Stable Pressure Range Research Articles

Predicted hot superconductivity in LaSc2H24 under pressure

The recent theory-driven discovery of a class of clathrate hydrides (e.g., CaH6, YH6, YH9, and LaH10) with superconducting critical temperatures (Tc) well above 200 K has opened the prospects for "hot" superconductivity above room temperature under pressure. Recent efforts focus on the search for superconductors among ternary hydrides that accommodate more diverse material types and configurations compared to binary hydrides. Through extensive computational searches, we report the prediction of a unique class of thermodynamically stable clathrate hydrides structures consisting of two previously unreported H24 and H30 hydrogen clathrate cages at megabar pressures. Among these phases, LaSc2H24 shows potential hot superconductivity at the thermodynamically stable pressure range of 167 to 300 GPa, with calculated Tcs up to 331 K at 250 GPa and 316 K at 167 GPa when the important effects of anharmonicity are included. The very high critical temperatures are attributed to an unusually large hydrogen-derived density of states at the Fermi level arising from the newly reported peculiar H30 as well as H24 cages in the structure. Our predicted introduction of Sc in the La-H system is expected to facilitate future design and realization of hot superconductors in ternary clathrate superhydrides.

Numerical study of a fractal-like tree node micromixer based on Murray’s law

Abstract This article focuses on the influence of fractal-like tree node (FTN) on the mixing efficiency and pressure drop of the micromixer. The mixing efficiency of FTN micromixers with different branch angle δ = 30°, 60° and 90° are compared at six kinds of Reynolds (Res). We can get that the micromixer with δ = 90° has higher mixing efficiency at any Re. The mixing results of the center FTN and the stagger FTN micromixer show that the center FTN has better mixing effect. The angle of FTN and the number of FTN are the key to improve the mixing efficiency. They are also the key to change the pressure drop in the microchannel. The FTN can slow down the pressure drop and maintain the stable pressure drop between two adjacent FTNs. The way to obtain a more stable pressure range is to increase the distance between two adjacent FTN. This provides a reliable reference for maintaining a stable pressure in the microchannel.

Pressure-induced electrides and metallic phases in the Y–Cl system

Pressure can profoundly change the electronic structure, leading to the formation of new phases and materials with exotic properties. Herein, using evolutionary algorithms and density functional theory, we systematically investigate the behaviour of materials in the yttrium–chlorine binary system under pressure. Electrons are found to be spatially confined at low pressures in yttrium chlorides and tend to form new electrides. In particular, a novel yttrium chloride, Y3Cl2, is predicted to be thermodynamically and lattice dynamically stable at approximately 10 GPa. Further analyses of the electron localization function and partial charge density identify trigonal Y3Cl2 as a new 2D high-pressure electride with partially localized electrons contributing to the conduction. By further increasing the pressure, electrons in the yttrium–chlorine binary system tend to delocalize with the electrides decomposing into two new compounds (Y2Cl and YCl2) and a new YCl phase (space group P63/mmc) above 20 GPa. These newly discovered phases are all metallic in their stable pressure range according to band structure simulations without interstitial electron localization. The discovery of these unconventional yttrium chlorides may inspire strategies to search for low-pressure electrides in other rare-earth halogenide systems.

First-principles comprehensive study of electronic and mechanical properties of novel uranium hydrides at different pressures

The systematic investigation on the U–H binary system up to 300 GPa has been performed by means of first-principles calculations in combination with the variable-composition evolutionary algorithm. Twenty uranium hydrides, including UHx (x = 1, 2, 3, 4, 5, 6, 7, 8, 9, 17), U2Hy (y = 3, 5, 7, 13, 15, 17), U3H8, U3H10, U4H5 and U4H9 have been found under different pressures. Besides thirteen compounds that are in nice agreement with previously reported structural search, new uranium hydrides in terms of the derived convex hull of the formation enthalpies have also been found in the present investigation. These seven novel compounds including Cmcm-UH3, Fmmm-UH4, R3‾m-U2H7, Pm–U2H15, Cm–U3H8, C2–U4H9 and C2/m-U4H5, are found to be dynamically and thermodynamically stable, and their stable pressure range has been determined. At last, the electronic and mechanical properties of these seven novel structures have further been calculated.

High-pressure stable phases in mercury azide

Exploring the bonding properties and polymerization mechanism of the polymer phases of nitrogen-rich compounds is one of the goals of high-pressure research. Considering first-principles calculations, a particle swarm optimization structure search method has been used to study the structural evolution behavior of nitrogen in HgN3 up to 200 GPa. Three new phases with P-1, P21/m, and P-1 structures at pressures of 38 GPa, 125 GPa, and 148 GPa are identified for the first time. The theoretical calculations show that the two P-1 structures are dynamically stable at 50 GPa and 200 GPa. In these two phases, the nitrogen atoms form an infinite one-dimensional zigzag chain and connected N6 ring, respectively. Two stable structures have semiconductor properties throughout the stable pressure range, primarily due to sp2 hybridization of nitrogen atoms. Our studies provide a theoretical basis for the synthesis of polymeric nitrogen in high-pressure experiments and indicate the direction for future studies of mercury azide.

Transitions in pressure-amorphized clathrate hydrates akin to those of amorphous ices.

Type II clathrate hydrates (CHs) were studied by thermal and dielectric measurements. All CHs amorphize, or collapse, on pressurization to 1.3 GPa below 135 K. After heating to 160 K at 1 GPa, the stability of the amorphous states increases in a process similar to the gradual high density to very high density amorphous ice (HDA to VHDA) transition. On a subsequent pressure decrease, the amorphized CHs expand partly irreversibly similar to the gradual VHDA to expanded HDA ice transformation. After further heating at 1 GPa, weak transition features appear near the HDA to low density amorphous ice transition. The results suggest that CH nucleation sites vanish on heating to 160 K at 1 GPa and that a sluggish partial phase-separation process commences on further heating. The collapsed CHs show two glass transitions (GTs), GT1 and GT2. GT1 is weakly pressure-dependent, 12 K GPa-1, with a relaxation time of 0.3 s at 140 K and 1 GPa; it is associated with a weak heat capacity increase of 3.7 J H2O-mol-1 K-1 in a 18 K range and an activation energy of only 38 kJ mol-1 at 1 GPa. The corresponding temperature of GT2 is 159 K at 0.4 GPa with a pressure dependence of 36 K GPa-1; it shows 5.5 times larger heat capacity increase and 4 times higher activation energy than GT1. GT1 is observed also in HDA and VHDA, whereas GT2 occurs just above the crystallization temperature of expanded HDA and only within its ∼0.2-0.7 GPa stable pressure range.

Ab initio studies of copper hydrides under high pressure

The crystal structure, electronic structure, and superconductivity of copper hydrides at high pressure have been studied by ab initio calculation. Consistent with experimental report, results show that the predicted stoichiometry Cu2H with the P-3m1 space group is stable above 16.8 GPa. The stoichiometry of CuH with the Fm-3m space group is predicted to be synthesized above 30 GPa, but it is metastable and dynamical instable up to 120 GPa. The electronic band calculations reveal that Cu2H is a good metal at a stable pressure range, whereas CuH is an insulator. Moreover, the other hydrogen-rich compounds CuH2 and CuH3 are thermodynamically and dynamically unstable, respectively. The calculated superconducting transition temperature (Tc) of Cu2H at 40 GPa is 0.028 K by using the Allen-Dynes modified McMillan equation.

Negative activation volume of oxygen self-diffusion in forsterite

Oxygen self-diffusion coefficients (DOx) were measured in single crystals of dry synthetic iron-free olivine (forsterite, Mg2SiO4) at a temperature of 1600 K and under pressures in the range 10−4 to 13 GPa, using a Kawai-type multi-anvil apparatus and an ambient pressure furnace. Diffusion profiles were obtained by secondary ion mass spectrometry operating in depth profiling mode. DOx in forsterite increases with increasing pressure with an activation volume of −3.9 ± 1.2 cm3/mol. Although Mg is the fastest diffusing species in forsterite under low-pressure conditions, O is the fastest diffusing species at pressures greater than ∼10 GPa. Si is the slowest throughout the stable pressure range of forsterite. Based on the observed positive and negative pressure dependence of DOx and DMg (Mg self-diffusion coefficient), respectively, DOx + DMg in forsterite decreases with increasing pressure, and then increases slightly at pressures greater than 10 GPa. This behavior is in agreement with the pressure dependence of ionic conductivity in forsterite based on conductivity measurements (Yoshino et al., 2017), and can be used to explain the conductivity increase from ∼300 km depth to the bottom of the asthenosphere.

Polymerization of nitrogen in cesium azide under modest pressure.

Alkali metal azides can be used as starting materials in the synthesis of polymeric nitrogen, a potential high-energy-density material. The structural evolutionary behaviors of nitrogen in CsN3 have been studied up to 200 GPa using particle swarm optimization structure search combining with density functional theory. Three stable new phases with C2/m, P21/m, and P-1 structure at pressure of 6, 13, and 51 GPa are identified for the first time. The phase transition to chain like structure (P-1 phase) occurs at a modest pressure 51 GPa, the azide ions N3 (-) (linear chains of three N atoms with covalent bonds and interact weakly with each other) begin to show remarkable polymeric N properties in the CsN3 system. Throughout the stable pressure range, the structure is metallic and consists of N atoms in sp(2) hybridizations. Our study completes the structural evolution of CsN3 under pressure and reveals that the introduced Cs atoms are responsible for the decreased synthesis pressure comparing to pure molecular nitrogen under compression.

Polymerization of nitrogen in lithium azide

Additional electrons can drastically change the bonding trend of light elements. For example, N atoms in alkali metal azides form the linear N3(-) anions instead of N2 molecules with the introduction of additional electrons. The effect of the additional electrons on the polymerization of N under pressure is important and thus far unclear. Using first principles density functional methods and the particle swarm optimization structure search algorithm, we systematically study the evolution of LiN3 structures under pressures up to 600 GPa. A stable structure featuring polymerized N under pressures higher than 375 GPa is identified for the first time. It consists of zig-zag N polymer chains that are formed by N5(-) five-member rings sharing N-N pairs. Throughout the stable pressure range, the structure is insulating and consists of N atoms in sp(3) hybridizations. Comparing with the atomic and electronic structures of previous phases, our study completes the structural evolution of LiN3 under pressure and reveals the structural changes which are accompanied and driven by the change of atomic orbital hybridization, first from sp to sp(2) and then from sp(2) to sp(3).

Monodispersed water-in-oil emulsions prepared with semi-metal microfluidic EDGE systems

Monodispersed water-in-oil emulsions were prepared with EDGE (Edge based Droplet GEneration) systems, which generate many droplets simultaneously from one junction. The devices (with plateau height of 1.0 μm) were coated with Cu and CuNi having the same hydrophobicity but different surface roughness. Emulsification was performed by using water as dispersed phase and oils with different viscosities (hexadecane, decane, hexane and sunflower oil) as continuous phases; lecithin, polyglycerol polyricinoleate (PGPR) and span80 were used as emulsifiers. The roughness affected the emulsification behaviour significantly. The smoother Cu surface exhibited droplet formation over the entire length of the droplet formation unit, while the rougher CuNi surface showed non-uniform filling of the plateau and much lower droplet formation frequency. In spite of this different behaviour, monodispersed droplets (CV <10 %) were produced by both systems (with span80 and PGPR), with a size six times the plateau height (d avg ≈ 6.0 μm). The droplet size decreased with increasing viscosity ratio and remained constant above some critical value. The emulsification process was stable over a wider range of pressures as previously found for silicon-based systems. The amount of PGPR influenced the pressure stability, but the system could be used effectively, while with lecithin and span80 the stable pressure range was very small. The pressure and viscosity stability of these semi-metal systems with rough surfaces show that the EDGE system has potential for practical applications, especially since overall productivity is not affected.

Structural stability of polymeric nitrogen: A first-principles investigation

The search for the stable single-bonded (polymeric) solid nitrogen attracted much attention in view of its potential application as a high energy density material. In this study, the stability of different candidate polymeric structures of nitrogen has been studied using ab initio calculations based on density-functional theory for the first time, from the angles of thermodynamic stabilities, mechanical stabilities, and dynamical stabilities in the pressure range from 0 to 360 GPa, respectively. According to our results, only Cmcm, A7, rcg, cg, BP, P2(1)2(1)2(1), and Pba2 are competitive structures and more favorable than sc, ch, LB, and cw strcutrues; their stable pressure range were also presented. Among the competitive structures, BP, Pba2, and P2(1)2(1)2(1) are the novel ones for their enthalpies are lower than the cg structure above 170 GPa. We further identify that the P2(1)2(1)2(1) phase can transform to cg structure at pressure below 60 GPa. Also a new phase transition sequence with increasing pressure has been presented, which is from the molecular phase epsilon-N(2) to cg at 47 GPa, to Pba2 at 170 GPa, and then to P2(1)2(1)2(1) at 307 GPa.

Parallelized edge-based droplet generation (EDGE) devices

We here report on three parallelized designs of the new edge-based droplet generation mechanism, which, unlike existing mechanisms, produces many equally sized droplets simultaneously at a single droplet formation unit. Operation of the scaled-out systems is straight forward; only the oil inlet pressure has to be controlled to let all the units produce oil droplets, given certain basic design constraints. For systems with a typical nozzle depth of 1.2 microm, the mean droplet diameter is 7.5 microm and the coefficient of variation is below 10%. The number of droplets that is formed per unit can easily be increased by increasing the length of the unit. The stable pressure range in which monodisperse droplets are formed can be extended by small adjustments to the design. Overall, the EDGE devices are simple in design and robust in use, making them suitable for massive outscaling.

磁石内蔵形正マグネトロン真空計

Aiming at elimination of the sudden change and inflection of the discharge current at a pressure, five type magnetron gauges containing a magnet inside of the electrode are investigated. One is a hand drum type magnetron gauge. Others are normal cylindrical magnetron gauges of various sizes. It is found that a normal cylindrical magnetron gauge, which contains rather big magnet inside of the cathode with the magnetic flux density of 0.091 [T] at 1.8 mm from the cathode surface, has wider stable pressure range and discharge voltage range, and shows good linearity of the pressure vs the discharge current characteristics in log-log plots. The sensitivity I/P is 3.96 (at 1 × 10-4 [Pa]) and 0.861.06 (at 1 × 10-6 [Pa]) [10-2 A/Pa], the slope of the pressure vs the discharge current characteristics in the log-log plots is 1.097 (at 1 × 10-4 [Pa]) and 1.684 (at 1 × 10-6 [Pa]) at the discharge voltage of 6 [kV] without any sudden change and inflection of the discharge current. The others also have good linearity of the pressure vs the discharge current characteristics in log-log plots at the discharge voltage of 6 [kV]. But, these gauges have sudden changes and inflections, except for 6 [kV] of the discharge voltages.

Stability relation of (Mg,Fe)SiO 3 garnets, major constituents in the Earth's interior

High-pressure and high temperature experiments at 20 GPa on (Mg,Fe)SiO 3 have revealed stability fields of two types of aluminium-free ferromagnesian garnets; non-cubic garnet and cubic garnet (majorite). Majorite garnet is stable only within a limited compositional variation, 0.2 < Fe/(Mg + Fe)< 0.4, and in the narrow temperature interval of ∼ 200°C around 2000°C, while the stability of non-cubic garnet with more iron-deficient compositions persists up to higher temperatures. These two garnets show fractional melting into iron-deficient garnet and iron-rich liquid, and the crystallization field of cubic garnet extends over Fe/(Mg + Fe)= 0.5. The assemblage silicate spinel and stishovite is a low-temperature phase, which also occurs in the iron-rich portion of the MgSiO 3—FeSiO 3 system. The sequence as given by the Fe/(Mg + Fe) value for the coexisting phases with the two garnets at 2000°C and 20 GPa is: silicate modified spinel ∼ aluminium-free garnets ≪ silicate spinel. Natural majorite in shock-metamorphosed chondrites is clarified to be produced at pressures above 20 GPa and temperatures around 2000°C. Similar shock events may cause the occurrence of non-cubic garnet in iron-deficient meteorites. Non-cubic garnet could be a stable phase in the Earth's mantle if a sufficiently low concentration of aluminium is present in the layer corresponding to the stable pressure range of non-cubic garnet. The chemical differentiation by melting in the deep mantle is also discussed on the basis of the present experimental results and the observed coexistence of majorite garnet with magnesiowüstite in chondrites.