Ultra-fine grained Nd–Fe–B by high pressure reactive milling and desorption

This paper reports on the grain refinement in dynamic hydrogenation disproportionation desorption and recombination (d-HDDR) processed Nd-rich Nd₂Fe₁₄B and stoichiometric Nd₂Fe₁₄B powders using high pressure reactive milling (HPRM) followed by a subsequent desorption and recombination. In contrast to the dynamic-HDDR processed anisotropic powder with a grain size of the Nd₂Fe₁₄B phase of 300 nm, the new approach yields a further reduction of the Nd₂Fe₁₄B₁ grain size to less than 70 nm. Nd-rich Nd₂Fe₁₄B powder produced by HPRM and subsequent desorption exhibits a coercivity μ_0iH_c=1.35 T and a remanence of 0.80 T. In the stoichiometric material, the reduction of the Nd-content leads to an increase in remanence to 0.85 T. Additionally, it is demonstrated that highly anisotropic powders can also be obtained by dynamic-HDDR processing of stoichiometric Nd₂Fe₁₄B powders.     

Remaining of ϵ-iron structure at atmospheric pressure and superlattice formation by shearing at high pressure

Transmission X-ray diffraction pattern of iron sheared at high pressure show rings whose interplanar spacings correspond to those of ?-iron and their integral multiple, in spite of the fact that it has been kept at atmospheric pressure for ～3 months from the shearing. This and other related phenomena suggest that the pattern corresponds to the remains of the ?-iron structure in which superlattice formed. The volume of the specimen at atmospheric pressure after elapsing ～3 months at atmospheric pressure from the shearing was 86% of that before the shearing.     

Structural and electrical properties of Ga–Te systems under high pressure

First-principles evolutionary calculation was performed to search for all probable stable Ga–Te compounds at extreme pressure. In addition to the well-known structures of P6_3/mmc and Fm-3 m Ga Te and I4/m Ga_2 Te_5, several new structures were uncovered at high pressure, namely, orthorhombic I4/mmm GaTe_2 and monoclinic C2/m Ga Te_3, and all the Ga–Te structures stabilize up to a maximum pressure of 80 GPa. The calculation of the electronic energy band indicated that the high-pressure phases of the Ga–Te system are metallic, whereas the low-pressure phases are semiconductors. The electronic localization functions(ELFs) of the Ga–Te system were also calculated to explore the bond characteristics. The results showed that a covalent bond is formed at low pressure, however, this bond disappears at high pressure, and an ionic bond is formed at extreme pressure.     

Ceramic synthesis of 0.08BiGaO_3–0.90BaTiO_3–0.02LiNbO_3 under high pressure and high temperature

In this paper, the preparation of 0.08BiGaO_3–0.90BaTiO_3–0.02LiNbO_3 is investigated at pressure 3.8 GPa and temperature 1100–1200?C. Experimental results indicate that not only is the sintered rate more effective, but also the sintered temperature is lower under high pressure and high temperature than those of under normal pressure. It is thought that the adscititious pressure plays the key role in this process, which is discussed in detail. The composition and the structure of the as-prepared samples are recorded by XRD patterns. The result shows that the phases of Ba TiO_3, BaBiO_(2.77), and Ba_2Bi_4Ti_5O_(18) with piezoelectric ceramic performance generate in the sintered samples. Furthermore, the surface morphology characteristics of the typical samples are also investigated using a scanning electron microscope. It indicates that the grain size and surface structure of the samples are closely related to the sintering temperature and sintering time. It is hoped that this study can provide a new train of thought for the preparation of lead-free piezoelectric ceramics with excellent performance.     

Fracture toughness evaluation of WC–10 wt% Co hardmetal sintered under high pressure and high temperature

This work focused on fracture toughness studies of WC–10?wt% Co hardmetal fabricated through the high pressure/high-temperature technique. A powder mixture of WC–10?wt% Co was sintered at 1500–1900°C under a pressure of 7.7?GPa for 2 and 3?min. Vickers hardness test at two different loads of 15 and 30?kgf was done and fracture toughness of the sintered bodies was measured using the indentation method to obtain the effect of sintering parameters. Structural analyses were also performed via X-ray diffraction to investigate structure-related properties. Full density was achieved for high sintering temperature along with abnormal grain growth that reduced hardness. High hardness was observed ranging from 1200 to 1670?HV and fracture toughness increased with increasing sintering temperature up to the highest value of 17.85?MPa/m^1/2.     

XPS study of CeTbO3+δ synthesized by high pressure and temperature method

The samples of CeTbO₃₊ synthesized by high pressure and high temperature method were studied by XPS. It was found that Tb⁴⁺ ion began to transform to Tb³⁺ at about 600° C and Ce⁴⁺ to Ce³⁺ about 800° C. Single phase compound of CeTbO₃₊ having fluorite structure was formed at 1000° C, and in the compound the Ce ions had been in mixed valence state. Existence of Ce³⁺ ions in compounds could be detected with the shift of the 888 eV peak and the change of relative intensity of it to the 882 eV peak. The duration stability of CeTbO₃₊ synthesized by high pressure and temperature method was investigated.The project supported by National Natural Science Foundation of China     

Effects of Mg on diamond growth and properties in Fe–C system under high pressure and high temperature condition

Diamond crystal crystallized in Fe–Mg–C system with Archimedes buoyancy as a driving force is established under high pressure and high temperature conditions. The experimental results indicate that the addition of the Mg element results in the nitrogen concentration increasing from 87 ppm to 271 ppm in the diamond structure. The occurrence of the {100}plane reveals that the surface character is remarkably changed due to the addition of Mg. Micro-Raman spectra indicate that the half width of full maximum is in a range of 3.01 cm~(-1)–3.26 cm~(-1), implying an extremely good quality of diamond specimens in crystallization.     

Condensed matter chemistry under ‘extreme’ high pressure–high temperature conditions

Improved techniques for high-pressure experiments have led to new studies of the structure and physical properties of materials compressed to extremely high densities. Now we must fully enable the field of condensed matter chemistry under extreme high-pressure conditions. This will require development of strategies for the analysis and control of the chemical composition during reactions between solid, liquid and fluid phases. Such approaches already exist within the fields of experimental geochemistry and petrology, and they can be readily adapted to the wider area of chemistry. The first consideration is the manipulation and determination of stable and metastable pressure–temperature phase diagrams, illustrated here for the one-component system Si. Next, relationships between P, T and the chemical composition, X, expressed in terms of the chemical potential (μ) or the activity–composition relations, can be used to constrain and determine components within the system. This is illustrated by examples drawn from our recent work on high-pressure syntheses of boron suboxides (B₆O_1???δ) and (Si, Ge)₃N₄ nitride spinels.     

Synchrotron x-ray-diffraction study of α-cristobalite at high pressure and high temperature

Abstract

Energy-dispersive x-ray diffraction using synchrotron radiation was carried out on α-cristobalite to 3 GPa and 350°C in a cubic anvil press. A cascading structural phase transition occurred beyond 0.61 GPa at room temperature. The transition was accompanied by a splitting of most of the a-cristobalite reflections: the (111) reflection at 0.61 GPa through the (211) reflections at 2.13 GPa, with many other lines between. The pressure of this transition decreased with increasing temperature.     

Size reduction of “reformed casein micelles” by high-power ultrasound and high hydrostatic pressure

We investigated the effect of ultrasound (US) and high hydrostatic pressure (HHP) on the size of reformed casein micelles (RMCs) obtained by titrating calcium and phosphorous solution into sodium caseinate solutions. Both US and HHP reduced the size of the RMCs. A decrease in size from ~200 nm to ~170 nm when US (20 kHz, 0.46 W/mL) was applied for 30 min; and down to ~85 nm when HHP was applied 500 MPa for 15 min. Electron microscopic analysis showed that the RMCs before and after US are similar to milk native casein micelles, and that HHP extensively disintegrated the RMCs. Small angle X-ray scattering and SDS-PAGE showed that the internal structure of the RMCs as well as the casein molecules are not affected by the US and HHP treatments.     

Semiconductor–metal transition in GaAs nanowires under high pressure

We investigate the structural phase transitions and electronic properties of GaAs nanowires under high pressure by using synchrotron x-ray diffraction and infrared reflectance spectroscopy methods up to 26.2 GPa at room temperature.The zinc-blende to orthorhombic phase transition was observed at around 20.0 GPa.In the same pressure range, pressureinduced metallization of GaAs nanowires was confirmed by infrared reflectance spectra.The metallization originates from the zinc-blende to orthorhombic phase transition.Decompression results demonstrated that the phase transition from zincblende to orthorhombic and the pressure-induced metallization are reversible.Compared to bulk materials, GaAs nanowires show larger bulk modulus and enhanced transition pressure due to the size effects and high surface energy.     

Thermoelastic parameter αKT of sodium chloride at high pressure and high temperature

Two different potential models to the molecular dynamics (MD) simulations have been applied to investigate the thermoelastic parameter αK_T of sodium chloride (NaCl) under high pressure and high temperature. The first one is the shell model (SM) potential that due to the short-range interaction when pairs of ions are moved together as is the case in that polarization of a crystal due to the motion of the positive and negative ions, and the second one is the two-body rigid-ion Born–Mayer–Huggins–Fumi–Tosi (BMHFT) potential with full treatment of long-range Coulomb forces. Particular attention is paid to the comparison of the SM- and BMHFT-MD simulations with the Debye model for the first time, and this model combines with ab initio calculations within local density approximation (LDA) and generalized gradient approximation (GGA) using ultrasoft pseudopotentials and a plane-wave basis in the framework of density functional theory (DFT), and it takes into account the phononic effects within the quasi-harmonic approximation. Note that the MD calculated volumes using SM model is somewhat larger than both the DFT and experimental volumes despite not considering the temperature effect. Compared with SM potential, the MD simulated 300 K isotherm of NaCl with BMHFT potential is very successful in reproducing accurately the measured volumes and the GGA calculated volumes. Generally, it is found that there exist minor differences between the LDA and GGA computed the thermoelastic parameter αK_T of NaCl, with both average results giving good agreement with SM-MD simulations. At an extended pressure and temperature ranges, the variation of thermoelastic parameter αK_T which play a central role in the formulation of approximate equations of state has also been predicted. The properties of NaCl are summarized in the pressure range of 0–300 kbar and the temperature up to 2000 K.     

Formation and properties of rocksalt-type AlN and implications for high pressure phase relations in the system Si–Al–O–N

Pressure-dependent thermodynamic properties of the ambient and high pressure phases of aluminum nitride (w-AlN and rs-AlN) were calculated from first principles in order to determine their phase boundary in the p? T phase diagram. These predictions were checked by static HP/HT experiments, using a multianvil press and an Al/N/H precursor with low decomposition temperature as educt. The experimental data show that at temperatures between 1000 and 2000 K, the boundary line between the two phases is situated between 11 and 12 GPa, which is ～1.3 GPa lower than the theoretical result and generally lower than previously assumed. The hardness of rs-AlN – measured for the first time – is ～30 GPa (Knoop indenter at loads of 25–50 g), twice as hard as w-AlN. Shock wave recovery experiments on nano w-AlN allowed testing of the chemical and thermal stability of rs-AlN, and determination of its infrared absorption and ²⁷Al NMR data. The shock wave technique will eventually enable the synthesis of larger amounts of rs-AlN, making it available for technological use. Finally, implications on the high pressure stability of phases in the Si–Al–O–N system are discussed in the light of thermoelastic properties of AlN.     

Crystal structure of the high pressure phases of bismuth bi iii and bi iii′ by high energy synchrotron x-ray diffraction

Abstract

This paper reports the results of a synchrotron X-ray diffraction study on the crystal structures of Bi 111 and Bi 111′ which have been known to form under high pressure but have, for a long time, been unsolved. Powdered samples were compressed in a cubic-type multi-anvil press, MAXID, and diffraction data were collected using an Imaging Plate with monochromatized radiation of an energy of 49.7 keV. It was possible to identify at 3.8 GPa forty-eight reflections for Bi I11 in the sin θ / δ range from 1.6 nm^?1 to 5.6 nm^?1, which were indexed in terms of a tetragonal unit cell with a=0.8659 nm and c═ O·4238 nm (2=10). Analysis based on the observed intensities of the reflections led to a structure in which atoms form a distorted body-centered cubic lattice. It is of the same type as the structure of the high pressure phase of antimony Sb 11. When pressure was increased across the suggested transition pressure 4.3 GPa between Bi III and Bi III′ to 6.6 GPa, no change in the diffraction pattern was observed, indicating that there is no distinction between the two phases as long as the crystal structure is concerned. Discussion is given on the sequence of high pressure phase transitions in the Group Vb elements.     

Crystallographic aspects related to the high pressure–high temperature phase transformation of boron nitride

Crystallographic relations between different forms of boron nitride (BN) appearing at the high pressure–high temperature structural phase transformation have been revealed by high-resolution transmission electron microscopy (HRTEM). As starting materials, crystalline hexagonal BN (hBN) with different degrees of crystallinity, or with defects intentionally introduced, were used. Cubic BN (cBN) is formed only as a minor component, the rest consisting of different forms of sp ² bonded BN: hBN, compressed, monoclinic deformed hBN, or turbostratic BN (tBN). The small cBN crystallites (300–400?nm) contain many defects such as twins, stacking faults and nanoinclusions of other BN forms: tBN, rhombohedral BN (rBN) and wurtzite BN (wBN). The cBN phase grows epitaxially on the basal plane of hBN. The nucleation sites for cBN are revealed by HRTEM. They consist of nanoarches (sp ³ hybridized, highly curved nanostructures), frequently observed at the edges of the hBN crystallites in the starting materials. Based on HRTEM observations of specimens not fully transformed, a nucleation and growth model for cBN is proposed which is consistent with existing theoretical and experimental models.     

Superconductivity at 50 K in a mixed-phase Ca–P–O compound system treated by shock-wave pressure up to 65 GPa

Shock-wave pressure treatment up to 65 GPa has been applied to samples representing powdered mixtures of calcium and calcium phosphate in 1:1 volume ratio. Magnetometric measurements have revealed superconductivity of the samples at 50 K. By means of X-ray powder diffraction and magnetometric measurements, it has been found that superconductivity observed in the samples corresponds to instability at ambient pressure and room temperature of the phase/s formed in the samples during their shock-wave pressure treatment.     

Structural and electronic properties of YH 3 at high pressure – band calculation by the GW approximation

Using the GW calculation for one particle energy of electrons, we studied the pressure dependence of the band gaps in YH ₃ for controversial structures reported in experimental and theoretical studies. For some types of band structures, perturbational treatment taking only diagonal matrix elements of the self-energy into account, which is the most commonly used method in the GW calculation, fails to give band gaps. In those cases, calculations in which the non-diagonal matrix elements of the self-energy are taken into account are needed to get the band gaps. In the fcc-YH ₃, band gap disappears around 5 GPa which is much lower pressure than those reported in experimental studies for the metallization in YH ₃. The band gap by the GW calculation in the C2/m structure, which is theoretically predicted to be most probable up to around 40 GPa, survives to much higher pressures than those predicted by the generalized gradient approximation (GGA), and probably to over 60 GPa. The very recent report of metallization pressure around 70 GPa on the YH ₃ metallization by means of DC conductivity measurements suggests that some structures other than the C 2/m should appear as an intermediate structure before the fcc-YH ₃ will appear by the pressurization.     

Melting and Grüneisen parameters of NaCl at high pressure

The Buckingham potential has been employed to simulate the melting and thermodynamic parameters of sodium chloride (NaCl) using the molecular dynamics (MD) method. The constant-volume heat capacity and Grüneisen parameters have been obtained in a wide range of temperatures. The calculated thermodynamic parameters are found to be in good agreement with the available experimental data. The NaCl melting simulations appear to validate the interpretation of superheating of the solid in the one-phase MD simulations. The melting curve of NaCl is compared with the experiments and other calculations at pressure 0－30GPa range.