated from the Judd-Ofelt analysis previously reported), can be used to predict the temporal evolution of the main luminescent emission bands.

Modeling Oxygen Tricluster Formation in Calcium Aluminosilicate Supercooled Liquids and Glasses.

Calcium aluminosilicate glasses have technological importance for a variety of industrial applications. However, the short-range structure of this glass system remains widely debated regarding the formation of oxygen triclusters. It is argued that triclusters are observed in high percentages within molecular dynamics simulations because of the high melting temperatures and correspondingly high fictive temperatures. This work explores the formation of such structural units by first simulating various compositions at different liquid temperatures to understand thermodynamic factors affecting the formation of such species. Structural results are then implemented into a statistical mechanical model which can predict the formation of triclusters at a given fictive temperature. Results show temperature and composition dependence of these structures, with aluminum charge modification favored in the peraluminous regime. It is concluded that oxygen triclusters are the preferred method of charge compensation even when extrapolating to laboratory fictive temperatures, indicating that triclusters are not a byproduct of simulation timescales.

Passivation of Mid-Gap Electronic States at Calcium Aluminosilicate Glass Surfaces upon Water Exposure: An Ab Initio Study.

When a clean glass surface is exposed to humid air, a thin water layer forms on the hydrophilic surface. Using ab initio molecular dynamics, we simulate the changes in the electronic structure of a CaO-Al2O3-SiO2 glass model upon vacuum fracture and subsequent exposure to H2O. When the glass is fractured, dangling bonds form, which lower the band gap of the surface by ∼1.8 eV compared to the bulk value due to mid-gap surface states. When H2O adsorbs onto the vacuum-fractured surface, the band gap increases to a value closer to that of the bulk band gap. Using two different hydroxylation methods, we find that the calculated band gap of the glass surface depends on the hydroxylation state. Surfaces with ∼4.5 OH/nm2 have smaller band gaps due to unfilled surface states, and surfaces with ∼2.5 OH/nm2 have larger band gaps with no apparent unfilled surface states. The resulting changes in the electronic structure, quantified by electron affinity and work function values, are hypothesized to play an important role in the electrostatic charge transfer based on the principles of surface state theory, which posit that the density of electronic surface states determines the amount of electronic charge transfer to or from material surfaces.

Thermal conduction in a densified oxide glass: Insights from lattice dynamics

Thermal conductivity is an important property of oxide glasses, but its structural origins remain largely unknown. Here, we provide detailed modal information on thermal conductivity in a calcium aluminosilicate glass by relying on recent advances in lattice dynamics methods. We probe various structural features using molecular dynamics simulations by densifying the glass at pressures up to 100 GPa and studying the vibrational, mechanical, and thermal properties. We demonstrate good agreement between these simulations and complementary experiments, both of which indicate significant pressure-induced alteration of mechanical moduli, vibrational density of states, boson peak behavior, and thermal conductivity. We also find an intriguing correlation between the boson peak frequency and the total thermal conductivity in both the current glass series and a lithium borate glass series reported in literature. This correlation scales with the Debye frequency, suggesting that both parameters are associated with the transformation of the elastic medium under pressure.

Development of potentials for molecular dynamics simulations of dry and hydrated calcium aluminosilicate glasses by force matching and refinement

Potential development and refinement to improve the applicability and transferability of the forcefield is important to atomistic simulations of glass materials and their interactions with the environment. In this paper, we demonstrate potential development of calcium aluminosilicate glasses with and without water using a reactive potential framework by adopting the force matching technique and subsequent refinement. Accordingly, we have reproduced the forces on atoms of the system from a DFT based ab-initio molecular dynamics (AIMD) simulations by adjusting the potential parameters. We chose the diffuse charge reactive potential (DCRP) as the classical potential as it has been previously demonstrated to accurately and efficiently simulate interactions between water and silicate-glasses. The obtained force matched parameters were further refined to accurately reproduce the structures and dynamics of dry and hydrated calcium alumino silicate glass and gel structures. The Ca2+ behavior in solution was correctly reproduced with an average local coordination equal to 6.12 and a diffusion coefficient close to the experimental values. This force field also correctly reproduces the local environment of Al3+ in glass, but it falls short in describing Al3+ ion coordination in solutions as compared to AIMD results, suggesting a direction of future improvement. This set of potential can thus be used for simulations of calcium aluminosilicate glasses with various technological applications and hydrated gel structures resulted from corrosions of boroaluminosilicate glasses.

Joining of alumina using magnesium- or calcium-aluminosilicate glass–ceramic fillers

Magnesium- and calcium-aluminosilicate (MAS and CAS) glass–ceramics were used to join alumina with six different compositions. The fillers were applied onto the alumina by screen-printing, and then joining was performed slightly below and above the filler melting temperature (Tm). The evolution of various intermediate compounds upon heat treatment between the filler itself and at the joining interface was compared. MgAl2O4 and CaO·6Al2O3 was the main crystalline phase presented at the joining interface for the MAS and CAS system, respectively, while more intermediate compounds were observed when only filler was heat-treated. The formation of MgAl2O4 and CaO·6Al2O3 was attributed to the diffusion of Al ions from the alumina base, which is desirable for obtaining a sound joint due to the similar coefficient of thermal expansion to the base alumina. The maximum joint strength of 250 ± 41 and 301 ± 48 MPa was obtained for MAS and CAS filler system, respectively, after joining at T ≥ Tm due to complete interfacial wetting.