Ambient Phase Research Articles

Monoclinic distortion and magnetic transitions in FeO under pressure and temperature

Fe1-xO, although chemically simple, possesses a complex structural and magnetic phase diagram. The crystal structures of Fe1-xO and its magnetic properties at extreme conditions are still a matter of debate. Here, we performed a systematic investigation on Fe0.94O up to 94 GPa and 1700 K using synchrotron X-ray diffraction and synchrotron Mössbauer source spectroscopy. We observe a transition of Fe0.94O to the monoclinic phases above 40 GPa and at high temperatures and use the group theory analysis of the observed phases to discuss their properties and their relation to the ambient pressure phases. The Mössbauer spectra of the rhombohedral and the room temperature monoclinic phase contain a component attributed to Fe2.5+, caused by the electron exchange between the Fe3+ defect and neighboring Fe2+ atoms. Our results present a structural and magnetic transitional pressure-temperature diagram of Fe1-xO and show the complex physicochemical properties of simple Fe1-xO binary oxide under extreme conditions.

Pressure-induced structural, electronic, and superconducting phase transitions in TaSe3

Abstract TaSe3 has garnered significant research interests due to its unique quasi-one-dimensional crystal structure, which gives rise to distinctive properties. Using crystal structure search and first-principles calculations, we systematically investigated the pressure-induced structural and electronic phase transitions of quasi-one-dimensional TaSe3 up to 100 GPa. In addition to the ambient pressure phase (P21/m-I), we identified three high-pressure phases: P21/m-II, Pnma, and Pmma. For the P21/m-I phase, the inclusion of spin–orbit coupling (SOC) results in significant SOC splitting and changes in the band inversion characteristics. Furthermore, band structure calculations for the three high-pressure phases indicate metallic natures, and the electron localization function suggests ionic bonding between Ta and Se atoms. Our electron–phonon coupling calculations reveal a superconducting critical temperature of approximately 6.4 K for the Pmma phase at 100 GPa. This study provides valuable insights into the high-pressure electronic behavior of quasi-one-dimensional TaSe3.

Exploring the ambient metastability of yttrium substituted Bi2O3 electrolyte materials

The phase stability of (Bi1-xYx)2O3 (0.1 ≤ x ≤ 0.275) solid state electrolytes synthesized using the sol-gel method was investigated over prolonged periods under ambient conditions. The cubic polymorph was found to be metastable under ambient conditions, particularly for 0.1 ≤ x ≤ 0.15 where significant cubic-to-tetragonal transformation occurred. Spontaneous minor formation of both the rhombohedral polymorph and a bismuth subcarbonate phase was evident across the doping range but with varied reproducibility. Aging was significantly more prevalent for samples that had only been calcined (at 450 °C) as compared to those that were subsequently annealed (at 750 °C). The more highly substituted annealed materials (0.25 ≤ x ≤ 0.275) were initially phase pure cubic and far more stable, yet some rhombohedral and bismuth subcarbonate phase formation was also seen. Although the initial source of carbon which leads to the formation of the subcarbonate phase is not known at this stage, several suggestions are made. Pelletisation with additional sintering, as well as annealing powder samples under an inert atmosphere, was also shown to enhance the long-term phase stability characteristics of the cubic phase. This is the first longer term (over 2 years) ambient phase aging study of substituted bismuth oxides.

Well-posedness of an evaporation model for a spherical droplet exposed to an air flow

In this paper, we address the well-posedness of an evaporation model for a spherical liquid droplet taking into account the convective impact of an air flow in the ambient gas phase. From a mathematical perspective, we are dealing with a coupled ODE–PDE system for the droplet radius, the temperature distribution, and the vapor concentration. The nonlinear coupling arises from the evaporation rate modeled by the Hertz–Knudsen equation. Under physically meaningful assumptions, we prove existence and uniqueness of a weak solution until the droplet has evaporated completely. Numerical simulations are performed to illustrate how different air flows affect the evaporation process.

Uncertainty Quantification in Radial Anisotropy Models Based on Transdimensional Bayesian Inversion of Receiver Functions and Surface-Wave Dispersion: Case Study Sri Lanka

ABSTRACT In geophysical inference problems, quantification of data uncertainties is required to balance the data-fitting ability of the model and its complexity. The transdimensional hierarchical Bayesian approach is a powerful tool to evaluate the level of uncertainty and determine the complexity of the model by treating data errors and model dimensions as unknown. In this article, we take account of the uncertainty through the whole procedure, thus developing a two-step fully Bayesian approach with coupled uncertainty propagation to estimate the crustal isotropic and radial anisotropy (RA) model based on Rayleigh and Love dispersion as well as receiver functions (RFs). First, 2D surface-wave tomography is applied to determine period-wise ambient noise phase velocity maps and their uncertainty for Rayleigh and Love waves. Probabilistic profiles of the isotropic average VS and RA as a function of depth are then derived at station sites by inverting the local surface-wave dispersion and model errors and RFs jointly. The workflow is applied to a temporary seismic broadband array covering all of Sri Lanka. The probabilistic results enable us to effectively quantify the uncertainty of the final RA model and provide robust inferences. The shear-wave velocity results show that the range of Moho depths is between 30 and 40 km, with the thickest crust (38–40 km) beneath the central Highland Complex. Positive RA (VSH>VSV) observed in the upper crust is attributed to subhorizontal alignment of metamorphic foliation and stretched layers resulting from deformation. Negative RA (VSV>VSH) in the midcrust of central Sri Lanka may indicate the existence of melt inclusions and could result from the uplift and folding process. The positive RA in the lower crust could be caused by crustal channel flow in a collision orogeny.

Monoclinic LaSb2 Superconducting Thin Films.

Rare-earth diantimondes exhibit coupling between structural and electronic orders, which are tunable under pressure and temperature. Here we present the discovery of a new polymorph of LaSb2 stabilized in thin films synthesized using molecular beam epitaxy. Using diffraction, electron microscopy, and first-principles calculations we identify a YbSb2-type monoclinic lattice as a yet-uncharacterized stacking configuration. The material hosts superconductivity with a Tc = 2 K, which is enhanced relative to the bulk ambient phase, and a long superconducting coherence length of 1730 Å. This result highlights the potential thin film growth has in stabilizing novel stacking configurations in quasi-two-dimensional compounds with competing layered structures.

Investigation of Dynamic Viscoelastic Characteristics of Permeable Asphalt

In order to provide a basis for the structural analysis, design and maintenance of permeable asphalt pavements, and to promote their engineering promotion and application, this study investigated the dynamic viscoelastic properties of permeable asphalt mixtures (PAC-13) under complex stress states. A Simple Performance Tester (SPT) system was used to measure the dynamic modulus of the mix under complex stress states. The displacement factor and principal dynamic modulus curves were formed by fitting Sigmoidal functions and using 1stOpt (first optimization) software, the phase angle principal curves were further determined, and the dynamic modulus was predicted for the ambient phase (15–25 °C) using the Hirsch model. The results showed that the dynamic modulus of the mixtures decreases with an increasing temperature, and the maximum decrease in the dynamic modulus is 93% when the confining pressure is 100 kPa and the loading frequency is 10 Hz. The dynamic modulus increases with an increasing confining pressure and loading frequency, the maximum increase with an increasing confining pressure is 26.1% when the temperature is 25 °C and the loading frequency is 10 Hz, and the maximum increase with an increasing loading frequency is 411% when the temperature is 25 °C and the confining pressure is 100 Hz. The dynamic modulus has a strong frequency dependence at low temperatures, while it is stress-dependent at high temperatures. Meanwhile, based on the Hirsch model, a new modified prediction model was developed, which can well predict the dynamic modulus of permeable asphalt mixtures at room temperature.

High-pressure X-ray study of NbON oxynitride: direct transition from baddeleyite to cotunnite structure

Abstract The structural properties of NbON oxynitride under high pressure were investigated through in situ synchrotron X-ray diffraction (SXRD) up to 43 GPa. It was found that the bulk modulus of baddeleyite NbON (290 GPa) is larger than that of ZrO2 (150 GPa), indicating that the introduction of highly covalent nitrogen imparts greater stiffness. Furthermore, SXRD patterns reveal the emergence of a peak signaling a new crystalline phase above around 20 GPa. This is in contrast to TaON, where diffraction patterns only show an increase in background beyond 33 GPa. First-principle calculations suggest that the high-pressure phase adopts an orthorhombic cotunnite-type structure, distinguishing it from the oxide counterparts, wherein the ambient pressure phase transforms to a cotunnite structure via an orthorhombic-I structure.

Real-time tracking of coherent oscillations of electrons in a nanodevice by photo-assisted tunnelling

Coherent collective oscillations of electrons excited in metallic nanostructures (localized surface plasmons) can confine incident light to atomic scales and enable strong light-matter interactions, which depend nonlinearly on the local field. Direct sampling of such collective electron oscillations in real-time is crucial to performing petahertz scale optical modulation, control, and readout in a quantum nanodevice. Here, we demonstrate real-time tracking of collective electron oscillations in an Au bowtie nanoantenna, by recording photo-assisted tunnelling currents generated by such oscillations in this quantum nanodevice. The collective electron oscillations show a noninstantaneous response to the driving laser fields with a T2 decay time of nearly 8 femtoseconds. The contributions of linear and nonlinear electron oscillations in the generated tunnelling currents were precisely determined. A phase control of electron oscillations in the nanodevice is illustrated. Functioning in ambient conditions, the excitation, phase control, and read-out of coherent electron oscillations pave the way toward on-chip light-wave electronics in quantum nanodevices.

Air-soil cycling of oxygenated, nitrated and parent polycyclic aromatic hydrocarbons in source and receptor areas

Polycyclic aromatic hydrocarbons (PAHs) and their oxygenated and nitrated derivatives, OPAHs and NPAHs, are semivolatile air pollutants which are distributed and cycling regionally. Subsequent to atmospheric deposition to and accumulation in soils they may re-volatilise, a secondary source which is understudied.We studied the direction of air-soil mass exchange fluxes of 12 OPAHs, 17 NPAHs, 25 PAHs and one alkylated PAH in two rural environments being influenced by the pollutant concentrations in soil and air, by season, and by land cover. The OPAHs and NPAHs in samples of topsoil, of ambient air particulate and gas phases and in the gas-phase equilibrated with soil were analysed by GC-APCI-MS/MS. The pollutants soil burdens show a pronounced seasonality, a winter maximum for NPAHs and PAHs and a summer maximum for OPAHs. One order of magnitude more OPAH and parent PAH are found stored in forest soil than in nearby grassland soil. Among a number of 3–4 ring PAHs, the OPAHs benzanthrone and 6H-benzo(c,d)pyren-6-one, and the NPAHs 1- and 2-nitronaphthalene, 9-nitrophenanthrene and 7-nitrobenz(a)anthracene are found to re-volatilise from soils at a rural background site in central Europe in summer. At a receptor site in northern Europe, net deposition of polycyclic aromatic compounds (PACs) prevails and re-volatilisation occurs only sporadic.Re-volatilisation of a number of PACs, including strong mutagens, from soils in summer and even in winter indicates that long-range atmospheric transport of primary PAC emissions from central Europe to receptor areas might be enhanced by secondary emissions from soils.

Topography‐Incorporated Adjoint‐State Surface Wave Traveltime Tomography: Method and a Case Study in Hawaii

AbstractIn this study we recast surface wave traveltime tomography as an inverse problem constrained by an eikonal equation and solve it using the efficient adjoint‐state method. Specifically, recognizing that large topographic variations and high surface wave frequencies can make the topographic effect too significant to ignore, we employ an elliptically anisotropic eikonal equation to describe the traveltime fields of surface waves on undulated topography. The sensitivity kernel of the traveltime objective function with respect to shear wave velocity is derived using the adjoint‐state method. As a result, the newly developed method is inherently applicable to any study regions, whether with or without significant topographic variations. Hawaii is one of the most seismically and magmatically active regions. However, its significant topographic variations have made it less accurate to investigate using conventional surface wave traveltime tomography methods. To tackle this problem, we applied our new method to invert ambient noise Rayleigh wave phase traveltimes and construct a 3D shear wave velocity model. Our results reveal features that are consistent with geological structures and previous tomography results, including high velocities below Mauna Loa Volcano and Kilauea Volcano, and low velocities beneath the Hilina Fault Zone. Additionally, our model reveals a high‐velocity anomaly to the South of Hualalai's summit, which may be related to a buried rift zone. Our findings further demonstrate that including topography can lead to a correction of up to 0.8% in the shear wave velocity model of Hawaii, an island spanning approximately 100 km with volcanoes reaching elevations exceeding 4 km.

Crystal structure and properties of perovskite-type rubidium niobate, a high-pressure phase of RbNbO3.

We synthesized a perovskite-type RbNbO3 at 1173 K and 4 GPa from non-perovskite RbNbO3 and investigated its crystal structure and properties towards ferroelectric material design. Single-crystal X-ray diffraction analysis revealed an orthorhombic cell in the perovskite-type structure (space group Amm2, no. 38) with a = 3.9937(2) Å, b = 5.8217(3) Å, and c = 5.8647(2) Å. This non-centrosymmetric space group is the same as the ferroelectric BaTiO3 and KNbO3 but with enhanced distortion. Structural transition from orthorhombic to two successive tetragonal phases (Tetra1 at 493 K, Tetra2 at 573 K) was observed, maintaining the perovskite framework before reverting to the triclinic ambient phase at 693 K, with no structural changes between 4 and 300 K. The first transition is similar to that of KNbO3, whereas the second to Tetra2, marked by c-axis elongation and a significant cp/ap ratio jump (from 1.07 to 1.43), is unique. This distortion suggests a transition similar to that of PbVO3, where an octahedron's oxygen separates along the c-axis, forming a pyramid. Ab initio calculations simulating negative pressure like thermal expansion predicted this phase transition (cp/ap = 1.47 at -1.2 GPa), aligning with experimental findings. Thermal analysis revealed two endothermic peaks, with the second transition entailing a greater enthalpy change and volume alteration. Strong second harmonic generation signals were observed across Ortho, Tetra1, and Tetra2 phases, similar to BaTiO3 and KNbO3. Permittivity increased during the first transition, although the second transition's effects were limited by thermal expansion-induced bulk sample collapse. Perovskite-type RbNbO3 emerges as a promising ferroelectric material.

Metastable phase formation in europium hexaboride on compression to 187 GPa

Transition-metal and rare-earth borides are of considerable interest due to their electronic, mechanical, and magnetic properties as well as their structural stability under extreme conditions. Here, we report on a series of high-pressure Raman and x-ray diffraction experiments on the cubic rare-earth hexaboride EuB6 to an ultrahigh pressure of 187 GPa in a diamond anvil cell. In EuB6, divalent europium ions occupy the corners of the cubic structure, which encloses a rigid boron-bonded cage. So far, no structural phase transitions have been reported, while the nanoindentation studies indicate amorphization in nanoscale shear bands during plastic deformation. Our x-ray diffraction studies have revealed that the ambient cubic phase of EuB6 shows broadening and splitting of diffraction peaks starting at 72 GPa and the broadening continuing to 187 GPa. The high-pressure phase is recovered on decompression, and the Raman spectroscopy of the recovered sample from 187 GPa shows a downward frequency shift and broadening of T2g, Eg, and A1g modes of boron octahedron. The density functional theory simulations of EuB6 at 100 GPa have identified five possible lowest energy crystal structures. The experimental x-ray diffraction data at high pressures is compared with the theoretical predictions and the role of structural distortions induced by shear stresses is also discussed.

Pressure-induced phase transition, its mechanism and compressibility studies on nanocrystalline and bulk U3O8

High Pressure X-Ray Diffraction (HPXRD) studies were conducted on powder samples of U3O8 with crystallite sizes of 54 nm, 82 nm, as well as bulk U3O8. The investigation revealed that U3O8 undergoes a phase transition to a fluorite phase through an intermediate tetragonal structure, with the (200) plane of the orthorhombic structure playing a pivotal role. This transition occurs through the movement of uranium atoms while maintaining the overall integrity of the lattice. The phase transition is sluggish, and an extensive coexistence regime of the ambient and High-Pressure (HP) fluorite phase is observed in nano form as compared to bulk- U3O8. Moreover, the ambient phase of nano- U3O8 exhibits an elevated bulk modulus of 92 GPa, in contrast to the bulk sample's modulus of 78 GPa. Similarly, for the high-pressure phase, the bulk modulus is 419 GPa for nano- U3O8 and 367 GPa for bulk- U3O8. These findings provide valuable insights into the phase behavior and compressibility of U3O8, thereby carrying potential implications for nuclear technologists.

Preference for a pressure-induced 3D structure after 1T-HfSe2

Extensive crystal structure prediction searches provide evidence of two 3D structures with orthorhombic (Immm) and monoclinic (C2/m) space groups as reasonable candidates for the first pressure-induced phase of 1T-HfSe2. Our candidates are compared with two recent proposals that keep the 2D nature of the ambient conditions phase and display hexagonal (P63/mmc) and monoclinic (C2/m) symmetry, although the latter has a different structure than our proposed C2/m phase. Both of these 2D-like structures are discarded based on simple thermodynamic and kinetic arguments that can be extended to explain the pressure-induced polymorphic sequence of other transition metal dichalcogenides. The computed observables of our orthorhombic phase are fully consistent with the experimental structural and Raman data observed at low and high-pressure.

Pressure-induced successive phase transitions and Fano resonance engineering in lead-free piezoceramics KNbO3

We carried out detailed high-pressure Raman scattering studies on lead-free perovskite piezoceramics KNbO3 (KNO) with a smaller pressure interval so that the successive phase transition pressures are precisely determined (PO→T: 8.2 GPa; PT→C: 10.9 GPa). The pressure-quenched phase does not return to the ambient orthorhombic phase completely. In this work, the pressure-induced phase transition sequence is discussed in detail. Also, based on the pressure-dependent Raman spectra of KNO, we have discovered clear evidence of a pressure-induced Fano resonance. It reveals the role played by the Raman-active continuum and discrete energy states in the condensed matter system under high pressure and enables the high-pressure Fano resonances engineering in arbitrary geometries [q∈(−∞, 0)]. These findings highlight the opportunity for designing and tuning the wave transmission and optical switch properties of lead-free piezoceramics KNO via high pressure.

Neural-network-backed effective harmonic potential study of the ambient pressure phases of hafnia

Machine learning methods, and in particular neural-network force fields (NNFF), are bridging the gap between macroscopically relevant parameters and quantum mechanical simulations. This work describes an NNFF training strategy and uses it as the back end for an effective harmonic potential study of phase transitions in hafnia. While good agreement with experiment is found regarding the monoclinic-tetragonal transition, the commonly assumed transition to a Fm$\overline{3}$m cubic phase is found to be unlikely for the stoichiometric material

Ag2Mo3O10·2H2O nanorods under high pressure: In situ Raman spectroscopy

This work presents a pressure-dependent behavior of silver trimolybdate dihydrate (Ag2Mo3O10·2H2O) nanorods using in situ Raman scattering. The Ag2Mo3O10·2H2O nanorods were obtained by the hydrothermal method at 140 °C for 6 h. The structural and morphological characterization of the sample was performed by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). Pressure-dependent Raman scattering studies were performed on Ag2Mo3O10·2H2O nanorods up to 5.0 GPa using a membrane diamond-anvil cell (MDAC). The vibrational spectra under high pressure showed splitting and emergence of new bands above 0.5 GPa and 2.9 GPa. Reversible phase transformations under pressure were observed in silver trimolybdate dihydrate nanorods: Phase I - ambient phase (1 atm − 0.5 GPa) → Phase II (0.8 GPa − 2.9 GPa) → Phase III (above 3.4 GPa).

Pressure-Induced Anion Order-Disorder Transition in Layered Perovskite Sr2LiHOCl2.

While cation order-disorder transitions have been extensively investigated because of their decisive impact on chemical and physical properties, only few anion order-disorder transitions are known. Here, we show that Sr2CuO2Cl2-type layered perovskite Sr2LiHOCl2 exhibits a pressure-induced H-/O2- order-disorder transition. When synthesized at ambient and low pressures (≤2 GPa), Sr2LiHOCl2 is isostructural to orthorhombic Eu2LiHOCl2 (Cmcm) with a H-/O2- order at the equatorial sites. However, applying a higher pressure (5 GPa) during synthesis causes the equatorial anions to be disordered, leading to a tetragonal symmetry (I4/mmm) with a loss of the superstructure. The structural analysis revealed that, in the ambient pressure phase, HLi2Sr4 and OLi2Sr4 octahedra have distinct sizes to stabilize otherwise underbonded oxide ions, which is less important at the higher pressure. Anion-disordered Sr2LiHOBr2 and Ba2LiHOCl2 were also obtained at 5 GPa. Given the abundant layer-type anion order in perovskite-based oxyhydrides (e.g., La2LiHO3), the inclusion of additional anions (e.g., chloride) expands the frontiers of anion ordering patterns and their distribution control with the benefit of improving ionic conduction in solids.

Raman study of pressure-induced phase transitions in imidazolium manganese- hypophosphite hybrid perovskite

By using Raman spectroscopy, we demonstrate that [IM]Mn(H2POO)3 is a highly compressible material that undergoes three pressure-induced phase transitions. Using a diamond anvil cell we performed high-pressure experiments up to 7.1 GPa, using paraffin oil as the compression medium. The first phase transition, which occurs near 2.9 GPa, leads to very pronounced changes in the Raman spectra. This behavior indicates that this transition is associated with very large reconstruction of the inorganic framework and collapse of the perovskite cages. The second phase transition, which occurs near 4.9 GPa, is associated with subtle structural changes. The last transition takes place near 5.9 GPa and it leads to further significant distortion of the anionic framework. In contrast to the anionic framework, the phase transitions have weak impact on the imidazolium cation. Pressure dependence of Raman modes proves that compressibility of the high-pressure phases is significantly lower compared to the ambient pressure phase. It also indicates that the contraction of the MnO6 octahedra prevails over that of the imidazolium cations and hypophosphite linkers. However, compressibility of MnO6 strongly decreases in the highest pressure phase. Pressure-induced phase transitions are reversible.