Polyamorphic Transition Research Articles

Nanostructured Molecular-Network Arsenoselenides from the Border of a Glass-Forming Region: A Disproportionality Analysis Using Complementary Characterization Probes.

Binary AsxSe100-x alloys from the border of a glass-forming region (65 < x < 70) subjected to nanomilling in dry and dry-wet modes are characterized by the XRPD, micro-Raman scattering (micro-RS) and revised positron annihilation lifetime (PAL) methods complemented by a disproportionality analysis using the quantum-chemical cluster modeling approach. These alloys are examined with respect to tetra-arsenic biselenide As4Se2 stoichiometry, realized in glassy g-As65Se35, glassy-crystalline g/c-As67Se33 and glassy-crystalline g/c-As70Se30. From the XRPD results, the number of rhombohedral As and cubic arsenolite As2O3 phases in As-Se alloys increases after nanomilling, especially in the wet mode realized in a PVP water solution. Nanomilling-driven amorphization and reamorphization transformations in these alloys are identified by an analysis of diffuse peak halos in their XRPD patterning, showing the interplay between the levels of a medium-range structure (disruption of the intermediate-range ordering at the cost of an extended-range one). From the micro-RS spectroscopy results, these alloys are stabilized by molecular thioarsenides As4Sen (n = 3, 4), regardless of their phase composition, remnants of thioarsenide molecules destructed under nanomilling being reincorporated into a glass network undergoing a polyamorphic transition. From the PAL spectroscopy results, volumetric changes in the wet-milled alloys with respect to the dry-milled ones are identified as resulting from a direct conversion of the bound positron-electron (Ps, positronium) states in the positron traps. Ps-hosting holes in the PVP medium appear instead of positron traps, with ~0.36-0.38 ns lifetimes ascribed to multivacancies in the As-Se matrix. The superposition of PAL spectrum peaks and tails for pelletized PVP, unmilled, dry-milled, and dry-wet-milled As-Se samples shows a spectacular smoothly decaying trend. The microstructure scenarios of the spontaneous (under quenching) and activated (under nanomilling) decomposition of principal network clusters in As4Se2-bearing arsenoselenides are recognized. Over-constrained As6·(2/3) ring-like network clusters acting as pre-cursors of the rhombohedral As phase are the main products of this decomposition. Two spontaneous processes for creating thioarsenides with crystalline counterparts explain the location of the glass-forming border in an As-Se system near the As4Se2 composition, while an activated decomposition process for creating layered As2Se3 structures is responsible for the nanomilling-driven molecular-to-network transition.

Continuous polyamorphic transition in high-entropy metallic glass

Polyamorphic transition (PT) is a compelling and pivotal physical phenomenon in the field of glass and materials science. Understanding this transition is of scientific and technological significance, as it offers an important pathway for effectively tuning the structure and property of glasses. In contrast to the PT observed in conventional metallic glasses (MGs), which typically exhibit a pronounced first-order nature, herein we report a continuous PT (CPT) without first-order characteristics in high-entropy MGs (HEMGs) upon heating. This CPT behavior is featured by the continuous structural evolution at the atomic level and an increasing chemical concentration gradient with temperature, but no abrupt reduction in volume and energy. The continuous transformation is associated with the absence of local favorable structures and chemical heterogeneity caused by the high configurational entropy, which limits the distance and frequency of atomic diffusion. As a result of the CPT, numerous glass states can be generated, which provides an opportunity to understand the nature, atomic packing, formability, and properties of MGs. Moreover, this discovery highlights the implication of configurational entropy in exploring polyamorphic glasses with an identical composition but highly tunable structures and properties.

Structure and entropy control of polyamorphous transition in high-entropy metallic glasses

Recently, a putative phase transition has been discovered in metallic glasses that could lead to two distinct amorphous states. This phenomenon, known as polyamorphism, has garnered significant interest, but its origins are still not fully understood, and predicting which compositions may undergo this transition remains a daunting task. Here, through development and experimental analysis of 62 different high entropy metallic glasses (HEMGs), we have discovered that the polyamorphic transition of HEMGs is closely linked to the complexity of their parent crystalline phase. Specifically, the number of crystal phases observed in x-ray diffraction is consistently higher in compositions capable of exhibiting polyamorphism in HEMGs compared to those that cannot. Furthermore, we have identified a high-entropy effect that enhances the enthalpy of polyamorphous transition. These findings shed light on how the structure and entropy play a crucial role in controlling the polyamorphous transition and offer insights for materials design.

Pressure-induced reversal of Peierls-like distortions elicits the polyamorphic transition in GeTe and GeSe

While polymorphism is prevalent in crystalline solids, polyamorphism draws increasing interest in various types of amorphous solids. Recent studies suggested that supercooling of liquid phase-change materials (PCMs) induces Peierls-like distortions in their local structures, underlying their liquid-liquid transitions before vitrification. However, the mechanism of how the vitrified phases undergo a possible polyamorphic transition remains elusive. Here, using high-energy synchrotron X-rays, we can access the precise pair distribution functions under high pressure and provide clear evidence that pressure can reverse the Peierls-like distortions, eliciting a polyamorphic transition in GeTe and GeSe. Combined with simulations based on machine-learned-neural-network potential, our structural analysis reveals a high-pressure state characterized by diminished Peierls-like distortion, greater coherence length, reduced compressibility, and a narrowing bandgap. Our finding underscores the crucial role of Peierls-like distortions in amorphous octahedral systems including PCMs. These distortions can be controlled through pressure and composition, offering potentials for designing properties in PCM-based devices.

Composition dependence of polyamorphic transition in Pd–Ni–P metallic glasses

Composition dependence of polyamorphic transition in Pd–Ni–P metallic glasses

Yielding under compression and the polyamorphic transition in silicon

We investigate the behavior of amorphous silicon under hydrostatic compression using molecular simulations. During compression, amorphous silicon undergoes a discontinuous nonequilibrium transition from a low-density to a high-density structure at a pressure of around $13$-$16$~GPa. Ensemble-averaged density and elastic constants change discontinuously across the transition. Densification of individual glassy samples occurs through a series of discrete plastic events, each of which is accompanied by a vanishing shear modulus. This is the signature of a series of elastic instabilities, similar to shear transformation zones observed during shear yielding of glasses. We compare the structure obtained during compression with a near-equilibrium form of amorphous silicon obtained by quenching a melt at constant pressure. This gives structures identical to nonequilibrium compression at low and high pressure, but the transition between them occurs gradually rather than discontinuously. Our observations indicate that the polyamorphic transition is of a nonequilibrium nature, and it has the characteristics of a yield transition that occurs under compression instead of shear.

Glass Polymorphism in Hyperquenched Aqueous LiCl Solutions

We investigate the glass polymorphism of dilute LiCl-H2O in the composition range of 0-5.8 mol % LiCl. The solutions are vitrified at ambient pressure (requires hyperquenching with ∼106 K s-1) and transformed to their high-density state using a special high-pressure annealing protocol. Ex situ characterization was performed via isobaric heating experiments using X-ray diffraction and differential scanning calorimetry. We observe signatures from a distinct high-density and a distinct low-density glass for all solutions with a mole fraction xLiCl of ≤ 4.3 mol %, where the most notable are (i) the jumplike polyamorphic transition from high-density to low-density glass and (ii) two well-separated glass-to-liquid transitions Tg,1 and Tg,2, each pertaining to one glass polymorph. These features are absent for solutions with xLiCl ≥ 5.8 mol %, which show only continuous densification and relaxation behavior. That is, a switch from water-dominated to solute-dominated region occurs between 4.3 mol % LiCl and 5.8 mol % LiCl. For the water-dominated region, we find that LiCl has a huge impact only on the low-density form. This is manifested as a shift in halo peak position to denser local structures, a lowering of Tg,1, and a significant change in relaxation dynamics. These effects of LiCl are observed both for hyperquenched samples and low-density samples obtained via heating of the high-density glasses, suggesting path independence. Such behavior further necessitates that LiCl is distributed homogeneously in the low-density glass. This contrasts earlier studies in which structural heterogeneity is claimed: ions were believed to be surrounded by only high-density states, thereby enforcing a phase separation into ion-rich high-density and ion-poor low-density glasses. We speculate the difference arises from the difference in cooling rates, which are higher by at least 1 order of magnitude in our case.

Kinetics and Mechanisms of Pressure-Induced Ice Amorphization and Polyamorphic Transitions in a Machine-Learned Coarse-Grained Water Model.

Water glasses have attracted considerable attention due to their potential connection to a liquid-liquid transition in supercooled water. Here we use molecular simulations to investigate the formation and phase behavior of water glasses using the machine-learned bond-order parameter (ML-BOP) water model. We produce glasses through hyperquenching of water, pressure-induced amorphization (PIA) of ice, and pressure-induced polyamorphic transformations. We find that PIA of polycrystalline ice occurs at a lower pressure than that of monocrystalline ice and through a different mechanism. The temperature dependence of the amorphization pressure of polycrystalline ice for ML-BOP agrees with that in experiments. We also find that ML-BOP accurately reproduces the density, coordination number, and structural features of low-density (LDA), high-density (HDA), and very high-density (VHDA) amorphous water glasses. ML-BOP accurately reproduces the experimental radial distribution function of LDA but overpredicts the minimum between the first two shells in high-density glasses. We examine the kinetics and mechanism of the transformation between low-density and high-density glasses and find that the sharp nature of these transitions in ML-BOP is similar to that in experiments and all-atom water models with a liquid-liquid transition. Transitions between ML-BOP glasses occur through a spinodal-like mechanism, similar to ice crystallization from LDA. Both glass-to-glass and glass-to-ice transformations have Avrami-Kolmogorov kinetics with exponent n = 1.5 ± 0.2 in experiments and simulations. Importantly, ML-BOP reproduces the competition between crystallization and HDA→LDA transition above the glass transition temperature Tg, and separation of their time scales below Tg, observed also in experiments. These findings demonstrate the ability of ML-BOP to accurately reproduce water properties across various regimes, making it a promising model for addressing the competition between polyamorphic transitions and crystallization in water and solutions.

Polyamorphism mediated by nanoscale incipient concentration wave uncovering hidden amorphous intermediate state with ultrahigh modulus in nanostructured metallic glass

Comprehending the pressure-/temperature-induced structural transition in glasses, as one of the most fascinating issues in material science, is far from being well understood. Here, we report novel polyamorphic transitions in a Cu-based metallic glass (MG) with apparent nanoscale structural heterogeneity relating to proper Y addition. The low-density MG compresses continuously with increasing pressure, and then a compression plateau appears after ∼8.1 GPa, evolving into an intermediate state with an ultrahigh bulk modulus of ∼467 GPa. It then transforms to a high-density MG with significantly decreased structural heterogeneity above ∼14.1 GPa. Three-dimensional atom probe tomography reveals concentration waves of Cu/Zr elements with an average wavelength of ∼5–6 nm, which promote the formation of interconnected ringlike networks composed of Cu-rich and Zr-rich dual-glass domains at nanometer scale. Our experimental and simulation results indicate that steplike polyamorphism may stem from synergic effects of the abnormal compression of the Zr–Zr bond length at the atomic scale and the interplay between the applied pressure and incipient concentration waves (Cu and Zr) at several nanometer scales. The present work provides new insights into polyamorphism in glasses and contributes to the development of high-performance amorphous materials by high-pressure nanostructure engineering.

Structural length-scale of β relaxation in metallic glass.

Establishing the structure-property relationship is an important goal of glassy materials, but it is usually impeded by their disordered structure and non-equilibrium nature. Recent studies have illustrated that secondary (β) relaxation is closely correlated with several properties in a range of glassy materials. However, it has been challenging to identify the pertinent structural features that govern it. In this work, we show that the so-called polyamorphous transition in metallic glasses offers an opportunity to distinguish the structural length scale of β relaxation. We find that, while the glass transition temperature and medium-range orders (MROs) change rapidly across the polyamorphous transition, the intensity of β relaxation and the short-range orders (SROs) evolve in a way similar to those in an ordinary reference glass without polyamorphous transition. Our findings suggest that the MRO accounts mainly for the global stiffening of the materials and the glass transition, while the SRO contributes more to β relaxation per se.

In situ study on medium-range order evolution during the polyamorphous phase transition in a Pd-Ni-P nanostructured glass

• Bulk-sized nanostructured glasses that exceed millimeters have been prepared. • Short-range order structure stably remains before and after laser evaporation. • Medium-range order dominates the polyamorphous phase transitions induced by P and T. • Multiscale structures and properties can be tailored based on polyamorphism engineering. Engineering multiscale structural hierarchies in glassy alloys enable a broad spectrum of potential applications. Metallic glasses were born in hierarchical structures from atomic-to-nanometer scales. However, the frozen-in structures in traditional metallic glasses prepared by rapid quenching techniques are challenging to tailor. Here, we show that a Pd 40 Ni 40 P 20 bulk nanostructured glass of polyamorphous interfacial structures was prepared by inert-gas condensation with a laser evaporation source, and its multiscale structures could be engineered. In-situ scattering experiment results reveal polyamorphous phase transitions occurred in the interfacial regions, which are accompanied by the evolution of medium-range order and the nanoscale heterogeneous structures during the condensation process of glassy nanoparticles under high pressure and the following heating process. Moreover, changes in the cluster connectivity resulting from repacking of the local ordering induced by pressure and temperature could be observed. The thermophysical and mechanical properties, including boson peaks, hardness, and elasticity modulus, could be changed as a function of heat-treatment parameters. Our findings would shed light on the synthesis of bulk nanostructured glassy alloys with tailorable thermodynamic and dynamical behavior as well as mechanical properties based on the understanding of metastability for polyamorphous interfacial phases.

Pressure-annealed high-density amorphous ice made from vitrified water droplets: A systematic calorimetry study on water's second glass transition.

In previous work, water's second glass transition was investigated based on an amorphous sample made from crystalline ice [Amann-Winkel et al., Proc. Natl. Acad. Sci. U. S. A. 110, 17720 (2013)]. In the present work, we investigate water's second glass transition based on the genuine glassy state of high-density water as prepared from micron-sized liquid water droplets, avoiding crystallinity at all stages. All the calorimetric features of water's second glass transition observed in the previous work are also observed here on the genuine glassy samples. This suggests that the glass transition indeed thermodynamically links amorphous ices continuously with deeply supercooled water. We proceed to extend the earlier study by investigating the effect of preparation history on the calorimetric glass transition temperature. The best samples prepared here feature both a lower glass transition temperature Tg,2 and a higher polyamorphic transition temperature Tons, thereby extending the range of thermal stability in which the deeply supercooled liquid can be observed by about 4K. Just before the polyamorphic transition, we observe a spike-like increase of heat capacity that we interpret in terms of nucleation of low-density water. Without this spike, the width of water's second glass transition is 15K, and the Δcp amounts to 3 ± 1JK-1 mol-1, making the case for the high-density liquid being a strong liquid. We suggest that samples annealed at 1.9GPa to 175K and decompressed at 140K to ≥0.10GPa are free from such nuclei and represent the most ideal high-density amorphous glasses.

LiquidDiffract: software for liquid total scattering analysis

LiquidDiffract is an open source, Python-based graphical application for X-ray total scattering analysis of liquids and disordered solids. The software implements procedures to obtain information on macroscopic bulk properties and local atomic-scale structure of monatomic or polyatomic samples from X-ray total scattering data. LiquidDiffract provides an easy to use interface with tools to perform background subtraction; calculation, normalisation, and refinement of the reciprocal-space structure factor and real-space correlation functions; and the extraction of structural information such as bond lengths, coordination number, and bulk density. The software is well suited to investigations of amorphous materials at extreme conditions, such as studies of high-pressure melt structure, polyamorphic phase transitions, and liquid equations of state. The open-source distribution and graphical interface will be of particular benefit to researchers who are new to the field. In this article we describe the distribution, system requirements, and installation of LiquidDiffract, and detail the data processing workflow and underlying numerical methods.

Direct observation of reversible liquid–liquid transition in a trehalose aqueous solution

Water forms two glassy waters, low-density and high-density amorphs, which undergo a reversible polyamorphic transition with the change in pressure. The two glassy waters transform into the different liquids, low-density liquid (LDL) and high-density liquid (HDL), at high temperatures. It is predicted that the two liquid waters also undergo a liquid-liquid transition (LLT). However, the reversible LLT, particularly the LDL-to-HDL transition, has not been observed directly due to rapid crystallization. Here, I prepared a glassy dilute trehalose aqueous solution (0.020 molar fraction) without segregation and measured the isothermal volume change at 0.01 to 1.00 GPa below 160 K. The polyamorphic transition and the glass-to-liquid transition for the high-density and low-density solutions were examined, and the liquid region where both LDL and HDL existed was determined. The results show that the reversible polyamorphic transition induced by the pressure change above 140 K is the LLT. That is, the transition from LDL to HDL is observed. Moreover, the pressure hysteresis of LLT suggests strongly that the LLT has a first-order nature. The direct observation of the reversible LLT in the trehalose aqueous solution has implications for understanding not only the liquid-liquid critical point hypothesis of pure water but also the relation between aqueous solution and water polyamorphism.

The hardest amorphous material.

ABSTRACT Zhang et al developed the hardest and strongest amorphous carbon through relaxation of compressed fullerene C60 by regulating the synthetic temperature and pressure. This type of amorphous carbon exhibits excellent semiconducting behavior. As the first research group, they discovered the polyamorphic transition in carbon. Their discoveries greatly benefit the development of superhard, superstrong, and semiconducting amorphous materials.

Quantifying a partial polyamorphic transition in a cerium-based metallic glass during cooling

Cerium-based metallic glasses are prototype polyamorphous systems with pressure-induced polyamorphic transitions extensively reported. Cooling typically has a similar effect on materials as compression with regard to reducing volume. However, previous studies show dramatically different behavior of Ce-based metallic glasses between cooling and compression, whose origin remains unclear. Here, using in situ low-temperature synchrotron high-energy x-ray diffraction, the structural evolution of a Ce68Al10Cu20Co2 metallic glass is accurately determined and analyzed by a structure factor and a reduced pair distribution function (PDF) during cooling from 298 to 83 K. An unusually large linear thermal expansion coefficient is revealed, which is associated with both continuous but inconsistent structural changes between the two subpeaks of the first atomic shell in terms of average bond lengths and coordination numbers. These phenomena are suggested to be attributed to a gradual 4f electron delocalization of only a minimal amount (∼2.6% at 83 K) of Ce atoms by quantitative analysis of the PDF data. However, a previously expected global polymorphic transition from a low-density amorphous state to a high-density amorphous state with an abrupt volume collapse is not observed. Moreover, electrical resistivity also shows a continuous increase during cooling without any sharp change. It is clarified that cryogenic temperatures could facilitate but are not powerful enough alone to trigger a global polymorphic transition in the Ce68Al10Cu20Co2 metallic glass, suggesting a wide distribution of its local atomic environment.

Polyamorphic Transitions in Metallic Glasses

Polyamorphic Transitions in Metallic Glasses

Polyamorphism in a solute-lean Al–Ce metallic glass

Polyamorphism discovered in lanthanide-rich metallic glasses (MGs) has been attributed to the electronic transition of the lanthanide element as a solvent element. In this work, we report that pressure-induced polyamorphism still exists in a Ce-poor Al93Ce7 binary MG where the 4f electron element serves as a solute and solute–solute avoidance is expected. The polyamorphic transition, observed by in situ high-pressure synchrotron x-ray diffraction, is accompanied by a volume collapse of ∼0.78% and occurs over a narrow pressure range from ∼0.8 to ∼1.8 GPa. Further synchrotron Ce L3-edge x-ray absorption spectroscopy measurements reveal that pressure-induced 4f electron delocalization underlies the polyamorphic transition. Molecular dynamics simulations confirm that the Ce atoms in the MG are completely isolated by the solvent Al atoms. This result demonstrates that 4f element-bearing alloys with extremely dilute concentrations can also exhibit polyamorphic states originating from electronic transitions, extending the compositional space of polyamorphism of MGs into very dilute regions. Our work suggests that tunable properties under compressive stress could be achieved in MGs by even minor doping of elements prone to electronic transitions.

Structural evolution of heavy rare Earth-based metal glass under high pressure

The structural evolution of Er55Al25Co20 metallic glasses (MGs) at high pressure was studied through x-ray diffraction with synchrotron radiation. The compression ratio, differential structure factor, pair distribution function g(r), and relative resistance as functions of pressure were analyzed and discussed. A reversible polyamorphic transition with a clear hysteresis was detected in the Er55Al25Co20 MGs. The irreversible annihilation of free volume and voids led to a densification of the specimens. Electronic resistance measurements demonstrated that the transition was strongly correlated with the electronic structural evolution. The results provide a new insight into understanding the mechanisms of polyamorphism in MGs.

The structural and dynamic heterogeneities of Ni-P nanoglass characterized by stress-relaxation

The method of stress-relaxation is applied to study the structural and dynamic heterogeneities of Ni-P nanoglass (NG) prepared by pulse electro-deposition. We provide direct evidence that the Ni-P NG has more flow units with better plasticity than conventional Ni-P metallic glass (MG) prepared by rapid quenching. Moreover, an anomalous peak is observed in the activation energy spectra of NG at 435 K, which may relate to a hidden polyamorphous phase transition in Ni-P NG. Our study provides insights on the understanding of the discrepancy in structural heterogeneity and dynamic and thermodynamic properties between the NG and MG. • Ni-P NG has the stronger structural heterogeneity and more flow units than MG by stress-relaxation. • An anomalous thermal expansion was found in NG at 435 K. • A phase transition happend in NG at 435 K which is related to polyamorphous phase transition.