Equation of state of silicon nitride carbodiimide Si2CN4

The lattice parameters of silicon nitride carbodiimide Si₂CN₄ have been measured up to 8 GPa at room temperature using energy-dispersive X-ray powder diffraction with synchrotron radiation. A fit of the experimental p-V data to the Birch-Murnaghan equation of state yields the values of the bulk modulus of 8.8(2) GPa and its first pressure derivative of 3.4(1). The compression is found to be anisotropic, with the b-axis being significantly more compressible than the a-and c-axes.     

Variations of lattice constants and thermal expansion coefficients of indium at high pressure and high temperature

ABSTRACT

The effects of pressure and temperature on the lattice constants and thermal expansion coefficients of Indium were studied up to 18.6?GPa and 506?K based on in situ X-ray diffraction method with an externally heated diamond anvil cell. The results show that the measured axial ratio (c/a) decreases with increasing temperature and its temperature dependence decreases with increasing pressure. The thermal expansion coefficient of the a-axis decreases with increasing pressure up to 7?GPa and remains almost constant above 7?GPa, whereas that of the c-axis increases monotonously with pressure and changes from negative to positive at around 7?GPa. The observed behavior suggests that temperature reduces the tetragonal distortion on the lattice, and its effect is dominant below 7?GPa; in contrast, pressure enhances lattice distortion, and tends to have a stronger effect above 7?GPa.     

High pressure X-ray diffraction study of Fe2B

We report the results of a synchrotron based X-ray diffraction study of bct-Fe₂B under quasi-hydrostatic conditions from 0 to 50 GPa. Over this pressure range, no phase change or disproportionation has been observed. A weighted fit of the data to the Birch-Murnaghan equation of state yields a value of the bulk modulus, K, of 164±14 GPa and the first pressure derivative of the bulk modulus, K′, of 4.4±0.5. The compression is found to be anisotropic, with the a-axis being more incompressible than the c-axis.     

Equation of state of aluminum carbide Al4C3

Quasi-hydrostatic compression of aluminum carbide, Al₄C₃ has been studied to 6 GPa at room temperature using energy-dispersive X-ray powder diffraction with synchrotron radiation. A fit of the experimental p-V data to the Birch equation of state yields the values of the bulk modulus, B₀, of 130(5) GPa and the first pressure derivative of the bulk modulus, B′₀, of 4.6(9). The compression is found to be anisotropic, with the a-axis being more compressible than the c-axis.     

Gigantic uniaxial pressure effect in single crystals of iron-based superconductors

In order to elucidate the anisotropic pressure effect on superconductivity in an iron-based superconductor, magnetization measurements have been performed in Ba(Fe_0.92Co_0.08)₂As₂ single crystals under uniaxial pressures applied along the c-axis. Gigantic T_c suppression, dT_c/dP_//c = −15 K/GPa, was observed when the anisotropic deformation with the a-expansion and c-compression was induced by the c-pressure, which should be compared with dT_c/dP < +1 K/GPa in the isotropic pressure case. This suggests that the a-axis (c-axis) compression has a positive (negative) contribution to T_c.     

Prediction study of structural and elastic properties under pressure effect of M2SnC (M=Ti, Zr, Nb, Hf)

Using first-principles calculations, we have studied the structural and elastic properties of M₂SnC, with M=Ti, Zr, Nb and Hf. Geometrical optimization of the unit cell is in good agreement with the available experimental data. The effect of high pressures, up to 20 GPa, on the lattice constants shows that the contractions along the a-axis were higher than those along the c-axis. We have observed a quadratic dependence of the lattice parameters versus the applied pressure. The elastic constants and their pressure dependence are calculated using the static finite strain technique. A linear dependence of the elastic stiffnesses on the pressure is found. We derived the bulk and shear moduli, Young's moduli and Poisson's ratio for ideal polycrystalline M₂SnC aggregates. We estimated the Debye temperature of M₂SnC from the average sound velocity. This is the first quantitative theoretical prediction of the elastic properties of Ti₂SnC, Zr₂SnC, Nb₂SnC, and Hf₂SnC compounds.     

Pressure dependence of electronic structure and magnetic properties in Fe16N2

The electronic structures and magnetic properties of Fe₁₆N₂ system and their pressure dependence were investigated by using first-principles calculations based on the density functional theory. It has been found that the total magnetic moment in Fe₁₆N₂ system decreases monotonically as increasing pressure from 0 to 14.6 GPa. A phase transition from ferromagnetic (FM) to non-magnetic (NM) occurs with a volume collapse of around 0.008  at 14.6 GPa, The lattice constants a and c for magnetic results decrease monotonically as pressure increasing from 0 to 14.6 GPa, at 14.6 GPa, the lattice constant a decreases sharply, on the contrary, the lattice constant c increases abruptly. We think that the change of microscopic structure of Fe₁₆N₂ is responsible for the phase transition from FM to NM.     

Theoretical study of the structural, elastic, electronic and thermal properties of the MAX phase Nb2SiC

Structural, elastic, electronic and thermal properties of the MAX phase Nb₂SiC are studied by means of a pseudo-potential plane-wave method based on the density functional theory. The optimized zero pressure geometrical parameters are in good agreement with the available theoretical data. The effect of high pressure, up to 40 GPa, on the lattice constants shows that the contractions along the c-axis were higher than those along the a-axis. The elastic constants C_ij and elastic wave velocities are calculated for monocrystal Nb₂SiC. Numerical estimations of the bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio, average sound velocity and Debye temperature for ideal polycrystalline Nb₂SiC aggregates are performed in the framework of the Voigt-Reuss-Hill approximation. The band structure shows that Nb₂SiC is an electrical conductor. The analysis of the atomic site projected densities and the charge density distribution shows that the bonding is of covalent-ionic nature with the presence of metallic character. The density of states at Fermi level is dictated by the niobium d states; Si element has a little effect. Thermal effects on some macroscopic properties of Nb₂SiC are predicted using the quasi-harmonic Debye model, in which the lattice vibrations are taken into account. The variations of the primitive cell volume, volume expansion coefficient, bulk modulus, heat capacity and Debye temperature with pressure and temperature in the ranges of 0-40 GPa and 0-2000 K are obtained successfully.     

High pressure X-ray diffraction study on icosahedral boron arsenide (B12As2)

The high pressure properties of icosahedral boron arsenide (B₁₂As₂) were studied by in situ X-ray diffraction measurements at pressures up to 25.5 GPa at room temperature. B₁₂As₂ retains its rhombohedral structure; no phase transition was observed in the pressure range. The bulk modulus was determined to be 216 GPa with the pressure derivative 2.2. Anisotropy was observed in the compressibility of B₁₂As₂—c-axis was 16.2% more compressible than a-axis. The boron icosahedron plays a dominant role in the compressibility of boron-rich compounds.     

High pressure X-ray diffraction study on BaWO4-II

BaWO₄-II has been synthesized at 5 GPa and 610°C. Its high pressure behavior was studied by in situ synchrotron X-ray diffraction measurements at room temperature up to 17 GPa. BaWO₄-II retains its monoclinic structure. Bulk and axial moduli determined by fitting a third-order Birch–Murnaghan equation of state to lattice parameters are: K ₀=86.2±1.9 GPa, K ₀(a)=56.0±0.9 GPa, K ₀(b)=85.3±2.4 GPa, and K ₀(c)=146.1±3.2 GPa with a fixed K′=4. Analysis of axial compressible modulus shows that the a-axis is 2.61 times more compressible than the c-axis and 1.71 times more compressible than the b-axis. The beta angle decreases smoothly between room pressure and 17 GPa from 93.78° to 90.90°.     

High-pressure phase transition of carbon disulfide

The high-pressure phase transition of CS₂ was studied by combing ab initio molecular dynamics with total energy calculations. At 300 K the pieces of polymer structure were found to appear at 10 GPa in the molecular dynamics run, and further the CS₄ tetrahedral structure to appear at about 20 GPa. The phase transition was then studied in the structure of Cmca, α-quartz and β-quartz by using the first-principle total energy calculation method. A phase transition from Cmca to β-quartz was found at 10.6 GPa. The calculated lattice constants of β-quartz at atmospheric pressure are a=5.44 and c/a=1.138 with B₀=95 GPa. The calculation has also indicated that CS₂ decomposes at 20 GPa and below 1000 K.     

Structural and thermodynamic properties of WB at high pressure and high temperature

The structure parameters and electronic structures of tungsten boride (WB) have been investigated by using the density functional theory (DFT). Our calculating results display the bulk modulus of WB are 352±2 GPa (K′₀=4.29) and 322±3 GPa (K′₀=4.21) by LDA and GGA methods, respectively. We have analyzed the probable reason of the discrepancy from the bulk modulus between theoretical and experimental results. The compression behavior of the unit cell axes is anisotropic, with the c-axis being more compressible than the a-axis. By analyzing the bond lengths information, it also demonstrated that WB has a lower compressibility at high pressure. From the partial densities of states (PDOS) of WB, we found that the Fermi lever is mostly contributed by the d states of W atom and p states of B atom and that the contributions from the s, p states of W atom and s states of B atom are small. Moreover, using the Gibbs 2 program, the thermodynamic properties of WB are obtained in a wide temperature range at high pressure for the first time in this work.     

Mössbauer study of antiferromagnetic CuFeO2

We have studied the magnetic spin structure of antiferromagnetic CuFeO₂ by X-ray diffraction (XRD) and Mössbauer spectroscopy. Its crystal structure determined by XRD analysis was a rhombohedral structure (space group R-3m) and lattice constants a₀ and c₀ were 3.0333 and 17.1595 Å, respectively. In spite of 4-Fe sublattices in a delafossite CuFeO₂, its Mössbauer spectra were analyzed with 1-set (6-Lorentzian lines) below 10 K due to the collinear-commensurate spin structure, but the spectra were fitted with 4-sextet above 10 K due to the incommensurate spin structure. This phenomenon was attributed to the spin–lattice relaxation effect. Magnetic Néel temperature was also determined at 18 K, which corresponded to the high-spin Fe³⁺ valance state. On the other hand, CuFe_0.98Al_0.02O₂ powder with a noncollinear spin structure was fitted with 4-sextet at 4.2 K.     

Synthesis and characterization of CuFeO2+δ delafossite powders

Effects of oxygen off-stoichiometry have been investigated on CuFeO_2+δ delafossite-type powders prepared by solid state reaction. Materials annealed at different temperatures under air atmosphere were compared. Thermogravimetric analysis coupled with X-ray structural analysis showed that a powdered CuFeO₂ can be oxidized up to CuFeO_2+δ with δ = 0.18. Electrical measurements confirm the existence of oxidized CuFeO_2+δ phases. Particular attention is paid to the correlation between oxidation process and phase stabilities in the CuFeO₂ and copper spinel phase system.     

Compression mechanism of GaF3 and FeF3: a high-pressure X-ray diffraction study

The VF₃-type compounds MF₃ with M = Fe and Ga have been studied by high-pressure energy-dispersive X-ray diffraction. The compression mechanism was found to be highly anisotropic for both compounds, with the c-axis showing little pressure dependence. The volume reduction is mainly achieved through coupled rotations of the MF₆ octahedra around the c-axis, which reduces the length of the a-axis. The compression mechanism of both compounds is reasonably well described in terms of deformation of an 8/3/c2 sphere-packing model up to the pressures where the fluorine atoms become hexagonally close-packed. It is proposed that both compounds enter a phase with the fluorine atom arranged in a “super-dense” sphere packing at higher pressures. The zero pressure bulk modulus of FeF₃ and GaF₃ was determined as 12(2) and 37(3) GPa, respectively, and a scaling relation between the zero pressure bulk modulus and unit cell volumes was found for TiF₃, CrF₃, FeF₃ and GaF₃.     

Structure and high-pressure behavior of 2,5-di-(4-aminophenyl)-1,3,4-oxadiazole

The crystalline structures of two modifications of a compound containing the oxadiazole ring, 2,5-di-(4-aminophenyl)-1,3,4-oxadiazole (DAPO) were determined. One of these modifications contains water molecules in the crystal structure, which is observed for the first time for an oxadiazole crystal. Both crystals show an orthorhombic structure. The water free modification, DAPO I, belongs to the space group Pbca (61) and has the lattice parameters: a=13.461(5), b=7.937(3) and c=22.816(8) Å (CCDC 246608). The water containing pseudo-polymorph, DAPO II, has the space group Cmcm (63) and the lattice parameters: a=16.330(5), b=12.307(2) and c=6.9978(14) Å (CCDC 246609). To gain information on the inter molecular interactions within the crystals, X-ray experiments under compression at ambient temperature and under heating at vacuum conditions were performed. Neither DAPO I nor DAPO II undergo phase transitions in the ressure range up to 5 GPa, as could be concluded from X-ray and Raman experiments. X-ray and calorimetric studies indicate that DAPO II dehydrates into DAPO I under increasing temperature. Structural considerations suggest a two-stage process. The compression behavior of both substances is well described by the Murnaghan equation of state (MEOS) and the values of the bulk modulus and its pressure derivative are determined for these crystals. Additionally, in the case of DAPO I, also the thermal expansion coefficient α₀ was measured.     

X-ray diffraction study of molybdenum diselenide to 35.9 GPa

In situ high-pressure angle dispersive synchrotron X-ray diffraction studies of molybdenum diselenide (MoSe₂) were carried out in a diamond-anvil cell to 35.9 GPa. No evidence of a phase transformation was observed in the pressure range. By fitting the pressure-volume data to the third-order Birch-Murnaghan equation of state, the bulk modulus, K_0T, was determined to be 45.7±0.3 GPa with its pressure derivative, K′_0T, being 11.6±0.1. It was found that the c-axis decreased linearly with pressure at a slope of −0.1593 when pressures were lower than 10 GPa. It showed different linear decrease with the slope of a −0.0236 at pressures higher than 10 GPa.     

High pressure X-ray diffraction and electrical resistance study of the quasi-one-dimensional sulfide InV6S8

The ambient structural details and the results of room temperature high pressure angle dispersive X-ray diffraction and electrical resistance measurements on the quasi-one-dimensional sulfide, InV₆S₈, to a pressure of 25 GPa are reported. The material does not undergo a phase transition in this pressure range, though an anomaly in the c/a ratio has been observed around 10 Gpa. A fit of the Murnaghan equation of state to the V/V₀ versus pressure data, with the value of the derivative of B₀ with respect to pressure, B′₀, fixed at 4 has yielded a value of the bulk modulus, B₀, of 110 GPa. We also present data of the pressure dependence of the lattice constants, a and c, the ratio c/a, and the resistance at room temperature.     

Effects of uniaxial pressure and annealing on the resistivity of Ba(Fe1−xCox)2As2

Single crystals of underdoped Ba(Fe_1−xCo_x)₂As₂ were detwinned by applying uniaxial pressure. The anisotropic in-plane resistivity was measured using the Montgomery method without releasing pressure. The resistivity along the a-axis shows metallic behavior down to 5 K, while the resistivity along the b-axis shows an insulator-like behavior in some temperature range. Annealing the sample radically reduces the residual resistivity for x=0, and at the same time the anisotropy becomes much smaller at low temperatures.