Glass Formation Research Articles

Glass Formation in Ring Polymer Melts Having Variable Knot Complexity and Molecular Mass

Glass Formation in Ring Polymer Melts Having Variable Knot Complexity and Molecular Mass

Glass and nanocrystalline phase formation in CuZrAg alloys: Insights from combinatorial thin film libraries studied by mapping synchrotron X-ray diffraction

We report detailed diffraction peak analysis and parameters indicative of the transition between fully amorphous microstructures and nanocrystal formation in sputter deposited thin film metallic glasses. Specifically, we fabricated ternary CuZrAg alloy films (2µm thickness) with a large compositional gradient on flexible, X-ray transparent polymer substrates in high vacuum conditions. The combinatorial libraries were subjected to point-by-point structural (XRD synchrotron radiation) and chemical (X-ray fluorescence spectroscopy) analysis, characterizing roughly 172 alloys. A strong correlation was found between peak symmetry and width, and early stages of crystalline phase formation. These nanocrystals are difficult to detect from the evolution of the peak position. In view of current literature, our data questions the recently claimed universality of the peak width as indicator of high glass forming ability. The addition of Ag significantly improves the poor glass formation of binary CuZr (36 alloys) under identical deposition conditions, as fully amorphous alloys are found for the majority of the investigated composition space. A thorough understanding of the microstructure of CuZrAg alloys on flexible substrates is highly relevant in view of favourable antibacterial properties and potential application as coatings for biomedical surfaces.

Deciphering the Nd3+ environment and energy-transfer mechanisms in thermally stable novel calcium aluminate glasses: elucidation of broadband high-gain performance for laser applications

Rare-earth-doped barium calcium aluminate (BCA) glasses, having extended infrared (IR) transmission (6 μm), are attractive materials for near IR (NIR) photonic applications. Nd2O3-doped BCA glasses display broadband emission at 1.07 µm, but they are limited, with poor glass-forming ability (GFA) and low emission cross sections. In the present study, four different barium zinc calcium aluminate (BZCA) glasses are synthesized with varied ZnO concentrations (from 9.5 to 24.5 mol%) and doped with 0.5 mol% Nd2O3 to decipher the effect on GFA and spectroscopic properties. The addition of ZnO enhances the GFA, and the NdBZCA20 glass shows the maximum GFA. Ultraviolet (UV)–visible (Vis)–NIR absorption spectra reveal a decreasing trend in the nephelauxetic effect, while J–O parameters, emission, and gain properties lead to no significant alteration with increasing ZnO, and the structure–properties correlation is established accordingly. However, the emission cross sections for all ZnO concentrations are found ∼4.5 × 10−20 cm2 accompanied by broadband emission (Δλ eff ∼ 40 nm), which ensures the potentiality of these glasses for low-threshold high-gain laser applications as well as ultrashort pulse laser applications. Furthermore, a thorough analysis of 1.06 µm emission as a function of Nd concentration in the BZCA20 glass is reported here. The emission spectra and decay time indicate that 0.5 mol% is the optimized doping concentration. Inokuti–Hirayama and Burshtein equations are adopted to study the decay kinetics and energy-transfer mechanisms, which confirm that the energy-transfer process due to cross-relaxation is dominant up to 0.5 mol% concentration, whereas, beyond that concentration, excitation energy migration via the hopping mechanism supersedes.

Is Ortho-Terphenyl a Rigid Glass Former?

Ortho-terphenyl (OTP) has long been used as a model system to study the glass transition due to its apparent simplicity and a widespread assumption that it is a rigid molecule. Here, we employ terahertz time-domain spectroscopy and low-frequency Raman spectroscopy to investigate the rigidity of OTP by direct observation of the low-frequency vibrational dynamics. These terahertz phonons involve complex large-amplitude atomic motions where intramolecular and intermolecular displacements are often mixed. Comparison of experimental results with density functional theory and ab initio molecular dynamics simulations shows that the assumption of rigidity neglects important implications for the glass transition and must be revisited. These results highlight the significance of terahertz modes on elasticity, which will be even more critical in more complex systems such as biomolecules.

Universal mechanism of shear thinning in supercooled liquids

Soft glassy materials experience a significant reduction in viscosity η when subjected to shear flow, known as shear thinning. This phenomenon is characterized by a power-law scaling of η with the shear rate γ°\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\dot{\\gamma }$$\\end{document}, η∝γ°−ν\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\eta \\propto {\\dot{\\gamma }}^{-\ u }$$\\end{document}, where the exponent ν is typically around 0.7 to 0.8 across different materials. Two decades ago, the mode-coupling theory (MCT) suggested that shear thinning occurs due to the advection. However, it predicts too large ν = 1 ( > 0.7 to 0.8) and overestimates the onset shear rate by orders of magnitude. Recently, it was claimed that a minute distortion of the particle configuration is responsible for shear thinning. Here we extend the MCT to include the distortion, and find that both advection and distortion contribute to shear thinning, but the latter is dominant. Our formulation works quantitatively for several different glass formers. We explain why shear thinning is universal for many glassy materials.

Formation Conditions of Ignimbrites of the Khangar Volcano (Kamchatka)

Abstract —The study of minerals, melt inclusions, as well as natural glasses showed that two different melts contributed to the formation of ignimbrites of the Khangar Volcano. The first, providing the information on melt inclusions in plagioclase and quartz phenocrysts, represents the state of magma in a deep source. The other type of melt is responsible for the formation of glasses and microcrystals of feldspars in fiamme. Experimental and analytical studies of melt inclusions showed that crystallization of most plagioclase and quartz phenocrysts from ignimbrites of the Khangar Volcano occurred at temperatures of 840–960 °C and pressures up to 1.1 kbar, from the melt with water contents up to 3.23 wt.%, under the conditions of magma chamber. The presence of syngenetic primary melt and fluid inclusions in plagioclase and quartz phenocrysts from ignimbrites of the Khangar Volcano indicates phase separation (“boiling”) of the melt with mass formation of СО2 microbubbles in magma. The other type of melt is secondary relative to magmatic systems of the Khangar Volcano and is formed by sintering and melting of tuffogenic volcanoclastic material. This melt contributed to the formation of fiamme in the examined ignimbrites. Based on the study of glasses and microcrystals of feldspars in fiamme, it was found that crystallization of oligoclase occurred at temperatures of 770–840 °C in the melt between the spherules (with water content up to 2.91 wt.%). Sanidine crystals grew over spherules at lower temperatures, 680–760 °C.

The glass transition temperature of anhydrous amorphous calcium carbonate

Abstract Amorphous calcium carbonate (ACC) is the least stable polymorph of calcium carbonates. It has been identified to play an important role in nature (e.g., biomineralization and speleothem formation), where it acts as a precursor for the transformation to more stable polymorphs such as calcite. Furthermore, the use of ACC in technical applications requires a robust understanding of the material’s properties. We present the first study that reveals the existence of a glass transition for synthetic and anhydrous ACC. The glass transition occurs at 339 °C. Such measurements are impossible with conventional differential scanning calorimetry (DSC) due to the high tendency of ACC to crystallize. Fast scanning DSC with heating rates of 500 °C/s and higher, however, can be used to separate the endothermic glass transition signature from the exothermic crystallization event since crystallization is shifted to higher temperatures. This allows the detection and quantification of the glass transition for ACC. These observations indicate that ACC is a structural glass and are especially significant because the synthesis of ACC, precipitation from a solution followed by lyophilization, contrasts with the more conventional and well-known route of glass formation–the rapid cooling of a melt. Moreover, we prove that a structural glass can be produced from a simple single-component carbonate system.

The role of Cr in optimizing properties of Fe–B–C–P–Si–Mo–Cr metallic glasses for applications

With the rapid development of third-generation semiconductors, there is an urgent need to develop high-performance soft magnetic Fe-based metallic glasses tailored particularly for their high-frequency applications. In this work, new Fe76−yB7C7P7Si3Moy−xCrx (y = 0, 1, 2, 3 at.%, x ≤ y) alloys with relatively high glass-forming ability (GFA) were developed. The effects of replacing Mo with Cr on GFA, thermodynamic properties, soft magnetic properties, electrical resistivity (ρ), and corrosion resistance at different Fe contents were systematically studied. The possible causes of GFA variation were discussed. The results show that the addition of a small amount of Cr replacing Mo under different Fe contents would not lead to a decrease in GFA. The critical sizes of Cr-containing glassy alloys are 1–2.5 mm. These alloys possess relatively high saturation magnetization (Ms) of 1.29–1.41 T and lower coercivity (Hc) of 0.7–1.8 A/m, contributing to the reduction of hysteresis loss. In addition, Cr increases ρ of the alloys, reaching up to 162 μΩ cm, which is beneficial to reducing eddy current loss at high frequency. Furthermore, Cr effectively enhances corrosion resistance, thereby increasing the service life of the alloys in harsh environments. The role of Cr in these aspects makes it a beneficial element in soft magnetic metallic glasses for high-frequency applications.

The Impact of Internal Structure Changes on the Damping Properties of 3D-Printed Composite Material

This article investigates the impact of changes in the internal structure of composite materials on their dynamic properties. The present research focuses on 3D-printed specimens with different reinforcement fiber arrangements. The specimens are printed on a Markforged Mark Two 3D printer. The base material is nylon filled with chopped carbon fibers (Onyx) and the reinforcement is in the form of long carbon, glass and Kevlar fibers. The experiment is carried out by the impact method. The principle of this method is to expose the specimen to a short impulse of force while monitoring its frequency response. The obtained results determine the natural frequencies and internal damping of the individual structures. We found that the highest damping is achieved by specimens with glass and Kevlar fibers in 45°, 90° and ±45° configurations. On the other hand, the lowest damping is achieved by specimens with carbon fibers and 0° and 0°,90° configurations. Also, the specimens with circumferential reinforcement show lower damping coefficient values. The knowledge and results of this work can be used in the development of new components; for example, in the transport industry, where the low weight and sufficient strength of components are important factors. These components have to absorb vibrations from various sources, such as motors and external influences.

Nonlinear dielectric response in glass formers: Restoring forces and avoided spin-glass criticality.

Experimental measurements of nonlinear dielectric response in glass formers like supercooled glycerol or propylene carbonate have been interpreted as providing evidence for a growing thermodynamic length scale when lowering temperature. A heuristic picture based on coherently flipping "superdipoles" with disordered internal structure has been argued to capture the essence of the experimentally reported behavior, pointing to the key role of effectively disordered interactions in structural glasses. We test these ideas by devising an explicit one-dimensional model of interacting spins incorporating both the spin-glass spirit of the superdipole argument and the necessary long-time decorrelation of structural disorder, encoded here in a slow dynamics of the coupling constants. The frequency-dependent third-order response of the model qualitatively reproduces the typical humped shape reported in experiments. The temperature dependence of the maximum value is also qualitatively reproduced. In contrast, the humped shape of the third-order response is not reproduced by a simple kinetically constrained spin model with noninteracting spins. To rationalize these results, we propose a two-length-scale scenario by distinguishing between the characteristic length of dynamical heterogeneities and a rigidity length that accounts for the local tendency of spins to flip coherently as a block, in the presence of interactions. We show that both length scales are identical in the kinetically constrained spin model, while they have significantly different dynamics in the model of interacting spins.

Evolution of short-range order and dynamics of medium-range order influence on the glass-forming ability of CuZrAg alloys

The glass-forming ability (GFA) of metallic glasses (MGs) is influenced by both short-range order (SRO) and medium-range order (MRO). However, experimentally examining the dynamic evolution of these microstructures across various time scales remains challenging. Therefore, this study employs molecular dynamics (MD) simulations to investigate the evolution of SRO and relaxation dynamics of MRO impacting on the GFA of Cu60Zr40-xAgx (x = 5, 10, 15, 20, 25) ternary alloys during their rapid solidification process. The GFA is characterized by the width of the supercooled liquid region, with Cu60Zr35Ag5 exhibiting the most prominent GFA among the five alloys. The reverse tracking method was utilized to analyze the inheritance and transformation of defective icosahedral clusters within the SRO. The defective icosahedral heritability and transformation rate are indicative of a more ordered and stable structure, significantly influencing the GFA. Furthermore, the decrease of Ag content leads to the increase of the average size of MRO clusters. The systems with larger MRO nanoclusters exhibit pronounced dynamic heterogeneity and a robust “cage effect”, thus hindering crystallization and promoting GFA. This study approaches GFA analysis from a microstructural evolution and dynamics perspective, aiming to provide theoretical backing for the discovery of alloys with superior GFA.

Glass-Forming Ability, Mechanical Properties, and Energetic Characteristics of ZrCuNiAlNbHfY Bulk Metallic Glasses.

The effects of partially substituting Al for Cu in Zr59.62Cu18.4-xNi12Al6+xNb3Hf0.78Y0.2 (x = 0, 2, 4, 6, 8 at.%) bulk metallic glasses (BMGs) on their glass-forming ability (GFA), quasi-static and dynamic mechanical properties, and energy characteristics were investigated. The results showed that an appropriate substitution of Al for Cu can improve GFA and reach a critical casting size up to 10 mm. Additionally, with Al replacement of Cu, the change in the distribution and content of free volume inside the BMGs was the main reason for the quasi-static compression plasticity. In contrast, the BMGs exhibited no plasticity during dynamic compression and high-speed impact, owing to the short loading time and thermal softening effect. In terms of energy characteristics, all alloys have a high combustion enthalpy. And on the surface of the fragments collected from impact, the active elements Zr, Al, and Nb reacted because of the adiabatic temperature rise. Further, x = 4 at.% Zr-based BMG with its superior overall performance could penetrate a 6 mm Q235 plate at a speed of 1038 m/s, combining excellent mechanical properties and energy characteristics. This study contributes to the development of Zr-based BMGs as novel energetic structural materials.

Oxide Scale Microstructure and Scale Growth Kinetics of the Hot-Pressed SiBCN-Ti Ceramics Oxidized at 1500 °C.

In this study, the SiBCN-Ti series ceramics with different Ti contents were fabricated, and the oxidation resistance and microstructural evolution of the ceramics at 1500 °C for different times were explored. The results show that with the increase in oxidation time, pores and bubbles are gradually formed in the oxide layer. When the oxidation time is less than or more than 4 h, the Ti(C, N) in the ceramics will maintain its initial structure or mostly transform to TiN. The introduction of Ti content can promote the formation of rutile silicate glass, thus healing the cracks and improving the oxidation resistance of the ceramics effectively.

Decoding the role of bismuth oxide in advancing structural, thermal, and nuclear properties of [B2O3–Li2O–SiO2]-Nb2O5 glass systems

This paper investigates the pivotal role of bismuth oxide (Bi₂O₃) in the enhancement of nuclear safety, structural, and thermal properties of glasses, specifically in the BNLS system. BNLS system has the formula [B2O3–Li2O–SiO2]-Nb2O5(20-x)–(Bi2O3)x (where x = 0.0,5.0,10.0,15.0 and 20.0 mol%). Through a comparative study, the potential advantages, and limitations of integrating Bi₂O₃ in place of traditional elements are highlighted, emphasizing its importance in the field of advanced glass materials. FTIR analysis showed the presence of Bi–O vibrations of the tetrahedral [BO4] groups and the Bi–O–Bi linkages. DSC testified the glass formation with increasing thermal stability of the formed glass with the inclusion of Bi2O3 into the glass system. Through the quantification of the Gamma Linear Attenuation Coefficient (GLAC) and Gamma Mass Attenuation Coefficient (GMAC), the work identifies the attenuation behavior against varying photon energies. Notably, a concentration-dependent rise in attenuation characteristics is observed, with BNLS20 exhibiting the most potent radiation shielding. Glass Half-Value Layer (GHVL) parameters and Mass Gamma Photon Penetration (GMFP) were measured, reinforcing that glasses with higher Bi2O3 concentrations and lower GHVL are better attenuators. The transmission factor (ln(I/Io)) was also studied, confirming that BNLS20 possesses the most effective radiation shielding capabilities. This research establishes that adding Bi₂O₃ to the [B2O3–Li2O–SiO2]-Nb2O5 glass system markedly improves its thermal stability and radiation shielding capabilities. BNLS20, in particular, emerges as a standout for radiation protection, surpassing both other BNLS variants and conventional shielding materials, thereby positioning it as an exceptional choice for advanced nuclear safety applications.

Structure and slow dynamics of protein hydration water with cryopreserving DMSO and trehalose upon cooling.

We study, through molecular dynamics simulations, three aqueous solutions with one lysozyme protein and three different concentrations of trehalose and dimethyl sulfoxide (DMSO). We analyze the structural and dynamical properties of the protein hydration water upon cooling. We find that trehalose plays a major role in modifying the structure of the network of HBs between water molecules in the hydration layer of the protein. The dynamics of hydration water presents, in addition to the α-relaxation, typical of glass formers, a slower long-time relaxation process, which greatly slows down the dynamics of water, particularly in the systems with trehalose, where it becomes dominant at low temperatures. In all the solutions, we observe, from the behavior of the α-relaxation times, a shift of the Mode Coupling Theory crossover temperature and the fragile-to-strong crossover temperature toward higher values with respect to bulk water. We also observe a strong-to-strong crossover from the temperature behavior of the long-relaxation times. In the aqueous solution with only DMSO, the transition shifts to a lower temperature than in the case with only lysozyme reported in the literature. We observe that the addition of trehalose to the mixture has the opposite effect of restoring the original location of the strong-to-strong crossover. In all the solutions analyzed in this work, the observed temperature of the protein dynamical transition is slightly shifted at lower temperatures than that of the strong-to-strong crossover, but their relative order is the same, showing a correlation between the motion of the protein and that of the hydration water.

Measuring the density, viscosity, and surface tension of molten titanates using electrostatic levitation in microgravity

Rare earth and barium titanates are useful as ferroelectric, dielectric, and optical materials. Measurements of their thermophysical properties in the liquid state can help guide melt processing technologies for their manufacture and advance understanding of fragile liquids' behavior and glass formation. Here, we report the density, thermal expansion, viscosity, and surface tension of molten BaTi2O5, BaTi4O9, and 83TiO2-17RE2O3 (RE = La or Nd). Measurements were made using electrostatic levitation and droplet oscillation techniques in microgravity, which provide access to quiescent liquid droplets and deep supercooling of 510–815 K below the equilibrium melting points. Densities were measured over 900–2400 K. Viscosities were similar for all four compositions, increasing from ∼10 mPa s near 2100 K to ∼30 mPa s near 1750 K. Surface tensions were 450–490 dyn cm−1 for the rare earth titanates and 383–395 dyn cm−1 for the barium titanates; surface tensions of all compositions had small or negligible temperature dependence over 1700–2200 K. For solids recovered after melt quenching, x-ray microtomography revealed the fracture mechanics in crystalline products and minimal internal porosity in glass products, likely arising from entrapped gas bubbles. Internal microstructures were generally similar for products processed either in microgravity or in a terrestrial aerodynamic levitator.

Thermal stability, glass-forming ability, and fragility nature of phase-change alloys of Se90Pb10−xSnx (0 ≤ x ≤ 8) system

Thermal stability, glass-forming ability, and fragility nature of phase-change alloys of Se90Pb10−xSnx (0 ≤ x ≤ 8) system

A unique Fe-based soft magnetic alloy and its magnetic softening mechanism

Fe-based amorphous alloys with good glass-forming ability (GFA), superior soft magnetic properties, low cost, and a wide heat treatment window have long been pursued in the field of soft magnetic materials due to their importance for mass production and broad applications. In the present study, by strategically adjusting the composition of a low-cost Fe-Si-B-P-Cu-C alloy, we achieved a saturation magnetization (Ms) of approximately 186 emu/g and a coercivity (Hc) of about 6 A/m for the Fe82.5 alloy with a good GFA. Specifically, the limited Cu content and suitable contents of metalloid elements played pivotal roles in enhancing the nuclei barrier and stabilizing the amorphous matrix. This, in turn, facilitated the formation of a finely uniform nanocrystalline structure dispersed within the amorphous matrix, enhancing soft magnetic properties during annealing. Notably, this magnetic softening behavior occurred at a lower heating rate. Structural characterizations revealed that a transient metalloid-rich shell and a stable amorphous matrix contributed to the slow growth of the α-Fe (Si) during prolonged isothermal annealing. This is in contrast to the agglomeration of small nanograins into larger clusters at high heating rates, which enhances the versatility and potential applicability of the alloy. The successful development of this novel nanocrystalline alloy offers promising guidance for addressing the challenges associated with the mass production of soft magnetic materials.

Evaluation of GlassNet for physics‐informed machine learning of glass stability and glass‐forming ability

AbstractGlassy materials form the basis of many modern applications, including nuclear waste immobilization, touch‐screen displays, and optical fibers, and also hold great potential for future medical and environmental applications. However, their structural complexity and large composition space make design and optimization challenging for certain applications. Of particular importance for glass processing and design is an estimate of a given composition's glass‐forming ability (GFA). However, there remain many open questions regarding the underlying physical mechanisms of glass formation, especially in oxide glasses. It is apparent that a proxy for GFA would be highly useful in glass processing and design, but identifying such a surrogate property has proven itself to be difficult. While glass stability (GS) parameters have historically been used as a GFA surrogate, recent research has demonstrated that most of these parameters are not accurate predictors of the GFA of oxide glasses. Here, we explore the application of an open‐source pre‐trained neural network model, GlassNet, that can predict the characteristic temperatures necessary to compute GS with reasonable performance and assess the feasibility of using these physics‐informed machine learning (PIML)‐predicted GS parameters to estimate GFA. In doing so, we track the uncertainties at each step of the computation—from the original ML prediction errors to the compounding of errors during GS estimation, and finally to the final estimation of GFA. While GlassNet exhibits reasonable accuracy on all individual properties, we observe a large compounding of error in the combination of these individual predictions for the PIML prediction of GS, finding that random forest models offer similar accuracy to GlassNet. We also break down the performance of GlassNet on different glass families and find that the error in GS prediction is correlated with the error in crystallization peak temperature prediction. Lastly, we utilize this finding to assess the relationship between top‐performing GS parameters and GFA for two ternary glass systems: sodium borosilicate and sodium iron phosphate glasses. We conclude that to obtain true ML predictive capability of GFA, significantly more data needs to be collected.

Synergistic effect of polymers in stabilizing amorphous pretomanid through high drug loaded amorphous solid dispersion.

Pretomanid (PTM), an oral antibiotic used in the treatment of adults with pulmonary extensively drug-resistant, nonresponsive multidrug-resistant tuberculosis (MDR-TB). It is a poor glass former, that shows high recrystallization tendency from the amorphous and supersaturated state, resulting in low aqueous solubility and suboptimal absorption through the gastrointestinal tract. The present investigation aimed to develop high drug loaded ternary amorphous solid dispersions (ASDs) of PTM with improved stability and enhanced biopharmaceutical performance by utilizing a combination of polymers. The polymers were comprehensively screened based on drug-polymer miscibility and saturation solubility analysis. A combination of Hydroxypropyl Methylcellulose Acetate Succinate (HPMCAS-HF) and Polyvinylpyrrolidone K-30 (PVP K-30) showed synergism in drug-polymer miscibility as evidenced through pronounced depression in the melting endotherm of PTM. The Powder X-ray Diffraction (P-XRD) diffractograms of 30% w/w PTM loaded ternary ASDs displayed the halo pattern, contrary to the binary ASDs. Drug-polymer interactions (hydrophobic forces) involved between PTM and polymers were detected through Fourier Transform Infrared Spectroscopy (FT-IR) and Nuclear Magnetic Resonance Spectroscopy (13C-NMR) which contributed to the synergistic enhancement in solubility and dissolution of ternary ASDs with sustained release over 12h. Ternary ASDs demonstrated better in-vivo performance compared to the binary ASDs, showing a 4.63-fold increase in maximum plasma concentration. All ASDs remained stable and resisted phase separation during short-term stability studies for 3 months at ambient conditions. It was concluded that the hydrophobic and hydrophilic polymeric combination (HPMCAS-HF and PVP K-30, respectively) effectively prevented the crystallization and ensured sustained drug release with improved in-vivo absorption of PTM.