Glass Behavior Research Articles

Fracture behavior of NiNb and NiNbP bulk metallic glasses

While it is known that phosphorous additions enhance the hardness, strength, and glass forming ability of NiNb(P) bulk metallic glasses, nothing is known about the trade-offs regarding the fracture characteristics. The fracture toughness and bending deformation behavior of Ni62Nb38 and Ni59.2Nb38.8P2 BMGs were studied, both of which have been reported to have very high compressive yield strength near 3GPa. The binary NiNb BMG exhibited ~4% plastic bending strain and a precracked fracture toughness of KQ = 50MPa√m which gives an excellent combination of strength and toughness relative to other engineering materials. With the addition of 2at.% phosphorus, the glass forming ability was maximized, but the BMG was hardened and embrittled, fatigue precracking was no longer possible, and micronotched toughness values, which should overestimate the precracked fracture toughness, were in the range of KQ = 19 − 26MPa√m. Additionally, a progressive hardening and bending embrittlement was observed for intermediate P additions of 1 and 1.5at.% phosphorus. Transmission electron microscopy revealed larger medium range order clusters in the relatively softer NiNb BMG which were thought to contribute to easier shear transformations and plastic deformation by shear banding.

Influence of the substitution of CaO by SrO on the structure, degradation and in vitro apatite formation of sol–gel derived SiO2–CaO–SrO–P2O5system bioactive glasses

The present study investigates the influence of the substitution of CaO by SrO on the structure, degradation and in vitro apatite formation of sol–gel-derived bioactive glasses with composition of 58SiO2–(38-x)CaO–xSrO–4P2O5, where x varies between 0 and 10 mol.%. The IV-type nitrogen adsorption/desorption isotherms and pore size values (ranging from 5.41 to 12.56 nm) confirmed the mesoporous structure of the synthesized glasses. The detailed structural analysis was carried out by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR). As network modifiers, the addition of Ca and Sr oxides disrupted the bonds of bridging oxygens (BOs) and resulted in the formation of non-bridging oxygens (NBOs), where the substitution of Ca with Sr led to an increase in Q1 units and a decrease in Q3 units. The effects of the addition of Sr on sample degradation and apatite formation were assessed using an assay in tris-(hydroxymethyl)-aminomethane and hydrochloric acid (Tris–HCl) and simulated body fluid (SBF). The results demonstrated that the substitution of CaO by SrO in the CaO–SiO2–P2O5 bioglass system altered the glass structure, resulting in reduced sample degradation and delayed apatite formation. This suggests that the incorporation of Sr into bioactive glasses may serve as a promising strategy to regulate the structure, dissolution behavior and apatite formation of silicate-based glasses, particularly concerning their long-term applications within the human body.

Bessel Beam Femtosecond Laser Interaction with Fused Silica Before and After Chemical Etching: Comparison of Single Pulse, MHz-Burst, and GHz-Burst

We investigate the elongated modifications resulting from a Bessel beam-shaped femtosecond laser in fused silica under three different operation modes, i.e., the single-pulse, MHz-burst, and GHz-burst regimes. The single-pulse and MHz-burst regimes show rather similar behavior in glass, featuring elongated and slightly tapered modifications. Subsequent etching with Potassium Hydroxide exhibits an etching rate and selectivity of up to 606 μm/h and 2103:1 in single-pulse operation and up to 322 μm/h and 2230:1 in the MHz-burst regime, respectively. Interestingly, in the GHz-burst mode, modification by a single burst of 50 pulses forms a taper-free hole without any etching. This constitutes a significant result paving the way for chemical-free, on-the-fly drilling of high aspect-ratio holes in glass.

Pressure-induced structural variations and mechanical behavior of silicate glasses: Role of aluminum and sodium

This study investigates the effects of pressure-induced densification on the structural and mechanical properties of albite-like (12.5 % Na2O·12.5 % Al2O3·75 % SiO2) and sodium silicate (12.5 % Na2O·87.5 % SiO2) glasses using Molecular Dynamics simulations. Densification increased the coordination numbers of Al and Na, facilitated Al-O-Al clustering and formation of three-bridging oxygens, reduced T-O-T angles, and packed sodium ions in albite glass. Sodium silicate glass exhibited densification primarily through increased Na coordination, reduction of Si-O-Si angle and reduced Na-Na distances. Elastic modulus calculations revealed increased stiffness with densification due to enhanced atomic packing and glass reticulation. Uniaxial tensile tests showed densified glasses had higher ductility and strength than undensified counterparts, highlighting the positive effects of pressure-induced structural rearrangements. Hydrostatic compression tests demonstrated reversible densification under varying pressure loads, with pre-treatment conditions significantly affecting residual densification.

Unveiling the boson peaks in amorphous phase-change materials

The Boson peak is a universal phenomenon in amorphous solids. It can be observed as an anomalous contribution to the low-temperature heat capacity over the Debye model. Amorphous phase-change materials (PCMs) such as Ge-Sb-Te are a family of poor glass formers with fast crystallization kinetics, being of interest for phase-change memory applications. So far, whether Boson peaks exist in PCMs is unknown and, if they do, their relevance to PCM properties is unclear. Here, we investigate the thermodynamic properties of the pseudo-binary compositions on the tie-line between Ge15Te85and Ge15Sb85from a few Kelvins to the liquidus temperatures. Our results demonstrate the evidence of the pronounced Boson peaks in heat capacity below 10 K in the amorphous phase of all compositions. By fitting the data using the Debye model combined with a modification of the Einstein model, we can extract the characteristic parameters of the Boson peaks and attribute their origin to the excess vibrational modes of dynamic defects in the amorphous solids. We find that these parameters correlate almost linearly with the Sb-content of the alloys, despite the nonmonotonic behaviors in glass forming abilities and thermal stabilities. In a broader context, we show that the correlations of the characteristic parameters of the Boson peaks with Tg and kinetic fragility, vary according to the type of bonding. Specifically, metallic glasses and conventional covalent glasses exhibit distinct patterns of dependence, whereas PCMs manifest characteristics that lie in between. A deeper understanding of the Boson peaks in PCMs holds the promise to enable predictions of material properties at higher temperatures based on features observed in low-temperature heat capacity.

Tunable rejuvenation behavior of Zr55Cu35Al10 metallic glass at the atomic scale during recovery annealing and pressure treatment

In this study, molecular dynamics (MD) simulations were employed to investigate atomic structure characteristics of Zr55Cu35Al10 metallic glasses under various annealing temperature and pressure. Following the initial formation of amorphous, the samples annealed at temperatures ranging from 800 K to 1100 K exhibited a transition from an aged state to a rejuvenated state during the subsequent heat treatment stage. In the third stage of heat treatment, increasing the pressure in samples from 0 to 50 GPa significantly enhanced the degree of rejuvenation compared to raising the temperature. Additionally, applying pressure dramatically enhanced the short-range order in the metallic glass system, altered the proportion of icosahedral cluster types, and contributed to a transformation of Voronoi polyhedrons (VPs) from low local five-fold symmetry to high local five-fold symmetry. Notably, the <0,0,12,0> VP, which represents high local five-fold symmetry, reached a peak proportion of 12.5 %, thereby strengthening the amorphous forming ability.

The magnetic characteristics of spinel-type MnCo2O4 at low temperatures

We report the magnetic properties of spinel oxide MnCo2O4 at low temperatures which is prepared through the sol-gel reaction process. The XPS results suggest that Mn3+ atoms exist in the octahedral sublattice originally occupied by Co3+ atoms. Afterwards, the AC susceptibility was measured at various frequencies, confirming a spin glass behavior at low temperatures. Additionally, analysis of the hysteresis loops revealed the presence of the exchange bias effect in our sample. The coexistence of spin glass behavior and the exchange bias effect in MnCo2O4 is attributed to the competition between ferromagnetic and antiferromagnetic interaction. The disorders of magnetic atoms in the lattice will also provide synergy for these magnetic behaviors.

Unlocking high photosensitivity direct laser writing and observing atomic clustering in glass

The direct laser writing (DLW) of photoluminescent metal clusters is inspiring intensive research in functional glasses. However, understanding the influence of the host structure on cluster formation and visualizing DLW-induced clusters at the atomic scale remains challenging. In this work, we develop a highly photosensitive fluorophosphate glass through fluorine incorporation. The addition of fluorine establishes a conducive environment for Ag+ ions before DLW and enhances the availability of reducing agents and diffusion pathways during DLW. These advantages facilitate the formation of Ag clusters under low-energy single-pulsed DLW. Increasing laser energy results in a combination of Ag clusters and glasses defect, forming a dot + ring photoluminescent pattern. Atom probe tomography (APT), a technique capable of mapping the elemental spatial distribution and identifying clustering, is employed to gain more information on laser-induced clusters. Comparison of APT results between samples without and with DLW reveals the formation of Ag clusters after laser writing. The design concept and characterization enrich the understanding of Ag cluster behavior in glasses. This knowledge opens the possibility of rational design of clusters confined in glasses and inspires their synthesis for various applications.

Unique Energy‐Storage Behavior Driven by High Entropy in Metallic Glasses

AbstractThe rejuvenation or energy‐storage behavior in metallic glasses (MGs) has been extensively explored for its theoretical and practical significance. However, very limited research focuses on the rejuvenation of high entropy metallic glasses (HEMGs), leaving uncertainties about how configurational entropy influences this process. In this study, cryogenic temperature cycling (CTC) is utilized to unlock the rejuvenation potential of a series of La‐based MGs with different entropy values. Comparative analysis of these MGs reveals that increased entropy boosts the maximum rejuvenation degree from 37% to 65% and widens the range of energy states where rejuvenation occurs. The changed rejuvenation behavior induced by entropy increase, which has never been reported other studies, are related to glass's structures, fragility and coupling degree between β and α relaxations. Besides, a new rejuvenation mechanism is revealed in HEMGs, which differs significantly from unrestricted growth and interconnection of flow units observed in most MGs. The atomic motion in HEMGs is confined within the icosahedral backbone network during CTC. Surprisingly, this local motion can propagate through strong interactions between adjacent atoms, facilitating the activation of α relaxation. These discoveries offer novel approaches to tune energy‐storage behavior of MGs by modulating icosahedral network structures through entropy control.

Nanoindentation-induced serrated flow behavior and deformation mechanism in metallic glass: A combined experiments and molecular dynamics simulation

In this study, the deformation behaviors of bulk metallic glass (BMG) during the nanoindentation are presented via the experiments and molecular dynamics (MD). The relationship between shear transformation zone (STZ) formation and serrated flow dynamics are developed to explain the deformation characterization evolution of BMG. It is found that as the peak load increases, the hardness and elastic modulus significantly decrease. Creep behavior at room temperature was also revealed by analyzing the creep displacement curve and the stress index under different peak loads.The accumulation of free volume during the deformation process promotes more uniform creep deformation. Furthermore, the serrated flow behaviors were analyzed innovatively using the shear stress drops further statistically. At lower loads, the occurrence of serrated retention is due to energy exceeding the potential barrier required for flow unit activation, ultimately released in the form of kinetic energy. At higher loads, the transition from intermittent curve to smooth curve exhibits a typical self-organized critical (SOC) state dynamic characteristics, and ISE phenomenon is also observed. The results also suggested that the shear deformation of the spherical indenter is more pronounced, with the shear band forming at a 45° angle to the direction of the downward pressure. And based on the Cooperative shear model (CSM) theory, the STZ size was estimated and verify that the increment of STZ makes it easier to generate stronger plastic strain to dissipate STZ, ultimately leading to complete plastic deformation. Combining five fold symmetry and gradient atoms, the majority of atoms with five fold symmetry (LFFS>0.5) have stronger resistance to plastic deformation when the load rate is low.

Structural, morphological, and magnetic characterizations of (Fe0.25Mn0.75)2O3 nanocrystals: A comprehensive stoichiometric determination

This report aims to investigate in depth FeMnO3, a material of interest due to its fascinating magnetic and multiferroic properties and its many applications in fields including lithium-ion batteries, microwave devices, and catalysis. However, understanding the precise stoichiometry of the material is crucial for a better comprehension of its physical properties. A cheap, simple, and repeatable sol-gel process was used to fabricate the FeMnO3 nanocrystals. Comprehensive multi-technique characterization of the as-fabricated FeMnO3 indicates that the main phase (94 wt%) is Fe0.5Mn1.5O3, although hematite appears as the minority phase (6 wt%). Magnetic characterization shows core-shell spin-glass like behavior, as well as paramagnetic-ferrimagnetic transitions and a Griffiths phase regime. EPR measurements revealed a strong and broad resonance line across the temperature range of 4.3 K–300 K, primarily influenced by the majority phase. The g-value decreases monotonically from 2.93 at 50 K to 2.18 at 300 K. There is a notable change in the resonance field and linewidth between 40 and 50 K, attributed to surface spin glass behavior. The EPR data below 50 K are in line with the core-shell model of (Fe0.25Mn0.75)2O3 nanoparticles. Below 50 K, the shell's spin system undergoes a transition from paramagnetic to spin-glass-like, with a critical temperature around 43 K. Above 50 K, the superparamagnetic minority phase significantly affects the temperature dependence of the resonance linewidth. These results hold particular importance as they advance our understanding of the intricate magnetic interactions present in FeMnO3. For the best possible use of this material platform in new technologies, such insights are essential.

Impact of Eu3⁺ on the self-crystallization of CsPbBr1.5Cl1.5 in glass-ceramics for precision temperature sensing applications

All-inorganic perovskite QDs, such as CsPbX3(X = Cl, Br, I), have garnered significant attention in the field of optoelectronics as emerging photonic materials. Rare-earth (RE) doping is an effective strategy for enhancing the optical properties of CsPbX3 perovskite quantum dot glasses. Therefore, investigating the crystallization behavior of rare-earth ion-doped CsPbX3 glass and the energy transfer mechanisms between rare-earth ions and CsPbX3 is crucial for advancing the development of rare-earth-doped perovskite glass materials. The paper systematically introduces the preparation methods, structural characteristics, and applications of CsPbBr1.5Cl1.5 QDs in optoelectronic devices. Firstly, the detailed effects of Eu3+ and F⁻ doping on the structure and optical properties of CsPbBr1.5Cl1.5 quantum dot glass are discussed. Subsequently, the crystal structure, size distribution, and morphology of CsPbBr1.5Cl1.5 QDs are characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Furthermore, the application of CsPbBr1.5Cl1.5 QDs in LEDs and temperature sensing optoelectronic devices is explored, highlighting their performance and potential value in these applications. This study provides important references and guidance for further research and application of CsPbBr1.5Cl1.5 QDs in the field of optoelectronics.

Effects of B2O3 on the structural evolution and biological behavior of borate bioactive glasses by sol-gel and melting methods

Borate bioactive glasses (BGs) have become indispensable in biomedicine for their exceptional bioactivity and tunable degradation characteristics. This study presents the synthesis and comprehensive evaluation of BGs within the xB2O3-CaO-Na2O-K2O-MgO-P2O5 system, featuring varying compositions of B2O3 (x = 40, 55, and 70 mol.%), using both sol-gel and melting techniques. A systematic investigation of their structural evolution, degradation kinetics, apatite-forming capabilities, and cytotoxicity has been conducted. The results demonstrate that the borate BGs with elevated B2O3 content significantly accelerates the degradation rate and enhances bioactivity across both synthesis methods, as B2O3 content increases from 40 to 70 mol%. Notably, the sol-gel derived BG samples demonstrate pronounced degradation, with mass loss reaching up to 90 %, and superior hydroxyapatite formation in simulated body fluid, surpassing the performance of their melting-derived counterparts. Cytotoxicity assays with MC3T3-E1 cells reveal no significant inhibitory effects from any of the borate bioglasses. Moreover, ab initio molecular dynamics simulations have been utilized to elucidate the relationship between structural alterations and in vitro bioactivity, with a particular emphasis on the boron coordination number. These findings provide a promising strategy for the development of borate BGs with tailored degradation profiles and excellent bioactivity, making them as strong candidates for various biomedical applications.

Excellent thermoelectric performance in alkali metal phosphides M3P (M = Na and K) with phonon-glass electron-crystal like behaviour.

Identifying ideal thermoelectric materials presents a formidable challenge due to the intricate coupling relationship between thermal conductivity and power factor. Here, based on first-principles calculations, along with self-consistent phonon theory and the Boltzmann transport equation, we theoretically investigate the thermoelectric properties of alkali metal phosphides M3P (M = Na and K). The evident 'avoided crossing' phenomenon indicates the phonon glass behavior of M3P (M = Na and K). Due to the strong lattice anharmonicity induced by alkali metal elements, accounting for quartic anharmonic corrections, the lattice thermal conductivities of Na3P and K3P at room temperature are merely 0.25 and 0.12 W m-1 K-1, respectively. Furthermore, the high degeneracy and 'pudding-mold-type' band structure lead to high p-type PF in M3P (M = Na and K). At 300 K, the p-type power factors (PF) of Na3P and K3P can reach 3.90 and 0.80 mW mK-2, respectively. The combination of ultralow κL and high PF leads to excellent thermoelectric figure of merit (ZT) values of 1.70 (3.38) and 1.18 (2.13) for p-type Na3P and K3P under optimal doping concentration at 300 K (500 K), respectively, surpassing traditional thermoelectric materials. These findings demonstrate that M3P (M = Na and K) exhibits behavior similar to phonon-glass electron crystals, thereby indicating a direction for the search for high-performance thermoelectric materials.

Magnetic properties of binary alloys Ni[formula omitted]Mo[formula omitted] and Ni[formula omitted]Cu[formula omitted] close to critical concentrations

The search for the ferromagnetic quantum critical point (FM QCP) has always been a captivating research topic in the scientific community. In pursuit of this goal, we introduced nonmagnetic transition metals to alloy with elemental nickel, and studied the magnetic properties of nickel binary alloys Ni1−xMox and Ni1−yCuy as a function of x and y up to the critical concentrations xcr and ycr at which the FM transition TC disappears. TC−x(y) phase diagrams were constructed via the Arrott–Noakes scaling of magnetization data. An enhanced Sommerfeld coefficient (the value of C/T as T→0) is observed near xcr and ycr, manifesting the effect of quantum fluctuations. However, the spin glass behavior is identified through the ac magnetic susceptibility measurements. This observation rules out the possibility of the existence of the FM QCP in both systems.

Structural Distortions and Short‐Range Magnetism in a Honeycomb Iridate Cu3ZnIr2O6

Layered honeycomb iridates receive significant attention in the materials chemistry and physics fields due to the relevance of their crystal structures to the Kitaev model of a quantum spin liquid (QSL). In quest of liquid‐like magnetic ground state signatures, first‐generation alkali metal iridates A2IrO3 ≡ A3[AIr2]O6 (A = Li, Na) and second‐generation iridates T3[AIr2]O6 (T = Cu, Ag, H) are developed. T3[AIr2]O6 is synthesized from A3[AIr2]O6 via metathesis reactions replacing alkali ions located between honeycomb layers. Herein, the next level of chemical and structural complexity is introduced by synthesizing the honeycomb iridate, Cu3ZnIr2O6, in which alkali ions between and within the honeycomb layers are both selectively exchanged with two different transition metals. Analysis of powder X‐Ray diffraction data reveals corrugation of the honeycomb layers in Cu3ZnIr2O6 that hinders complete magnetic frustration and results in a spin glass behavior observed from magnetization and specific heat data. Thus, Cu3ZnIr2O6 represents yet another model, which broadens understanding of intricate relationships between intralayer distortions and magnetism of prospective Kitaev QSL compounds.

Electron tailoring of thermal and magnetocaloric properties in Tb55TM17.5Al27.5 (TM = Fe, Co, and Ni) metallic glasses

Transition metal (TM) elements play a key role in determining properties of magnetocaloric materials. However, the effect of TM elements on the thermodynamic behavior and magnetocaloric effect (MCE) of metallic glasses (MGs) remains elusive. In this work, ternary Tb55TM17.5Al27.5 (TM = Fe, Co, and Ni) MGs without the complexities induced by high-entropy effects were designed. It is found that both the glass transition temperature (Tg) and the initial crystallization temperature (Tx) significantly increase with decreasing 3d electron number. It leads to the low values of Trg, γ, and γm for Tb55Fe17.5Al27.5, which is consistent with its poor glass forming ability (GFA) as evidenced by the obvious lattice fringes and structural order. Despite the mediocre value of magnetic entropy change (|ΔSMpk|) for Tb55Fe17.5Al27.5, its broader magnetic transition temperature of 110.4 K associated with ∼26% evident structural order yields the maximum relative cooling power (RCP) of 546.04 J kg−1 among three MGs. Moreover, a novel weighted method for evaluating 3d electron number by consideration of the concentration and species of TM elements was adopted to reveal an inverse correlation between the 3d electron number and Tg/Tx, as well as curie temperature (Tc), |ΔSMpk|, and RCP. It is found that with the decrease of the weighted 3d electron number of TM elements, the thermal stability of rare-earth-base MGs is effectively enhanced ascribed to the strong f - d orbital hybridization effect, along with the enhanced 3d - 3d exchange interaction that induces a high Tc. This work would help us more deeply understand the role of TM elements from the perspective of electronic structure, which is crucial for designing the novel MGs with a tunable MCE and GFA applied in various cryogenic refrigeration fields.

Deformation behavior of thermally rejuvenated Zr-Cu-Al-(Ti) bulk metallic glass

The deformation behavior of metallic glasses has been shown in prior studies to be often dependent on its structural state, namely higher energy “rejuvenated” state versus lower energy “relaxed” state. Here, the deformation behavior of thermally rejuvenated Zr-Cu-Al-(Ti) bulk metallic glasses (BMGs) was evaluated. Rejuvenation was achieved by cryogenic thermal cycling with increase of free volume measured in terms of enthalpy of relaxation. Hardness, stiffness, and yield strength of the BMGs were all found to decrease while plasticity increased after rejuvenation. More free volume in the rejuvenated BMG resulted in homogeneous plastic deformation as was evident from the high strain rate sensitivity and more pronounced shear band multiplication during uniaxial compression. Shear transformation zone (STZ) volume was calculated by cooperative shear model and correlated well with the change in structural state after rejuvenation. The enhanced plasticity with the addition of 1 at. % Ti as well as after cryogenic thermal cycling was explained by lower activation energy for shear flow initiation due to increased heterogeneity induced in the system. Molecular dynamics simulation demonstrated that the variation in plastic deformation behavior is correlated with local atomic structure changes.

Enhancing the luminescent properties of strontium phosphate glass via controlled crystallization and rare earth dopants

The study focused on investigating the photoluminescence behavior of pure strontium phosphate glasses with a composition of 62.5% P2O5 and 37.5% SrO. Then it was extended to investigate the effects of adding rare earth elements (Pr3+, Sm3+, Eu3+, Dy3+) and the crystallization process on improving luminescent properties of the parent glass. Various spectroscopic measurements, including XRD, SEM & EDAX, and FTIR, were conducted to examine the relationship between structural changes and their impact on luminescent performance. The optical measurements showed a characteristic enhancement resulting from the addition of RE3+-dopants and the crystallization process. The crystallization of glasses yielded a single phase from Sr(PO3)2 with an extended emission peak at 671 nm and heightened intensity compared to the glassy sample. The development of efficient and stable luminescent glasses via crystallization and dopant type can lead to advancements in applications such as glowing devices, optical detectors, and photonics innovations.

Ductile behavior of glass–ceramics with precipitated CaF&lt;sub&gt;2&lt;/sub&gt;, xonotlite, and cristobalite

Ductile behavior of glass–ceramics with precipitated CaF&lt;sub&gt;2&lt;/sub&gt;, xonotlite, and cristobalite