Compression behavior and phase transition of β-Si_3N_4 under high pressure

The compressibility and pressure-induced phase transition of β-Si_3N_4 were investigated by using an angle dispersive x-ray diffraction technique in a diamond anvil cell at room temperature. Rietveld refinements of the x-ray powder diffraction data verified that the hexagonal structure(with space group P63/m, Z = 2 formulas per unit cell) β-Si_3N_4 remained stable under high pressure up to 37 GPa. Upon increasing pressure, β-Si3 N4 transformed to δ-Si_3N_4 at about 41 GPa. The initial β-Si_3N_4 was recovered as the pressure was released to ambient pressure, implying that the observed pressureinduced phase transformation was reversible. The pressure–volume data of β-Si_3N_4 was fitted by the third-order Birch–Murnaghan equation of state, which yielded a bulk modulus K_0= 273(2) GPa with its pressure derivative K_0= 4(fixed)and K0= 278(2) GPa with K 0= 5. Furthermore, the compressibility of the unit cell axes(a and c-axes) for the β-Si_3N_4 demonstrated an anisotropic property with increasing pressure.     

Synthesis and Strong Blue—Green Emission Properties of ZnO Nanowires

ZnO nanowires were catalytically grown on Au-coated silicon substrates by the carbon thermal reduction method. The process involved addition of a low partial pressure of hydrogen sulphide to the argon carrier flow. The addition of H2S led to the higher yield and longer nanowires without any morphology change, and no sulphuric content was observed by the energy dispersive x-ray spectroscopy in the resulting nanowires. The nanowires exhibited strong blue-green emission at room temperature and an increasing intensity when the partial pressure of H2S was raised. The temperature-dependent photoluminescence spectra show that intensity of the blue-green emission, almost without shift, decreases slowly with increasing temperature. Heat treatments indicated that quenching resulted in a higher ratio of blue-green emission to ultraviolet emission.     

Enhancement of Magnetoresistance in Granular CrO2／Polystyrene Composites

We present a study of magnetotransport in CrO2/polystyrene (PS) composites over a range of polystyrene concentration (0-30 wt. %). In the experiment, an obvious enhancement in magnetoresistance (MR) is observed at 77K and at room temperature as the hadf-metadlic Cr02 particles are encapsulated with a thin layer of insulating polystyrene. The enhanced MR can be interpreted in terms of spin-dependent intergranular tunnelling with 4-nm-thick PS barrier. Moreover, it is found that the novel PS barrier contributes to room-temperature MR more significantly than that at 77K. Temperature dependence of resistance is good agreement with -T^-1/4 in the temperature range from 77 to 298K.     

Superconductivity in Topological Semimetal θ-TaN at High Pressure

Recently,θ-TaN was proposed to be a topological semimetal with a new type of triply degenerate nodal points.Here,we report studies of pressure dependence of transport,Raman spectroscopy and synchrotron x-ray diffraction on θ-TaN up to 61 GPa.We find that θ-TaN becomes superconductive above 24.6 GPa with T_c at 3.1 K.The θ-TaN is of n-type carrier nature with carrier density about 1.1 × 10~(20)/cm~3 at 1.2 GPa and 20 K, while the carrier density increases with the pressure and saturates at about 40 GPa in the measured range.However,there is no crystal structure transition with pressure up to 39 GPa,suggesting the topological nature of the pressure induced superconductivity.     

High pressure effects on the luminescent properties and crystal structure of magnesium 8—hydroxyquinoline complex

The fluorescence emission and X-ray diffraction of magenesium 8-hydroxyquinoline complex(Mgq2) have been measured at high pressure up to 14 GPa.It has been found that pressure can influence the emission dramatically.At relative lower pressure(less than 2.5GPa) the fluorescence of Mgq2 changes slightly,but the emission drops quickly with increase of the pressure when the pressure gets higher than 2.5GPa.The results of in situ energy dispersive X-ray diffraction at high pressure with synchrotron radiation indicate that there is a phase transition at about 2.5-3GPa for Mgq2 crystal.2001 Elsevier Science B.V.All rights reserved.     

Unusual softening behavior of yield strength in niobium at high pressures

In situ synchrotron angle-dispersive x-ray diffraction experiments on niobium powders have been conducted at pressures up to 61 GPa and room temperature using the diamond anvil cell technique. From the full width at half maximum of the measured diffraction lines, the yield strength was derived with the line-width analysis theory. The niobium powder sample was found to be compressed more packed firstly and then yielded at~14 GPa–18 GPa. Following an initial increase in the yield strength with pressure, an obvious decrease was observed occurring at ~42 GPa–47 GPa accompanying with a typical pressure dependence above 47 GPa. The experimentally observed anomalous softening of the yield strength in niobium surprisingly follows the trend of the predicted unusual softening in the shear modulus by the recent theoretical investigations. The possible mechanisms, applicable to interpret the yield strength softening of materials at high pressure,were also discussed in detail.     

Polycrystalline cubic boron nitride prepared with cubic-hexagonal boron nitride under high pressure and high temperature

Polycrystalline cubic boron nitride(Pc BN) compacts, using the mixture of submicron cubic boron nitride(c BN) powder and hexagonal BN(h BN) powder as starting materials, were sintered at pressures of 6.5–10.0 GPa and temperature of1750℃ without additives. In this paper, the sintering behavior and mechanical properties of samples were investigated.The XRD patterns of samples reveal that single cubic phase was observed when the sintering pressure exceeded 7.5 GPa and h BN contents ranged from 20 vol.% to 24 vol.%, which is ascribed to like-internal pressure generated at grain-to-grain contact under high pressure. Transmission electron microscopy(TEM) analysis shows that after high pressure and high temperature(HPHT) treatments, the submicron c BN grains abounded with high-density nanotwins and stacking faults, and this contributed to the outstanding mechanical properties of Pc BN. The pure bulk Pc BN that was obtained at 7.7 GPa/1750℃ possessed the outstanding properties, including a high Vickers hardness(～ 61.5 GPa), thermal stability(～ 1290℃ in air),and high density(～ 3.46 g/cm~3).     

Growth and Characterization of a Kind of Nitrogen-Rich Niobium Nitride for Bolometer Applications at Terahertz Frequencies

Niobium is sputtered onto a single crystalline silicon substrate in N2：Ar=4：1 gas mixture at the total pressure of 2 Pa. The temperature coefficient of resistance of the sample is about 0.5% at 30OK, and up to 7% at 77K, indicating the possibility of using it to make room-temperature bolometers with performances better than those based on Pt, Bi, or Nb. For a 60-nm-thick sample, the rms surface roughness is 0.45nm over an area of 2 μm × 2 μm. Analyses based on x-ray diffraction and x-ray photoelectronic spectroscopy indicate that the samples are Nb5N6 thin films in which there is a combination of Nb^3＋ and Nb^5＋, or Nb^4＋.     

Influence of Pressure on the Annealing Process of β-Ca_2SiO_4(C_2S) in Portland Cement

Portland cement is the most common type of cement in general use around the world as a basic ingredient of concrete, mortar, stucco, and non-speciality grout. Dicalcium silicate(Ca_2SiO_4) is the primary constituent of a number of different types of cement. The β-Ca_2SiO_4 phase is metastable at room temperature and will transform into γ-Ca_2SiO_4 at 663 K. In this work, Portland cement is annealed at a temperature of 950 K under pressures in the range of 0–5.5 GPa. The high pressure experiments are carried out in an apparatus with six anvil tops. The effect of high pressure on the obtaining nano-size β-Ca_2SiO_4(C_2 S) process is investigated by x-ray diffraction and transmission electron microscopy. Experimental results show that the grain size of the C_2 S decreases with the increase of pressure. The volume fraction of the C_2 S phase increases with the pressure as the pressure is below3 GPa, and then decreases(P 3 GPa). The nano-effect is very important to the stabilization of β-Ca_2SiO_4. The mechanism for the effects of the high pressure on the annealing process of the Portland cement is also discussed.     

Structural stability and electrical properties of AlB2-type MnB2 under high pressure

The structural stability and electrical properties of AlB2-type MnB2 were studied based on high pressure angledispersive x-ray diffraction, in situ electrical resistivity measured in a diamond anvil cell(DAC) and first-principles calculations under high pressure. The x-ray diffraction results show that the structure of AlB2-type MnB2 remains stable up to 42.6 GPa. From the equation of state of MnB2, we obtained a bulk modulus value of 169.9±3.7 GPa with a fixed pressure derivative of 4, which indicates that AlB2-type MnB2 is a hard and incompressible material. The electrical resistance undergoes a transition at about 19.3 GPa, which can be explained by a transition of manganese 3d electrons from localization to delocalization under high pressure.     

Synchrotron small angle X-ray scattering study on the conformation of polystyrene in compressed CO<Subscript>2</Subscript>-toluene mixture

Synchrotron small angle X-ray scattering (SAXS) was performed to investigate the effect of dissolved CO₂ in toluene on the conformation of polystyrene (PS) in the solution. It has been found that the second virial coefficientA ₂ and the radius of gyrationR _g decrease with the increasing antisolvent CO₂ pressure. The scattering intensity of PS chain followedI(h) ∞h ^−α under different antisolvent pressures (0, 0.6, 1.5, 2.4, 3.3, and 4.2 MPa), suggesting that the PS chain has self-similar structure behavior or a fractal structure in the presence of antisolvent CO₂. All this reveals a large effect of antisolvent pressure or the solubility of CO₂ in the solution on PS structure. The fractal dimensions increase with the increasing antisolvent pressure, indicating that the polymer chain changes from a swollen coil into a rather dense globule in the course of adding antisolvent CO₂.     

Equation of state and structural transition at high hydrostatic pressures in the BiFeO<Subscript>3</Subscript> crystal

Change in the crystal structure of the BiFeO₃ multiferroic at high pressures up to 70 GPa in a diamond anvil cell has been studied by the method of synchrotron x-ray diffraction at room temperature. The experiment has been carried out under hydrostatic conditions with helium as a pressure-transferring medium. An anomaly has been observed in the behavior of the structural parameters at pressures P _c ≈ 40?50 GPa. This anomaly correlates with the effect of the magnetic collapse of iron moments revealed in this pressure range. It has been found that the bulk compression modulus is equal to B ₀ = (75.5 ± 15.5) GPa in the interval 0 < P < P _c and is almost quadrupled to a value of B = (292 ± 9) GPa in the interval P > P _c. When the pressure decreases, the behavior of the structural parameters is completely reversible in correlation with the reversibility of the magnetic transition. The “diffuseness” of the structural transition in pressure is explained by thermal fluctuations between the high-and low-spin states of Fe³⁺ ions in the transition region.     

Effect of pressure on the superconducting transition in Bi-Sr-Ca-Cu-O system

Abstract

The effect of pressure on T_c was studied on 110 K class Bi-Sr-Ca-Cu-O (1:1:1:2) compounds. T_c was varied with current in I^3/2 , and defined at the value extrapolated to zero current. dT_c /dP = + 0.18 K/kbar was obtained up to 10.9 kbars.     

Adsorption of CO2 on PbO at ambient temperature

The adsorption of CO₂ on metal oxides at ambient temperature received less study largely due to the small adsorption amount. However, the adsorption is of interest in refreshing the atmosphere of isolated spaces. It was shown in the present work that P_bO was sensitive to low concentration CO₂ in the presence of water. An XPS examination indicated that P_bO changed to P_bCO₃ after the adsorption of CO₂; therefore, the adsorption is chemical in nature. In order to enlarge the CO₂ capacity, P_bO was dispersed on the surface of a silica gel with large surface area (710 m²/g). Both CO₂ capacity and adsorption rate indicated that the optimal dispersion manner of P_bO is the mono-molecular layer surface coverage. Breakthrough experiments showed that the prepared adsorbent could effectively capture low-concentration CO₂ at ambient temperature and pressure yielding a CO₂ capacity of 59.1 mg g⁻¹. The saturated adsorbent was regenerated on heating at 380 °C and the CO₂ capability was recovered.     

Effect of pressure and magnetic field on bilayer La1.25Sr1.75Mn2O7 single crystal

We report the temperature dependence of susceptibility for various pressures, magnetic fields and constant magnetic field of 5 T with various pressures on La_2−2xSr_1+2xMn₂O₇ single crystal to understand the effectiveness of pressure and magnetic field in altering the magnetic properties. We find that the Curie temperature, T_c, increases under pressure (dT_c/dP=10.9 K/GPa) and it indicates the enhancement of ferromagnetic phase under pressure up to 2 GPa. The magnetic field dependence of T_c is about 26 K for 3 T. The combined effect of pressure and constant magnetic field (5 T) shows dT_c/dP=11.3 K/GPa and the peak structure is suppressed and broadened. The application of magnetic field of 5 T realizes 3D spin ordered state below T_c at atmospheric pressure. Both peak structure in χ_c and 3D spin ordered state are suppressed, and changes to 2D-like spin ordered state by increase of pressure. These results reveal that the pressure and the magnetic field are more competitive in altering the magnetic properties of bilayer manganite La_1.25Sr_1.75Mn₂O₇ single crystal.     

The decomposition of formic acid on Ni(100)

The decomposition of HCOOD was studied on Ni(100). Low temperature adsorption of HCOOD resulted in the desorption of D₂O, CO₂, CO, and H₂. The D₂O was evolved below room temperature. CO₂ and H₂ were evolved in coincident peaks at a temperature above that at which h₂ desorbed following H₂ adsorption and well above that for CO₂ desorption from CO₂ adsorption; CO desorbed primarily in a desorption limited step. The decomposition of formic acid on the clean surface was found to yield equal amounts of H₂, CO, and CO₂ within experimental error. The kinetics and mechanism of the decomposition of formic acid on Ni (110) and Ni(100) single crystal surfaces were compared. The reaction proceeded by the dehydration of formic acid to formic anhydride on both surfaces. The anhydride intermediate condensed into islands due to attractive dipole-dipole interactions. Within the islands the rate of the decomposition reaction to form CO₂ was given by:

$\text{Rate = 6 × 10}{}^{15}\text{exp{?[25,500 + ω(}\text{c}\text{c}{}_{\mathrm{sat}}\text{)]/RT} × c}$

, where c is the local surface concentration, c_sat is the saturation coverage for the particular crystal plane, and ω is the interaction potential. The interaction potential was determined to be 2.7 kcal/mole on Ni(110) and 1.4 kcal/mole on Ni(100); the difference observed was due to structural differences of the surfaces relating to the alignment of the dipole moments within the islands. These attractive interactions resulted in an autocatalytic reaction on Ni(110), whereas the interaction was not strong enough on Ni(100) to sustain the autocatalytic behavior. Formic acid decomposition oxidized the Ni(100) surface resulting in the formation of a stable surface oxide. The buildup of the oxide resulted in a change in the selectivity reducing the amount of CO formed. This trend indicated that on the oxide surface the decomposition proceeded via a formate intermediate as on Ni(110) O.     

Magnetic and structural properties of Y2Fe15·3Si1·7 alloy under high pressure

Abstract

The pressure dependence of the crystal structure of a powder sample of Y₂Fe_15·3Si_1·7 was studied in the pressure range from 0 to 2 GPa, using the D-2 diffractometer with hydrostatic liquid pressure cell at the IVV-2M reactor (Ekaterinburg) and DN-12 time-of-flight diffractometer with a sapphire anvil cell at the IBR-2 pulsed reactor (Dubna). Also the pressure dependence of the Curie temperature T_c (P) of the alloy was studied. The correlation between the decreases of both T_c and Fe-Fe interatomic distances in “dumbbell” site 4f under pressure was obtained.     

Effect of hydrostatic and chemical pressure on BaF2 and BaF2: Eu2+ crystals

The effect of hydrostatic pressure on a BaF₂ crystal was studied within the shell model in the pair-wise potential approximation. The structural phase transition from the cubic to orthorhombic phase was simulated. The behavior of the unit-cell parameters of the α-and β-BaF₂ phases under hydrostatic pressure (from 0 to 12 GPa) was investigated. The fundamental vibration frequencies of BaF₂ under hydrostatic pressure (0–3.5 GPa) were calculated for both phases. The effect of chemical pressure on the BaF₂ crystal was studied by simulating Ba_1?x Me_xF₂ mixed crystals (Me=Ca, Sr). It was shown that at impurity concentrations up to 15–20 at. % the lattice constant varies in the same way as it does when hydrostatic pressure increases to P _c , which corresponds to a phase transition to the orthorhombic phase. The effect of chemical and hydrostatic pressure on BaF₂: Eu²⁺ doped crystals was also studied. The dependence of the absorption and luminescence zero-phonon line shift on the Eu²⁺-ligand distance was calculated.     

The kinetics and mechanism of the autocatalytic decomposition of HCOOH on clean Ni(110)

The flash decomposition of DCOOH was studied on a clean nickel (110) surface following adsorption at 37°C. The reaction proceeded by a two-dimensional autocatalytic mechanism to form D₂, CO₂ and CO products. The results indicated DCOOH adsorbed dissociatively at 37°C by splitting off H₂O and forming an adsorbed molecule composed of DCO and DCOO. Above ten percent of saturation coverage these molecules formed a condensed phase or island structure. The decomposition of the molecules was rate determining for the formation of CO₂ and D₂ products. Theoretical calculations for branched chain mechanisms and coadsorption experiments with CO and H₂ separately with DCOOH indicated the intermediate involved in the explosion was not associated with the observed product molecules. The intermediate in the explosive decomposition was shown by interrupted flashes to be stable at 37°C. The autocatalytic flash decomposition curves were explained by reaction occurring at bare metal sites within the islands, and as product molecules desorbed the number of sites increased, causing the rate to accelerate. The rate of decomposition was well described by the $\text{equation Rate = ?k(}\text{c}\text{c}{}_{\mathrm{I}}\text{)(c}{}_{\mathrm{I}}\text{?c + fc}{}_{\mathrm{I}}\text{)}$, where c is the surface concentration, c_I is the initial surface concentration, and f is the density of initiation sites. The activation energy of 26.6kcal/mol was determined from heating rate variation. The narrow flash curves were fit with a first order pre-exponential factor of 1.6 × 10¹⁵ sec^?1 with a density of initiation sites of 0.004.     

X-ray preionized CO2 laser

A short pulse (100 ns) high-energy x-ray source has been used to preionize a transversely excited carbon dioxide gas discharge laser of 600 cm³ active volume. The maximum output power of 60 MW in a 50 ns FWHM pulse was achieved from a CO₂–N₂–He–CO–Xe static gas mixture at 600 Torr pressure. The energy conversion efficiency was 6%.