Glass Structure Research Articles

Insights on the structure and properties of sodium iron phosphate glasses from molecular dynamics simulations

Iron phosphate glasses are promising nuclear waste forms while more detailed understanding of their structures and structure-property relations are still needed to better design waste glass compositions. In this work we report studies of three series of sodium iron phosphate (NFP) glasses: 60P2O5-(40-x)Fe2O3-xNa2O (x = 0→40), (100–2x)P2O5-xFe2O3-xNa2O (x = 5→17.5) and one with different iron redox ratio, to understand the composition as well as the iron redox effects on the structure and properties of these glasses using molecular dynamics simulations with effective two-body and three-body potentials. Structural analyses, including pair distribution function, bond angle distribution, Qn distribution, and polyhedral connectivity, were performed to obtain in-depth information on short-range and medium-range structural features. The P-O pair distributions showed a first peak splitting with phosphorus-bridging and non-bridging oxygen contributions. This and the average P-O and other cation-oxygen bond distances are in excellent agreement with experiments. The coordination number of P5+ remained four while that of Fe3+ increased from 4.30 to 4.72 with decreasing Fe/Na ratio. Polyhedral linkage analysis showed [PO4] units linked with [PO4] and [FeOx] through corner-sharing while the [PO4]-[FeOx] linkages become dominant for compositions with Fe2O3 larger than 15 mol%. The effect of iron redox ratio on the structure of NFP glasses was also studied and it was found that bond lengths and coordination numbers were not strongly affected, while the reduction of iron introduced higher network distortions, as evident by O-P-O bond angle and Qn distribution. The glass transition temperature (Tg) showed a monotonic increase with Fe2O3 in the first series, in good agreement with experiments, while those of the second series showed a maximum at P2O5 = 82 mol%. Calculated elastic moduli were found to increase with Fe2O3 in the first glass series, which was be explained by the increase of network connectivity, while those of the second series decrease with Fe2O3 due to decrease of P2O5.

Effect of partial substitution of barium oxide by lanthanum oxide on the structure and properties of iron-based aluminosilicate glass

Silica-aluminum borates (SiO2-R2O3-R2O-RO-ZrO2 system) with La2O3 replacing BaO were preparing using the conventional melt quenching process. The impact of substituting BaO with La2O3 on the glass structure was examined using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and Raman. The density, thermal properties, alkali resistance and dielectric properties of the glasses were measured and compared using Archimedes, Differential Scanning Circuit (DSC), Thermal Expansion Calorimetry (TEC), Weight Reduction and Impedance Spectroscopy. The viscosity of the glass system was calculated from the thermal properties and discussed in comparison with the wetting angle at 1000 °C. The results showed that the glass does not undergo precipitation. With the increase of La2O3 to BaO substitution, the Q4 in the glass network structure transforms to Q0+Q1 and Q2, causing depolymeriation of the glass structure. This results in an increase in the density of the glass, as well as an increase and subsequent decrease in the thermal expansion coefficient. Additionally, the glass transition temperature and glass softening temperature decrease and then increase, which was due to the high field strength of La3+. When substituting 5 wt% of BaO with La2O3, The glass displayed the lowest dielectric constant and dielectric loss, along with the best alkali resistance. Viscosity calculations showed that the viscosity gradually increases at 1000 °C with the increase of La2O3 substitution, which was consistent with the wettability results. The glass components in the 0-5 wt% weight range all satisfy the iron-sealed glass wetting angle requirements.

Modifying ring structures in lithium borate glasses under compression: MD simulations using a machine-learning potential

Modifying ring structures in lithium borate glasses under compression: MD simulations using a machine-learning potential

Water Promotes Melting of a Metal-Organic Framework.

Water is one of the most reactive and abundant molecules on Earth, and it is thus crucial to understand its reactivity with various material families. One of the big unknown questions is how water in liquid and vapor forms impact the fast-emerging class of metal-organic frameworks (MOFs). Here, we discover that high-pressure water vapor drastically modifies the structure and hence the dynamic, thermodynamic, and mechanical properties of MOF glasses. In detail, we find that an archetypical MOF (ZIF-62) is extremely sensitive to heat treatments performed at 460 °C and water vapor pressures up to ∼110 bar. Both the melting and glass transition temperatures decrease remarkably (by >100 °C), and simultaneously, hardness and Young's modulus increase by up to 100% under very mild treatment conditions (<20 bar of hydrothermal pressure). Structural analyses suggest water to partially coordinate to Zn in the form of a hydroxide ion by replacing a bridging imidazolate-based linker. The work provides insight into the role of hot-compressed water in influencing the structure and properties of MOF glasses and opens a new route for systematically changing the thermodynamics and kinetics of MOF liquids and thus altering the thermal and mechanical properties of the resulting MOF glasses.

Effect of manganese on the structure of CMAS slag glass–ceramics

With the acceleration of industrialization, environmental issues have received great attention from governments and societies around the world. Utilizing solid wastes containing valuable heavy metals and exploring their role and application in materials is one of the focal issues of environmental protection in recent years. In this paper, in order to explore the effect of Mn content on the crystallization of CaO-MgO-Al2O3-SiO2 glass–ceramics, glass–ceramics with different content of MnO2 were prepared by sintering method and the effect of MnO2 doping on the crystalline properties, glass stability and heavy metal fixation properties of the stainless steel slag glass–ceramics was investigated by differential scanning calorimetry (DSC), Raman spectroscopy, X-ray diffraction (XRD) and scanning electron microscope (SEM). The analysis using crystallization kinetics showed that surface crystallization dominated the whole crystallization process in the range of 0% to 10% MnO2 content. The peak glass crystallization and depolymerisation temperatures of the glass–ceramics increased gradually with increasing MnO2 content, and the main crystallization mode of the samples was one-dimensional crystallization. The main crystalline phase of the resulting glass–ceramics was transformed from diopside to spinel, with a crystallization temperature of 860℃. Heavy metals solidified in the spinel phase. This study shows that heavy metals can be effectively immobilized in glass–ceramics. In summary, the use of solid waste to prepare final products with good environmental performance provides a feasible way to utilize solid waste resources.

Quantitative CT Texture Analysis of COVID-19 Hospitalized Patients during 3-24-Month Follow-Up and Correlation with Functional Parameters.

To quantitatively evaluate CT lung abnormalities in COVID-19 survivors from the acute phase to 24-month follow-up. Quantitative CT features as predictors of abnormalities' persistence were investigated. Patients who survived COVID-19 were retrospectively enrolled and underwent a chest CT at baseline (T0) and 3 months (T3) after discharge, with pulmonary function tests (PFTs). Patients with residual CT abnormalities repeated the CT at 12 (T12) and 24 (T24) months after discharge. A machine-learning-based software, CALIPER, calculated the CT percentage of the whole lung of normal parenchyma, ground glass (GG), reticulation (Ret), and vascular-related structures (VRSs). Differences (Δ) were calculated between time points. Receiver operating characteristic (ROC) curve analyses were performed to test the baseline parameters as predictors of functional impairment at T3 and of the persistence of CT abnormalities at T12. The cohort included 128 patients at T0, 133 at T3, 61 at T12, and 34 at T24. The GG medians were 8.44%, 0.14%, 0.13% and 0.12% at T0, T3, T12 and T24. The Ret medians were 2.79% at T0 and 0.14% at the following time points. All Δ significantly differed from 0, except between T12 and T24. The GG and VRSs at T0 achieved AUCs of 0.73 as predictors of functional impairment, and area under the curves (AUCs) of 0.71 and 0.72 for the persistence of CT abnormalities at T12. CALIPER accurately quantified the CT changes up to the 24-month follow-up. Resolution mostly occurred at T3, and Ret persisting at T12 was almost unchanged at T24. The baseline parameters were good predictors of functional impairment at T3 and of abnormalities' persistence at T12.

Connecting microscopic and mesoscopic mechanics in model structural glasses.

We present a novel formalism to characterize elastic heterogeneities in amorphous solids. In particular, we derive high-order strain-energy expansions for pairwise energies under athermal quasistatic dynamics. We then use the presented formalism to study the statistical properties of pairwise expansion coefficients and their link with the statistics of soft, quasilocalized modes, for a wide range of formation histories in both two- and three-dimensional systems. We further exploit the presented framework to access local yield stress maps by performing a non-linear stress-strain expansion within a cavity embedded in a frozen matrix. We show that our "bond micromechanics" compare well with the original "frozen matrix" method, with the caveat of overestimating large stress activations. We additionally show how local yield rules can be used as an input for a scalar elasto-plastic model (EPM) to predict the stress response of materials ranging from ductile to brittle. Finally, we highlight some of the limits of simple mesoscale models in capturing the aging dynamics of post-yielding systems. Intriguingly, we observe subdiffusive and diffusive shear band growths for particle-based simulations and EPMs, respectively.

Structure and thermal conductivity of high-pressure-treated silica glass. A molecular dynamics study

High-pressure treatment of oxide glasses can lead to significant alteration of various material properties such as increased density, ductility, and elastic moduli. In this study, a model of melt-quenched bulk silica glass was subject to high-pressure treatments (up to 16 GPa) using molecular dynamics simulations. The thermal conductivity of such prepared glass structures was determined using the equilibrium Green–Kubo method. We observed that, up to the pressure treatments of ∼6 GPa, the structure exhibits moderate density increase and a much steeper increase between 6 and 16 GPa, with associated density increase of fivefold silicon atoms. We also observed a noticeable increase (up to 20%) of the thermal conductivity in samples subjected to high-pressure treatments. The observed increases are somewhat, but not significantly, larger than those predicted by the minimum thermal conductivity model, accounting for density and elastic moduli increase.

Net gain in C+L band from LED pumped broadband emission in Er3+-doped oxyhalide tellurite glass

Expanding gain bandwidth into the L-band for erbium-doped fiber amplifiers (EDFAs) is a crucial strategy to overcome limitations in prevalent C-band focused commercial silica-based EDFAs, significantly boosting optical network transmission capacity. Herein, we synthesized Er3+-doped broadband near-infrared emission tellurite glasses utilizing the melt quenching process, systematically exploring the impact of ZnCl2 on the glass structure and optical properties. The 82TeO2–3Nb2O5–15ZnCl2–3Er2O3 (TNZ15) glass emerged as a standout candidate for broadband amplifiers around wavelength at 1.55 μm. With escalating ZnCl2 concentration, a discernible red shift in the emission peak wave lines was observed, accompanied by an expansion of the full width at half maximum (FWHM) from 98 nm to 106 nm. Noteworthy characteristics of all samples included exceptional thermal stability and elevated near-infrared (NIR) transmittance. Application of the Judd-Ofelt (J-O) theory facilitated the calculation of J-O parameter intensity, providing deeper insights into the optical behavior of the materials. Finally, the evaluation of TNZ15 planar optical waveguides, employing the vertical top pumping mode of two 980 nm LEDs, encompassed both the C-band (1530–1565 nm) and the L-band (1565–1625 nm). The results underscore the potential of TNZ15 glass as a promising gain material for broadband optical amplifiers and lasers, offering valuable insights into the development of next-generation optical amplification technologies.

Effects of TiO2 on fiber spinnability, structure, and mechanical properties of glasses derived from simulated lunar soils

The construction of lunar stations for research and habitation requires high-performance building materials that can adapt to the harsh lunar environment. One of the feasible building materials is fiber-reinforced composites, for which the composition of glass fibers can be designed like lunar soils, i.e., terrestrial basalt, and in turn the “lunar glass” can be drawn into fibers. Because of a wide variation of TiO2 in lunar soils, our study focused on a series investigation on the effect of TiO2 (0.55 wt%-6.14 wt%) on fiber spinnability and strength of the simulated “lunar glass and glass fibers”. The baseline glass composition was derived from a simulated TiO2-lean lunar soil and other glasses were made at different TiO2 doping levels. The addition of TiO2 was found to reduce the thermal stability of the melt, there appears a TiO2 threshold (6.14 wt%), at which fibers cannot be drawn without breakage because of melt devitrification. The fiber tensile strength exhibits a nonlinear characteristic with an apparent maximum at 1.52 wt% TiO2. FTIR and Raman spectroscopic studies were carried out to investigate the glass network structure responses to TiO2 modifications and show TiO2 functions as a network modifier, depolymerizing the silicate network. Statistical structure (FTIR & Raman based)–property modeling was attempted to further elucidate the effect of TiO2-induced structure change on Tg and fiber tensile strength. Good agreements were found between the model predictions and the measured values.

Medium-range order structure analysis of metallic glasses based on reverse Monte Carlo modeling

The elucidation of amorphous alloy characteristics presents a formidable challenge due to the absence of crystalline arrangements and enigmatic imperfections. This study aimed to tackle this challenge through a comprehensive investigation utilizing synchrotron X-ray diffraction (XRD), extended X-ray absorption fine structure spectroscopy (EXAFS), ab initio molecular dynamics (AIMD) simulations, and reverse Monte Carlo (RMC) modeling. The primary objective was to delve into the medium range order (MRO) structure of metallic glasses (MGs) containing CuXZr100-X, wherein X represents values of 50, 56, 60, and 64. The results obtained from this research demonstrate that an increase in the Cu atom concentration within Cu-Zr MGs leads to the formation of complete icosahedral clusters and high-coordination polyhedral connections, thereby bolstering the stability and heterogeneity of local structures. Examination of the stiff full icosahedral bones shows that defects exist in the network connections on the MRO, resulting in a lack of connectivity in the positive icosahedron. Conversely, the density of defects decreases with an increase in Cu content. The observation suggests that the observed low MRO defects in Cu64Zr36 MGs may be accountable for their excellent glass-forming ability and kinetic stability.

Phase-separation enhanced upconversion luminescence with regulated pure-red emission in manganese fluorosilicate glass

In this work, rare earth ions (REs) including Yb3+/Er3+, Yb3+/Ho3+ and Yb3+/Tm3+ co-doped manganese oxyfluoride glasses were fabricated using melt quenching method. By fully utilizing the upconversion luminescence (UCL) of REs and regulating energy transfer between the different energy levels of RE ions and the 4T1 level of Mn2+, the output of UCL was regulated and even pure-red light can be achieved. Moreover, owing to the selective partitioning caused by phase-separation network structure in the oxyfluoride glass, the UCL intensity of glasses annealed for 72 h is significantly enhanced 58 times compared to the rapidly quenched samples.

Overlap structure and free energy fluctuations in short-range spin glasses

We investigate scenarios in which the low-temperature phase of short-range spin glasses comprises thermodynamic states which are nontrivial mixtures of multiple incongruent pure state pairs. We construct a new kind of metastate supported on Gibbs states whose edge overlap values with a reference state fall within a specified range. Using this metastate we show that, in any dimension, the variance of free energy difference fluctuations between pure states within a single mixed Gibbs state with multiple edge overlap values diverges linearly with the volume. We discuss some implications of these results.

Comprehensive characterization of the structure of Zr-based metallic glasses

Structure of metallic glasses fascinates as the generic amorphous structural template for ubiquitous systems. Its specification necessitates determination of the complete hierarchical structure, starting from short-range-order (SRO) → medium-range-order (MRO) → bulk structure and free volume (FV) distribution. This link has largely remained elusive since previous investigations adopted one-technique-at-a-time approach, focusing on limited aspects of any one domain. Reconstruction of structure from experimental data inversion is non-unique for many of these techniques. As a result, complete and precise structural understanding of glass has not emerged yet. In this work, we demonstrate the first experimental pathway for reconstruction of the integrated structure, for Zr67Ni33\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{Zr}}_{{{67}}} {\ ext{Ni}}_{{{33}}}$$\\end{document} and Zr52Ti6Al10Cu18Ni14\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{Zr}}_{{{52}}} {\ ext{Ti}}_{{6}} {\ ext{Al}}_{{{10}}} {\ ext{Cu}}_{{{18}}} {\ ext{Ni}}_{{{14}}}$$\\end{document} glasses. Our strategy engages diverse (× 7) multi-scale techniques [XAFS, 3D-APT, ABED/NBED, FEM, XRD, PAS, FHREM] on the same glass. This strategy complemented mutual limitations of techniques and corroborated common parameters to generate complete, self-consistent and precise parameters. Further, MRO domain size and inter-void separation were correlated to identify the presence of FV at MRO boundaries. This enabled the first experimental reconstruction of hierarchical subset: SRO → MRO → FV → bulk structure. The first ever image of intermediate region between MRO domains emerged from this link. We clarify that determination of all subsets is not our objective; the essence and novelty of this work lies in directing the pathway towards finite solution, in the most logical and unambiguous way.

High-density stable glasses formed on soft substrates.

Enabled by surface-mediated equilibration, physical vapour deposition can create high-density stable glasses comparable with liquid-quenched glasses aged for millions of years. Deposition is often performed at various rates and temperatures on rigid substrates to control the glass properties. Here we demonstrate that on soft, rubbery substrates, surface-mediated equilibration is enhanced up to 170 nm away from the interface, forming stable glasses with densities up to 2.5% higher than liquid-quenched glasses within 2.5 h of deposition. Gaining similar properties on rigid substrates would require 10 million times slower deposition, taking ~3,000 years. Controlling the modulus of the rubbery substrate provides control over the glass structure and density at constant deposition conditions. These results underscore the significance of substrate elasticity in manipulating the properties of the mobile surface layer and thus the glass structure and properties, allowing access to deeper states of the energy landscape without prohibitively slow deposition rates.

Fabrication of a robust zwitterionic coating on glass with anti-fogging, anti-frosting, self-cleaning and antibacterial properties via UV-induced grafting polymerization

In this work, glass slides were separately silanized by silane coupling agents, 3-(trimethoxysilyl) propyl methacrylate (TPM) and 3-(mercaptopropyl) trimethoxysilane (MPS). Then, in presence of a photoinitiator, multifunctional hydrophilic coatings were fabricated facilely on these silanized glasses via UV-induced grafting polymerization of zwitterionic acrylic monomer methacryloxyethyl sulfobetaine (SBMA). The results showed that both TPM and MPS silanized glasses could participate in the UV-induced grafting polymerization of SBMA, while more SBMA could be grafted to the former glass to gain a little bit higher hydrophilicity. The structure, morphology and properties of the multifunctional glasses were investigated fully. As the hydrophilic polymer brushes poly(SBMA) (pSBMA) covalently attached to the glass surface, the glasses could render a series of excellent performances, including underwater superoleophobicity, anti-fogging, anti-frosting, abrasion resistance, self-cleaning and antibacterial adhesion, and especially high stability even after being immersed in water for 20 days. The strong interaction of pSBMA and water was confirmed via differential scanning calorimeter (DSC) and Raman spectrum analysis, to explicit the anti-fogging mechanism. Therefore, it is promising that the scalable multifunctional glass fabricated via UV-induced grafting polymerization could be potentially applied in the fields of automobile, bathroom, medical, etc.

The influence of phosphate glass structure on results of thermal poling

Two sodium phosphate glasses with different structure (meta- and orthophosphate ones) were thermally poled well below the glass transition temperatures. Glass with an orthophosphate structure (glass LA30) demonstrated a typical behavior of polarization current, that is, monotonic current decrease; however, in glass with a metaphosphate structure (glass LA10) the current first increased for 15–20 min and only then started monotonic decreasing. In spite of the similar sodium content, the current in LA10 glass exceeded the one in LA30 glass by about 10 times. This is explained by the capability of substituting intrinsic sodium ions by more mobile protons entering LA10 glass with a metaphosphate structure from the atmosphere. The other difference consists in the fact that the subanodic layer of LA10 glass after poling has many small cracks, while the subanodic layer of LA30 glass is crystallized. It should be emphasized that the crystallization of phosphate glasses under dc electric field below glass transition temperature is observed for the first time. In addition, after poling, no changes in the refractivity of both glasses were detected, but the generation of the second optical harmonic in LA30 glass was observed.

Influence of Nucleation on Relaxation, Molecular Cooperativity, and Physical Stability of Celecoxib Glass.

Although nucleation is considered the first step in the crystallization of glass materials, the structure and properties of the nuclei are not understood well. Influence of nucleation on the structure and dynamics of celecoxib glass was evaluated in this study. The nuclei for Form III were induced by annealing the glass at freezing temperature, and their impact on the relaxation behavior was investigated using thermal analysis and broadband dielectric spectroscopy to find accelerated α relaxation and suppressed β relaxation. In addition, observed after nucleation was a decrease in cooperativity of the molecular motion, presumably because of the appearance of void spaces in the glass structure. During long-term isothermal crystallization studies, crystal growth to Form III was accelerated in the presence of the nuclei, whereas this effect was less remarkable when a different crystal form dominated the crystallization behavior. These observations should provide more detailed insights into the nucleation mechanism and impact of nucleation on molecular dynamics including physical stability of pharmaceutical glasses. In addition, discussed is the remarkable acceleration of the crystallization rate of the celecoxib glass just below its Tg, which could be understood by diffusionless crystal growth.

Determination of SWCNT biosensor for bisphosphonate–2X(X = Mg2+, Ca2+, Sr2+) delivery in bone cell through electromagnetic and thermodynamic analysis using QM/MC methods

PurposeBisphosphonate (BP) medications can be applied to prohibit the damage of bone density and the remedy of bone illnesses such as osteoporosis. As the metal chelating of phosphonate groups are nearby large with six O atoms possessing the high negative charge, these compounds are active toward producing the chelated complexes through drug design method. BP agents have attracted much attention for the clinical treatment of some skeletal diseases depicted by enhancing of osteoclast-mediated bone resorption.Design/methodology/approachIn this work, it has been accomplished the CAM-B3LYP/6–311+G(d, p)/LANL2DZ to estimate the susceptibility of SWCNT for adsorbing alendronate, ibandronate, neridronate and pamidronate chelated to two metal cations of 2Mg2+, 2Ca2+, 2Sr2+ through nuclear magnetic resonance and thermodynamic parameters. Therefore, the data has explained that the feasibility of using SWCNT and BP agents becomes the norm in metal chelating of drug delivery system which has been selected through alendronate → 2X, ibandronate → 2X, neridronate → 2X and pamidronate → 2X (X = Mg2+/Ca2+/Sr2+) complexes.FindingsThe thermodynamic results have exhibited that the substitution of 2Ca2+ cation by 2Sr2+ cation in the structure of bioactive glasses can be efficient for treating vertebral complex fractures. However, it has been observed the most fluctuation in the Gibbs free energy for BPs → 2Sr2+ at 300 K. Furthermore, Monte Carlo simulation has resulted by increasing the dielectric constant in the aqueous medium can enhance the stability and efficiency of BP drugs for preventing the loss of bone density and treating the osteoporosis.Originality/valueAccording to this research, by incorporation of chelated 2Mg2+, 2Ca2+ and 2Sr2+ cations to BP drugs adsorbed onto (5, 5) armchair SWCNT, the network compaction would increase owing to the larger atomic radius of Sr2+ cation rather than Ca2+ and Mg2+, respectively.

Insight into the structure and crystallization of SiO2-Al2O3-P2O5-Na2O-MgO-CaO glass system with Mg-Ca substitution: A molecular dynamics study

Transparent glass ceramics (TGCs) have shown great prospects in many application fields. Understanding the effect of oxides on glass network structure and crystallization is essential for designing TGCs. A series of 18Na2O-(16-x)CaO-xMgO-3P2O5-2.5Al2O3-60.5SiO2 (mol%, x = 0, 4, 8, 12, 16) glass-ceramics were studied with Molecular dynamics (MD) simulations, and the effect of CaO substituted by MgO on the glass structure and crystallization was analyzed in details. The results show that MgO statistically behaves as a network former, and the overall network connectivity increases with the substitution of MgO for CaO. Further structure analysis shows that the complex glass system consists of Si-rich and P-rich phases, which respectively contain Si-Mg-rich regions with 2Mg1Si-related tricluster oxygens (TBOs) and P-Mg-rich regions. The energetically unfavorable TBOs and Mg4-O-Mg4 linkages provide favorable nucleation sites for homogeneous nucleation, and the so-called ‘Coordination matching’ principles are proposed to explain the type of crystals. These results help us understand the crystallization of Mg-containing glass ceramics and benefit the future design of novel spontaneous TGCs.