Extreme Pressure Conditions Research Articles

Competing Phases of Iron at Earth's Core Conditions From Deep‐Learning‐Aided ab‐initio Simulations

AbstractThe properties and relative stability of different structures of iron at the extreme conditions of pressure and temperature of relevance for the Earth's core were determined with ab‐initio atomistic simulations aided by a machine‐learning force‐field. We find that the body‐centered cubic (bcc) structure is mechanically stable at core temperatures, but its free energy is marginally higher than those of the hexagonal close‐packed and face‐centered cubic structures. The bcc structure is the only structure whose shear sound velocity matches seismic data. The small free‐energy difference between competing structures suggests that the role of impurities could be crucial in stabilizing the bcc structure in the inner core.

Structural phase transition in NH₄F under extreme pressure conditions.

Ammonium fluoride (NH₄F) exhibits a variety of crystalline phases depending on temperature and pressure. By employing Raman spectroscopy and synchrotron X-ray diffraction beyond megabar pressures (up to 140 GPa), we have here observed a novel dense solid phase of NH₄F, characterised by the tetragonal P4/nmm structure also observed in other ammonium halides under less extreme pressure conditions, typically a few GPa. Using detailed ab-initio calculations and reevaluating earlier theoretical models pertaining to other ammonium halides, we examine the microscopic mechanisms underlying the transition from the low-pressure cubic phase (P-43m) to the newly identified high-pressure tetragonal phase (P4/nmm). Notably, NH₄F exhibits distinctive properties compared to its counterparts, resulting in a significantly broader pressure range over which this transition unfolds, facilitating the identification of its various stages. Our analysis points to a synergistic interplay driving the transition to the P4/nmm phase, which we name phase VIII. At intermediate pressures (around 40 GPa), a displacive transition of fluorine ions initiates a tetragonal distortion of the cubic phase. Subsequently, at higher pressures (around 115 GPa), every second ammonium ion undergoes a rotational shift, adopting an anti-tetrahedral arrangement. This coupled effect orchestrates the transition process, leading to the formation of the tetragonal phase.

Pressure-induced extreme anisotropic behavior of thermoelectric properties in crystalline β-CuSCN

Applying hydrostatic pressure has emerged as a promising strategy for regulating the properties of thermoelectric materials, particularly in the case of β-CuSCN, which has garnered attention due to its ultra-low thermal conductivity and potential applications in thermoelectric devices. Herein, we investigate the intrinsic mechanism governing the electron-thermal transport properties of β-CuSCN under hydrostatic pressure. It was found that ZT decreased by 30 % along the in-plane direction while increasing by 24 % along the out-of-plane direction following the application of hydrostatic pressure, respectively. Our results reveal that the competitive relationship between pressure-driven effects on phonon dynamics and electronic structure influences the thermoelectric properties of β-CuSCN. For the transport mechanism, the compression alters phonon dispersion by enhancing atomic interactions, which leads to an increase in lattice thermal conductivity. On the other hand, despite strong coupling between electrical transport parameters, a net increase in power factor is achieved through pressure-induced bandgap narrowing. As a result, the thermoelectric properties demonstrate contrary variation tendency along the in-plane and out-of-plane directions. Our research deepens our understanding of transport behavior under extreme pressure conditions and provides valuable insights into the fundamental relationship between structural deformation and thermoelectric performance.

Melting temperature of iron under the Earth’s inner core condition from deep machine learning

Constraining the melting temperature of iron under Earth’s inner core conditions is crucial for understanding core dynamics and planetary evolution. Here, we develop a deep potential (DP) model for iron that explicitly incorporates electronic entropy contributions governing thermodynamics under Earth’s core conditions. Extensive benchmarking demonstrates the DP’s high fidelity across relevant iron phases and extreme pressure and temperature conditions. Through thermodynamic integration and direct solid–liquid coexistence simulations, the DP predicts melting temperatures for iron at the inner core boundary, consistent with previous ab initio results. This resolves the previous discrepancy of iron’s melting temperature at ICB between the DP model and ab initio calculation and suggests the crucial contribution of electronic entropy. Our work provides insights into machine learning melting behavior of iron under core conditions and provides the basis for future development of binary or ternary DP models for iron and other elements in the core.

Ionic Liquids as Extreme Pressure Additives for Bearing Steel Applications

The protection of steel surfaces from wear under extreme pressure conditions is of major importance in several industries as it provides better performance and longer life of machinery. The motivation for this work was to study the lubrication of steel by ionic liquids (ILs), which have recently emerged as greener alternatives to commercial lubricants and additives. Three ILs based on sulfur-containing anions, used as 2-wt% additives in polyethylene glycol base oil (MW 200; PEG 200), were tested in the lubrication of ASTM 52100 bearing steel contacts in extreme pressure conditions (under mixed lubrication with a Hertzian pressure of 1.12 GPa) using a mini traction machine (MTM). Due to the poor resistance to corrosion of bearing steel, a semi-ester of succinic acid derivative corrosion inhibitor (Lanxess RC 4801) was added to the mixtures at a 1 wt% concentration. The ILs 1-hexyl-methylimidazolium trifluoromethanesulfonate ([C6mim][TfO]) and 1-hexyl-4-picolinium trifluoromethanesulfonate ([C6-4-pic][TfO]) revealed promising results in terms of surface protection of bearing steel. In contrast, 4-picolinium hydrogen sulfate ([4-picH][HSO4]) as 2-wt% additive to PEG 200 + 1% RC 4801 did not show any improvement in wear performance compared to neat PEG 200 + 1% RC 4801. PEG 200 + 2% [C6mim][TfO] + 1%RC 4801 allowed for a decrease in wear up to ~ 76% and PEG 200 + 2% [C6-4-pic][TfO] + 1%RC 4801 up to ~ 46% when compared with neat PEG 200 + 1% RC 4801. Optical microscopy images suggest the formation of an adsorbed layer, which was further supported by chemical analysis via x-ray photoelectron spectroscopy (XPS) data for [C6mim][TfO].Graphical abstract

First-principles calculation of Hubbard U for Terbium metal under high pressure

Using density functional theory (DFT) and linear response approaches, we compute the on-site Hubbard interaction U of elemental Terbium (Tb) metal in the pressure range ∼ 0–65 GPa. The resulting first-principles U values with experimental crystal structures enable us to examine the magnetic properties of Tb using a DFT+U method. The lowest-energy magnetic states in our calculations for different high-pressure Tb phases—including hcp, α-Sm, and dhcp—are found to be compatible with the corresponding magnetic ordering vectors reported in experiments. The result shows that the inclusion of Hubbard U substantially improves the accuracy and efficiency in modeling correlated rare-earth materials. Our study also provides the necessary U information for other quantum many-body techniques to study Tb under extreme pressure conditions.

Advancing molecular understanding in high moisture extrusion for plant-based meat analogs: Challenges and perspectives

In recent years, meat analogs based on plant proteins have received increasing attention. However, the process of high moisture extrusion (HME), the method for their preparation, has not been thoroughly explored, particularly in terms of elucidating the complex interactions that occur during extrusion, which remain challenging. These interactions arise from the various ingredients added during HME, including proteins, starches, edible gums, dietary fibers, lipids, and enzymes. These ingredients undergo intricate conformational changes and interactions under extreme conditions of high temperature, pressure, and shear, ultimately forming the fibrous structure of meat analogs. This review offers a overview of these ingredients and the molecular interaction changes they undergo during the extrusion process. Additionally, it delves into the major molecular interactions such as disulfide bonding, hydrogen bonding, and hydrophobic interactions, providing detailed insights into each.

Automated lost circulation severity classification and mitigation system using explainable Bayesian optimized ensemble learning algorithms

Lost circulation and mud losses cause 10 to 20% of the cost of drilling operations under extreme pressure and temperature conditions. Therefore, this research introduces an integrated system for an automated lost circulation severity classification and mitigation system (ALCSCMS). This proposed system allows decision makers to reliability predict lost circulation severity (LCS) based on a few drilling drivers before starting drilling operations. The proposed system developed and compared a total of 11 ensemble machine learning (EML) based on collection 65,377 observations, the data was pre-processed, cleaned, and normalized to be filtered using factor analysis. For each generated algorithm, the proposed system performed Bayesian optimization to acquire the best possible results. As a result, the optimized random forests (RF) model algorithm was the optimal model for classification at 100% classification accuracy based on testing data set. Mitigation optimization model based on genetic algorithm has been incorporated to convert high severe classes into acceptable classes of lost circulation. The system classifies the LCS into 5 classes where the classes from 2 to 4 are converted to be class 0 or 1 to minimize lost circulation severity by optimizing the input parameters. Therefore, the proposed model is reliable to predict and mitigate lost circulation during drilling operations. The main drivers that served as LCS inputs were explained using the SHapley Additive exPlanations (SHAP) approach.

A miniature multi-anvil apparatus using diamond as anvils-MDAC: Multi-axis diamond anvil cell.

The diamond anvil cell (DAC) has been widely used in high-pressure research. Despite significant progress over the past five decades, the opposed anvil geometry in the DAC inevitably leads to a disk-shaped sample configuration at high pressure. This intrinsic limitation is largely responsible for the large pressure and temperature gradients in the DAC, which often compromise precise experiments and their characterizations. We designed and fabricated a multi-axis diamond anvil cell (MDAC) by adopting the concept of a multi-anvil apparatus but using single crystal diamonds as the anvil material. Preliminary data show that the MDAC can generate extreme pressure conditions above 100GPa. The advantages of the MDAC over a traditional opposed anvil DAC include thicker, voluminous samples, quasi-hydrostatic, or designed deviatoric stress conditions, and multidirectional access windows for optical applications and x-ray probes. In this article, we present the design and performance of a prototype MDAC, as well as the application prospects in high-pressure research.

Phase composition and stability of Gd2−x Th x Zr2O7 under extreme conditions

Abstract Introduction of Th into synthetic disordered fluorite-type Gd2Zr2O7 induces a transition to an ordered pyrochlore-type phase at a Th concentration of 10 % at the Gd site (Gd1.8Th0.2Zr2O7 composition). The degree of order of the fluorite-type phase reaches 50 % for a Th concentration of 25 % (Gd1.5Th0.5Zr2O7 composition). Upon application of high pressure, the Gd2Zr2O7 phase retains the fluorite-type structure until 33 GPa (K 0 = 167(1) GPa), where it undergoes reversible amorphization. The Gd1.7Th0.3Zr2O7 phase was found to be stable up to at least a pressure of 25 GPa (K 0 = 169(3) GPa). Upon heating to T max of 1135 K, the Gd2Zr2O7 phase retains its disordered fluorite-type structural arrangement (α = 3.03 × 10−5 K−1). The excellent stability of the Gd2−x Th x Zr2O7 phases under extreme conditions of temperature and pressure makes Gd2Zr2O7 a promising candidate as a host matrix for radioactive elements for safe long-term underground storage of nuclear waste.

Pressure-induced temperature-driven phase transition and compressibility studies on nanocrystalline and bulk -U3O8 at extreme conditions of pressure and temperature

The study investigates the structural transition pathways of U3O8 under varying temperature and pressure conditions, focusing on both bulk and nanocrystalline forms. The bulk U3O8 is known to undergo reversible phase transitions to a hexagonal structure at temperatures above 150°C and irreversible transitions to a fluorite structure under pressure at ambient temperature. High-pressure XRD experiments reveal a significant decrease in transition pressure for the hexagonal to fluorite phase transition in bulk U3O8, with the HT-hex phase exhibiting a bulk modulus of 155 ± 21 GPa at 450°C. In 82 nm nanocrystalline U3O8, the transition from orthorhombic to hexagonal phase is reversible up to 1.0 GPa and 500°C but becomes irreversible above 1.7 GPa. The bulk modulus of the hexagonal phase of nanocrystalline U3O8 is estimated to be 168±12 GPa and 146±16 GPa at 400°C and 500°C, respectively. The findings highlight the complexity of structural transformations in U3O8 and their dependence on temperature and pressure, offering insights valuable for materials science and nuclear reactor engineering.

EMA beamline at Sirius: A versatile platform to probe glass and glass ceramics under extreme thermodynamic conditions

AbstractGlass and glass ceramics are very functional materials, albeit their structural complexity. Their relevance ranges from fundamental science problems in the fields of physics, chemistry, and geoscience, to applications in health areas, engineering, or technological matters that require high performance. Enhancing our understanding of these materials' performance and refining sample preparation methods remains paramount in this field. Synchrotron facilities offer a suite of powerful techniques for the detailed characterization of glasses and glass ceramics. These methods provide valuable insights into their atomic and molecular structure, phase transformations, mechanical behavior, and thermal properties, ultimately contributing to the development of improved materials for a wide range of applications. In‐depth investigations conducted under extreme conditions of pressure and temperature have yielded pivotal insights into densification mechanisms, phase transitions, crystallization kinetics, and their consequential macroscopic properties. The emergence of fourth‐generation synchrotrons brings in a wave of novel experimental possibilities that may exert a profound influence on this field in the coming decade. In this study, we unveil a selection of the remarkable capabilities now accessible to researchers at the Brazilian Synchrotron Light Source—Sirius, within the realm of extreme methods of analysis (EMA) beamline for investigating vitreous systems under extreme conditions.

Room-temperature pressure-induced phase separation in glassy alloys

Understanding the structural evolution of glass-forming alloys (metallic glasses) under high pressure conditions is important, on one hand, for elucidating their phase stability, and on the other, for manipulating their structure and properties. In this study, we investigate the unique pressure-induced effect leading to the phase separation phenomenon in glassy alloys, the effect which was not observed in the earlier works. By subjecting the system to various levels of external isostatic pressure, we observed the emergence of a distinct phase-separated structure within some glassy alloys. Our results shed light on the underlying mechanisms of phase separation in glassy alloys under extreme pressure conditions, providing valuable information for possible control of their structure and properties. This demonstrates that pressure can be used along or instead of temperature to produce nano-structured polyphase metallic glasses.

High pressure melt line of nickel using a generalized embedded atomic method potential

As the second most abundant metal in the Earth's core, nickel plays an important role in determining the structure and temperature of the Earth's core. Yet, the melt line of Ni at pressures corresponding to the Earth's core has not been explored in the literature. Many previous experimental and simulation efforts have reported the melting point of Ni at pressures below 100 GPa, but there exist large discrepancies, most of which have persisted due to various experimental and simulation bottlenecks in handling extreme pressure and temperature conditions. We adopted the generalized embedded atom method, which overcomes the limitations of existing interatomic potentials, to probe phase stability and phase boundaries of Ni at pressures between 50 and 500 GPa. The potential was validated by comparing the cold curves, phonon dispersion curves, and enthalpies of fusion with ab initio density functional theory calculations. Our analysis shows that face centered cubic (FCC) is stable, and the hexagonal close packed (HCP) and body centered cubic (BCC) phases are metastable close to the melt line. Melting temperatures at different pressures were obtained from two-phase co-existence simulations and take the following functional form: Tm=1969.23+19.15P−0.012P2. In contrast to iron, differences between the melting points of the stable and metastable phases of Ni are less than 250 K at 300 GPa, and the difference in melting points of the metastable BCC and HCP phases changes sign at 500 GPa, which implies that the phase transition mechanisms during solidification can be very complex.

Water at negative pressure: nuclear quantum effects

Various condensed phases of water, spanning from the liquid state to multiple ice phases, have been systematically investigated under extreme conditions of pressure and temperature to delineate their stability boundaries. This study focuses on probing the mechanical stability of liquid water through path-integral molecular dynamics simulations, employing the q-TIP4P/F potential to model interatomic interactions in flexible water molecules. Temperature and pressure conditions ranging from 250 to 375 K and − 0.3 to 1 GPa, respectively, are considered. This comprehensive approach enables a thorough exploration of nuclear quantum effects on various physical properties of water through direct comparisons with classical molecular dynamics results employing the same potential model. Key properties such as molar volume, intramolecular bond length, H–O–H angle, internal and kinetic energy are analysed, with a specific focus on the effect of tensile stress. Particular attention is devoted to the liquid-gas spinodal pressure, representing the limit of mechanical stability for the liquid phase, at several temperatures. The quantum simulations reveal a spinodal pressure for water of − 286 and − 236 MPa at temperatures of 250 and 300 K, respectively. At these temperatures, the discernible shifts induced by nuclear quantum motion are quantified at 15 and 10 MPa, respectively. These findings contribute valuable insights into the interplay of quantum effects on the stability of liquid water under diverse thermodynamic conditions.

The Simulation of Ester Lubricants and Their Application in Weak Gel Drilling Fluids.

To enhance the performance and reduce the amount of ester-based lubricants used in weak gel drilling fluids, a shear dynamics simulation under extreme pressure conditions was employed to refine the formulation of the base oil and pressure additives. The simulation results were validated using fatty acid methyl, ethyl, and butyl esters. Fatty acid methyl ester demonstrated the lowest temperature increase and the highest load-bearing capacity post-shear. The four-ball friction test revealed that methyl oleate had a coefficient of friction of 0.0018, approximately a third of that for butyl oleate, confirming the simulation's accuracy. By using methyl oleate as the base oil and oleamide as the pressure-resistant component, the optimal shear stress was achieved with a 10% addition of oleamide. A lubricant composed of 90% methyl oleate and 10% oleamide was tested and showed a coefficient of friction of 0.03 when 0.5% was added to bentonite slurry, indicating a strong lubricating film. Adding 1% of this lubricant to a low gel drilling fluid system did not affect its rheological properties, and the gel structure remained stable after seven days of aging. Field tests at the Fu86-3 well in the Jiangsu Oilfield of Sinopec confirmed that adding 1% of the ester-based lubricant to the drilling fluid significantly improved drilling efficiency, reduced drag by an average of 33%, and increased the drilling rate to 22.12 m/h. This innovation effectively prevents drilling complications and successfully achieves the objectives of enhancing efficiency.

A Novel Coating System Based on Layered Double Hydroxide/HQS Hierarchical Structure for Reliable Protection of Mg Alloy: Electrochemical and Computational Perspectives.

Growing research activity on layered double hydroxide (LDH)-based materials for novel applications has been increasing; however, promoting LDH layer growth and examining its morphologies without resorting to extreme pressure conditions remains a challenge. In the present study, we enhance LDH growth and morphology examination without extreme pressure conditions. By synthesizing Mg-Al LDH directly on plasma electrolytic oxidation (PEO)-treated Mg alloy surfaces and pores at ambient pressure, the direct synthesis was achieved feasibly without autoclave requirements, employing a suitable chelating agent. Additionally, enhancing corrosion resistance involved incorporating electron donor-acceptor compounds into a protective layer, with 8-Hydroxyquinoline-5-sulfonic acid (HQS) that helps in augmenting Mg alloy corrosion resistance through the combination of LDH ion-exchange ability and the organic layer. DFT simulations were used to explain the mutual interactions in the LDH system and provide a theoretical knowledge of the interfacial process at the molecular level.

Pressure-driven modification of optoelectronic features of ACaCl3 (A = Cs, Tl) for device applications

Intending to advance the use of halide-perovskites in technological applications, in this research, we investigate the structural, electronic, optical, and mechanical behavior of metal-halide perovskites ACaCl3 (A = Cs, Tl) through first-principle analysis and assess their potential applications. Due to the applied hydrostatic pressure, the interaction between constituent atoms increases, thereby causing the lattice parameter to decrease. The band structure reveals that band gap nature transits from indirect to direct at elevated pressure. Moreover, at high pressure, the electronic band structure shows a notable band gap contraction from the insulator (>5.0 eV) to the semiconductor region, which makes them promising for electronic applications. The charge density map explores the ionic and covalent characteristics of Cs/Tl–Cl and Ca–Cl under pressured and unpressurized environments. Induced pressure enhances the optical conductivity as well as the optical absorption that moves toward the low-energy region (red shift), making ACaCl3 (A = Cs, Tl) advantageous for optoelectronic applications. Additionally, this study reveals that the mechanical properties of ductility and anisotropy were found to be improved at higher pressures than in ambient conditions. Overall, this study will shed light on the technological applications of lead-free halide perovskites in extreme pressure conditions.

Controlling the Fluctuating Tip-Enhanced Raman Spectra of Chloramben on Silver Nanocubes.

Tip-enhanced Raman (TER) scattering from molecules residing at plasmonic junctions can be used to detect, identify, and image single molecules. This is most evident for flat molecules interrogated under conditions of extreme temperatures and pressure. It is also the case for (bio)molecular systems that feature preferred orientations/conformations under ambient laboratory conditions. More complex molecules that can adopt multiple conformations and/or feature different protonation or charge states give rise to complex TER spectra. We illustrate how the latter can be controlled in the case of chloramben molecules coated onto plasmonic silver nanocubes. We show that characteristic molecular Raman spectra cannot be obtained when tunneling plasmons are operative, i.e., when the tip is in direct contact with the chemically functionalized plasmonic nanoparticles. We rationalize these observations and propose an approach to less invasive and hence more analytical TER spectral imaging.

Strong impact and engraving characteristics of multi-layer metallic materials under a two-stage combustion condition

Abstract This work is focused on the strong deformation motion mechanism of multi-layer metallic materials under extreme pressure conditions accompanied by a strong impact effect between the projectile composed of multi-layer metallic materials and the steel barrel of the launcher itself. Here, this transient engraving process of the projectile with complicated stress–strain based on a new type of structure and propulsion pattern is firstly studied by proposing a new physical and mathematical model with a coupling of dynamical equations and two-stage combustion ballistic equations. Comparisons of engraving distance of computational results are done with experimental studies, and a reasonable match has been obtained in these comparisons. Further, the thickness effect of the metal jacket of the projectile on the engraving stress and deformation level is analyzed to obtain universal engraving resistance equations. The results have also shown that the projectile's whole transient deformation motion process in the launcher can be divided into three periods due to the initial slide impact effect under the first-stage propellant gas and the later propelling effect as the second-stage propellant is ignited. However, the engraving durations are all less than 0.7 ms with different levels of elastic-plastic deformations between multi-layer metallic materials for different conditions.