Glass Formation Research Articles

Nearly close-packed atomic arrangements in BaTi2O5 glass

Recent advancements in glass synthesis have led to the creation of novel oxide glasses without tetrahedral corner-sharing networks. Of particular interest are glasses with high atomic packing densities, showcasing improved functionalities. Conventional analyses revealed the presence of not only four-coordinated polyhedra but also five- or six-coordinated polyhedra, which are connected via corner-sharing, edge-sharing, or face-sharing linkages. This study adapted the reduced atomic arrangement (RAA) method to analyze densely packed oxide glasses. The RAA method revealed a near-close-packed structure within a 10 Å range throughout BaTi2O5 glass, with Ba2+ and O2− ions arranged accordingly. Moreover, the structural model derived from relaxing the closest-packed arrangement via molecular dynamics simulations faithfully replicated the X-ray diffraction data. These findings suggest that minor deviations from the closest-packed atomic arrangement can initiate glass formation without corner-sharing tetrahedral networks. The RAA method proves highly effective in understanding glass formation mechanisms in unconventional oxide glasses.

ИЗУЧЕНИЕ ОСОБЕННОСТЕЙ СТЕКЛООБРАЗОВАНИЯ ЭМАЛЕВЫХ ФРИТТ ДЛЯ СТАЛЬНЫХ ОБЛИЦОВОЧНЫХ ПАНЕЛЕЙ

Cladding of buildings and structures, combining decorative, protective and thermal insulation functions, is currently in great demand in the construction industry. One of the effective areas for using vitreous and glass-crystalline enamel coat-ings is the protection of steel cladding panels for construction purposes. Therefore, there is a need to create and widely implement competitive enamel-coated panels made in Russia with specified properties. The work identifies the areas of glass formation and constructs a composition diagram in the SiO2–B2O3–Na2O–RxOy system of glass areas, which are the basis for the production of ground and top enamels. The physicochemical patterns of glass formation in the Na2O–B2O3–Al2O3–SiO2–RxOy system for the production of enamel coatings have been established by varying the values of the connectivity indicators of the aluminum-boron-silicon-oxygen framework.

Synchronously improving glass forming ability and mechanical properties by Pd alloying Zr-Al-Cu bulk metallic glass

In this work, the influences of Pd addition on the glass-forming ability (GFA), thermal behaviors, mechanical properties and microstructure of the Zr60Al10Cu30 bulk metallic glasses (BMGs) were systematically investigated. Our study shows that proper addition of Pd can simultaneously improve the GFA, strength and plasticity of BMGs. The BMGs with Pd contents of 2.5 at.% and 5 at.% exhibit high GFA of 10 mm and 12 mm, high strength of 1852 MPa and 1858 MPa, and good plasticity of 4.3 % and 5.9 %, respectively, all of them are much higher than those of Zr60Al10Cu30 BMGs. It is revealed that alloying BMGs with proper Pd promotes the formation of a higher degree of icosahedral clusters, which is responsible for improved GFA and strength, and simultaneously encourages a decrease in the volume of shear transition zone (STZ) and the amount of imperfect ordered packing (IOP) clusters, which are responsible for the enhanced plasticity. Our findings indicate that the synergistic effect of short-range ordered structures induced by alloying amorphous alloys plays an important role in simultaneously improving the GFA and mechanical properties, providing valuable insights for BMG design.

The scandium effect in Gd-rich BMGs: How and why does this ingredient work better than others?

Scandium is commonly known as a superior modifier for most alloys and compounds, substantially improving their phase stability and physical properties, as well as glass-forming ability. A special case is rare-earth based magnetic metallic glasses, which are an unique platform for intra-elemental substitution due to the chemical affinity of the lanthanides, yttrium and scandium. The latter, used as an alloying additive and being the smallest atom among the entire family, can drastically affect structure formation and magnetism in these metallic glasses. The main issue is that its modifying role is not well understood due to scarce information on the scandium effects in such rare-earth systems. This study is focused on thermal and magnetic analysis of some popular Gd-based BMGs redesigned with minor Sc additives. Here, we consider temperature behavior of specific heat capacity and entropy functions for both amorphous and crystalline phases to estimate the scandium effect on GFA and thermal stability of the glasses. As well, we inspect magnetic and magnetocaloric properties of these BMGs to understand whether this very expensive metal can radically improve the alloy magnetism and make these materials suitable for potential applications.

Unifying the temperature dependent dynamics of glass formers.

Strong changes in bulk properties, such as modulus and viscosity, are observed near the glass transition temperature, Tg, of amorphous materials. For more than a century, intense efforts have been made to define a microscopic origin for these macroscopic changes in properties. Using transition state theory (TST), we delve into the atomic/molecular level picture of how microscopic localized unit relaxations, or "cage rattles," evolve to macroscopic structural relaxations above Tg. Unit motion is broken down into two populations: (1) simultaneous rearrangement occurs among a critical number of units, nα, which ranges from 1 to 4, allowing a systematic classification of glass formers, GFs, that is compared to fragility; and (2) near Tg, adjacent units provide additional free volume for rearrangement, not simultaneously, but within the "primitive" lifetime, τ1, of one unit rattling in its cage. Relaxation maps illustrate how Johari-Goldstein β-relaxations stem from the rattle of nα units. We analyzed a wide variety of glassy materials and materials with a glassy response using literature data. Our four-parameter equation fits "strong" and "weak" GFs over the entire range of temperatures and also extends to other glassy systems, such as ion-transporting polymers and ferroelectric relaxors. The role of activation entropy in boosting preexponential factors to high "unphysical" apparent frequencies is discussed. Enthalpy-entropy compensation is clearly illustrated using the TST approach.

Orientational ordering and correlation in quasi-one-dimensional hard-body fluids due to close-packing degeneracy.

We study the orientational ordering properties of some quasi-one-dimensional hard-body fluids, where the anisotropic particles are confined to a straight line, while they are free to rotate in a plane. We examine a class of models where the close-packing structure is degenerate, i.e., the highest possible density can be realized with different orientational ordering. We find that the close-packing degeneracy always gives rise to a diverging orientational correlation, which can be a marker of phase transition, glass formation, and jamming. In the case of isotropic or partially ordered phases at the close-packing density, the diverging orientational correlation indicates a tendency for being a strongly ordered nematic phase. However, the orientational divergence in the perfect nematic phase shows that the particles must rotate in concert to go from one closely packed structure to another.

Sulphuric precipitates in novel titanium-based, sulphur-bearing bulk metallic glass – a BMG composite?

ABSTRACT New titanium-based metallic glasses containing sulphur as a key element have recently been developed and are the subject of ongoing research related to the effects of sulphur introduction into glass-forming alloy systems. Here we report on the formation of sulphuric precipitates during solidification of a Ti40Zr35Cu17S8 alloy and on the occurrence of secondary intermetallic compound crystallization starting in sulphur-depleted zones around the precipitates. The alloy is a promising metallic glass for use as a structural and biomedical material as it shows a high yield strength and good corrosion resistance paired with a low density. The role of sulphur for the glass formation in the Ti-Zr-Cu-S system is discussed and specimens quenched into different structural states are investigated by means of high-energy synchrotron diffraction and electron microscopy. The electron microscopic findings reveal that sulphuric precipitates precede the crystallization of an intermetallic (Ti, Zr)2Cu phase, which is the primary phase when sulphur is not present in the system and thus lead to a higher glass-forming ability. The sulphuric precipitates are found in specimens of various casting thickness and differ in their volume percentages depending on the size of the cast sample, while the secondary phase (Ti, Zr)2Cu crystallizes heterogeneously in the interfaces between the sulphuric precipitates and the local matrix.

Temperature and composition dependence modeling of viscosity and electrical conductivity of low-activity waste glass melts

The development of models that accurately relate the properties of a glass melt to its temperature and composition is important for glass formulation, melter control, and modeling the melt flow, refractory corrosion, and production rate. Using a database consisting of more than 4,000 data points measured between 900 °C and 1250 °C for over 600 unique low-activity waste glass compositions, we developed models for the melt viscosity and electrical conductivity. Models based on the Gaussian process regression approach outperformed models based on the Vogel–Fulcher–Tammann equation according to four standard metrics and yielded reliable prediction intervals. The models found primarily linear effects between properties and individual components, except for the effect of the Na2O mass fraction on the electrical conductivity. The effects were found to be consistent with current theories on physical processes involved with those properties.

Current and Future Perspectives of Bioactive Glasses as Injectable Material.

This review covers recent compositions of bioactive glass, with a specific emphasis on both inorganic and organic materials commonly utilized as matrices for injectable materials. The major objective is to highlight the predominant bioactive glass formulations and their clinical applications in the biomedical field. Previous studies have highlighted the growing interest among researchers in bioactive glasses, acknowledging their potential to yield promising outcomes in this field. As a result of this increased interest, investigations into bioactive glass have prompted the creation of composite materials and, notably, the development of injectable composites as a minimally invasive method for administering the material within the human body. Injectable materials have emerged as a promising avenue to mitigate various challenges. They offer several advantages, including minimizing invasive surgical procedures, reducing patient discomfort, lowering the risk of postoperative infection and decreasing treatment expenses. Additionally, injectable materials facilitate uniform distribution, allowing for the filling of defects of any shape.

Are Critical Fluctuations Responsible for Glass Formation?

The dynamic heterogeneities occurring just before the transition to the glassy phase have been named as the cause of amorphization in supercooled systems. Numerous studies conducted so far have confirmed this hypothesis, and based on it, a widely accepted solution to the puzzle of glass transition has been developed. This report focuses on verifying the existence of a strong pretransitional anomaly near the glass transition Tg. For this purpose, supercooled liquid-crystalline systems with a strong rod-like structure were selected. Based on the obtained experimental data, we demonstrate in this article that the previously postulated dynamic heterogeneities exhibit a critical characteristic, meaning a strong pretransitional anomaly can be observed with the described critical exponent α=0.5. Due to this property, it can be concluded that these heterogeneities are critical fluctuations, and consequently, the transition to the glassy state can be described based on the theory of critical phenomena. To measure the pretransitional anomaly near Tg in supercooled liquid-crystalline systems, broadband dielectric spectroscopy (BDS) and nonlinear dielectric effect (NDE) methods were applied. The exponent α provides insight into the nature and intensity of critical fluctuations in the system. A value of α=0.5 suggests that the fluctuations become increasingly intense as the system approaches the critical point, contributing to the divergence in specific heat. Understanding the role of critical fluctuations in the glass transition is crucial for innovating and improving a wide range of materials for energy storage, materials design, biomedical applications, food preservation, and environmental sustainability. These advancements can lead to materials with superior properties, optimized manufacturing processes, and applications that meet the demands of modern technology and sustainability challenges.

Effect of La2O3 on the optical, thermal, structural and radiation shielding properties of TeO2–ZnO–BaO glasses

Influence of lanthanum oxide (La2O3) on various properties of melt quenched zinc barium tellurite glasses (TeO2–BaO–ZnO) have been investigated. Lanthanum was limited to 10 mol% beyond which the glass formation ability was affected leading to crystallization in the proposed tie-line. Glass transition temperature improved with lanthanum oxide incorporation, while the density and energy band gap values showed a minimum at 5 mol%. The observed variation with lanthanum oxide doping was clearly elucidated from Raman spectral data, which indicated their influence in modifying the host ternary glass network. Radiation shielding parameter calculations showed a larger mass and linear attenuation coefficients for glasses doped with 10 mol% lanthanum oxide, indicating the influence of heavier oxides in improving the shielding properties and consequently acting as replacement candidate for toxic lead-based compounds.

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.