High pressure and high temperature generation using small-sized cubic-type multi-anvil apparatus

High pressure and high temperature conditions of 4 GPa and 500°C were generated using a small-sized cubic-type multi-anvil apparatus, which was originally developed for high pressure and low temperature experiments. The drop in pressure was negligible as the temperature was increased from room temperature to 300°C at 4.5 GPa under conditions where the press was clamped. Two-dimensional X-ray diffraction images were successfully obtained from a pure aluminum specimen at 4 GPa and 500°C in the angle-dispersive mode.     

Physical and mechanical properties of C60 under high pressures and high temperatures

The physical and mechanical properties of a C₆₀ fullerene sample have been investigated under high pressure–high temperature conditions using a designer Diamond Anvil Cell. Electrical resistance measurements show evidence of C₆₀ cage collapse at 20 GPa, which leads to the formation of an insulating phase at higher pressure. Energy dispersive X-ray diffraction (EDXD) data indicated that the characteristic fcc reflections gradually decrease in intensity and eventually disappear above 28 GPa. A C₆₀ sample was laser-heated at a pressure of 35 GPa to a temperature of 1910±100 K and, subsequently, decompressed to ambient conditions. The photoluminescence spectra and the Raman spectrum of the pressure–temperature-treated sample were measured at a low temperature of 80 K. Raman peak at 1322.3 cm^?1 with full-width half-maximum of 2.9 cm^?1 was observed from the sample, which is attributed to the hexagonal diamond phase in the sample. The room temperature photoluminescence spectra showed a symmetric emission band centered in the red spectral range with a peak at 690 nm. The structural analysis of the pressure–temperature-processed C₆₀ sample using EDXD method showed strong internal structure orientation and a phase close to hexagonal diamond. Mechanical properties such as hardness and Young’s modulus were measured by nanoindentation technique and the values were found to be 90±7 and 1215±50 GPa, respectively and these values are characteristic of sp³-bonded carbon materials.     

In situ X-ray observation of decomposition of hydrous aluminum silicate AlSiO3OH and aluminum oxide hydroxide d-AlOOH at high pressure and temperature

We clarified the stability limit of phase Egg, AlSiO₃OH, a candidate for water reservoir in the siliceous sediment of slabs in the transition zone conditions by in situ X-ray observation using high energy X-ray from synchrotron radiation source of SPring-8. Phase Egg is stable at least up to 1625 °C at 17 GPa. We observed decomposition of phase Egg into δ-AlOOH and stishovite at pressures greater than 23 GPa at temperatures below 1200 °C. No water release occurs associated with the decomposition. At temperatures above 1200 °C at 23 GPa, we observed decomposition of phase Egg into corundum+stishovite+fluid. We also determined the phase boundary of the decomposition reaction of δ-AlOOH to corumdum+fluid based on the in situ X-ray diffraction at high pressure and temperature.     

Effect of deuterium on phase transformations in fullerenes at high temperatures and high pressures

The effect deuterium has on phase transformations is studied for amorphous and crystalline fullerenes C₆₀ and C₇₀ at high temperatures of up to 1300°C and high pressures (2–8 GPa). Amorphous fullerene phases are obtained via long grinding in a planetary mill. Structure is studied by means of neutron diffraction. In all cases, amorphous graphite (nanographite) forms in the temperature range of 800–1100°C. This material has different diffraction spectra distinguished by the heights of the halos observed on the graphite diffraction maxima and their relative intensities. These spectra (the structure of nanographite) are affected by preliminary amorphization, the number of carbon atoms in the fullerenes (C60 or C70), and the introduction of deuterium atoms. The different spectra of amorphous (disordered) graphite testify to its varying structure.     

The equation of state of triolein up to 1 GPa

In this paper, the compressibility studies of triolein up to 1 GPa at temperature range from 10°C to 50°C have been presented. The discontinuity of V(p) relation, characteristic for the first-order phase transition was observed. At higher temperatures (40°C and above), the time necessary for the phase transition rises considerably. Also the pressure–volume hysteresis due to the phase formation–decomposition cycle was enlarged.     

Pressure evolution of two polymorphs of Tb 2(MoO 4)3

We have studied the high pressure behavior of the α and β^′-phases of Tb ₂(MoO ₄)₃ using a combination of powder X-ray diffraction and ab initio calculations. The α-Tb ₂(MoO ₄)₃ phase did not undergo any structural phase transition in the pressure range from 0 up to the maximum experimental pressure of 21 GPa. We observed line broadening of the diffraction patterns at pressures above 7 GPa, which may be due to non-hydrostatic conditions. The complete amorphization of the sample was not reached in the pressure range studied, as expected from previous Raman studies. The behavior under pressure of the β^′-Tb ₂(MoO ₄)₃ phase is similar to that of other rare-earths trimolybdates with the same structure at room temperature. A phase transition was observed at 2 GPa. The new phase, which can be identified as the δ-phase, has never been completely characterized by diffraction studies. A tentative indexation has been performed and good refined cell parameters were obtained. We detect indications of amorphization of the δ-Tb ₂(MoO ₄)₃ phase at 5 GPa.     

The baddeleyite-type high pressure phase of Ca(OH)2

Abstract

A phase transition from Ca(OH)₂ I (portlandite) to Ca(OH)₂ II at high pressure and temperature has been confirmed, using in situ x-ray diffraction in a multianvil high pressure device (DIA). The structure was determined at 9.5 GPa and room temperature from data collected after heating the sample at 300°C at 7.2 GPa in a diamond anvil cell. Both the Le Bail fit and preliminary Rietveld refinement suggest that the new phase, which reverts to Ca(OH), I during pressure release, has a structure related to that of baddeleyite (ZrO₁); it is monoclinic (P2₁/c) with a= 4.887(2), b= 5.834(2), c = 5.587(2), β = 99.74(2)°. The coordination number of Ca increases from six to seven (5 + 2) across the transition. At 500°C, the phase boundary is bracketed at 5.7 ± 0.4 GPa by reversal experiments performed in the DIA.     

Synthesis and characterization of in situ nanocrystalline intermetallic phase reinforced AlTiSi amorphous matrix composite

Composites with partially amorphous matrix were synthesized by mechanical alloying of an Al₅₀Ti₄₀Si₁₀ elemental powder blend in a high energy planetary ball-mill, followed by high pressure (8 GPa) low temperature (350–450°C) sintering. Microstructural studies and compositional micro-analysis were carried out using scanning and transmission electron microscopy, and energy dispersive spectroscopy, respectively. Phase evolution as a function of milling time and isothermal temperature and their thermal stability was determined by X-ray diffraction at room or elevated temperature and differential scanning calorimetry, respectively. The microstructure of composites sintered between room temperature and 450°C showed nano-size (≈50 nm) crystalline precipitates of Al₃Ti dispersed in an amorphous matrix. The composites sintered at 400°C with 8 GPa pressure exhibited the highest density (3.58 Mg/m³), nanoindentation hardness (8.8 GPa), Young's modulus (158 GPa) and compressive strength (1940 MPa). A lower hardness and modulus on sintering at 450°C is attributed to additional amorphous to nanocrystalline phase transformation and partial coarsening of Al₃Ti.     

Synthesis of nano-polycrystalline diamond from glassy carbon at pressures up to 25 GPa

ABSTRACT

Nano-polycrystalline diamond (NPD) with various grain sizes has been synthesized from glassy carbon at pressures 15–25?GPa and temperatures 1700–2300°C using multianvil apparatus. The minimum temperature for the synthesis of pure NPD, below which a small amount of compressed graphite was formed, significantly increased with pressure from ～1700°C at 15?GPa to ～1900°C at 25?GPa. The NPD having grain sizes less than ～50?nm was synthesized at temperatures below ～2000°C at 15?GPa and ～2300°C at 25?GPa, above which significant grain growth was observed. The grain size of NPD decreases with increasing pressure and decreasing temperature, and the pure NPD with grain sizes less than 10?nm is obtained in a limited temperature range around 1800–2000°C, depending on pressure. The pure NPD from glassy carbon is highly transparent and exhibits a granular nano-texture, whose grain size is tunable by selecting adequate pressure and temperature conditions.     

Bridging room-temperature and high-temperature plasticity in decagonal Al–Ni–Co quasicrystals by micro-thermomechanical testing

Ever since quasicrystals were first discovered, they have been found to possess many unusual and useful properties. A long-standing problem, however, significantly impedes their practical usage: steady-state plastic deformation has only been found at high temperatures or under confining hydrostatic pressures. At low and intermediate temperatures, they are very brittle, suffer from low ductility and formability and, consequently, their deformation mechanisms are still not clear. Here, we systematically study the deformation behaviour of decagonal Al–Ni–Co quasicrystals using a micro-thermomechanical technique over a range of temperatures (25–500 °C), strain rates and sample sizes accompanying microstructural analysis. We demonstrate three temperature regimes for the quasicrystal plasticity: at room temperature, cracking controls deformation; at 100–300 °C, dislocation activities control the plastic deformation exhibiting serrated flows and a constant flow stress; at 400–500 °C, diffusion enhances the plasticity showing homogenous deformation. The micrometer-sized quasicrystals exhibit both high strengths of ~2.5–3.5 GPa and enhanced ductility of over 15% strains between 100 and 500 °C. This study improves understanding of quasicrystal plasticity in their low- and intermediate-temperature regimes, which was poorly understood before, and sheds light on their applications as small-sized structural materials.     

Electron transport properties of lithium and phase transitions at high pressures

The electric resistivity and thermopower of lithium have been precisely measured at high pressures (up to 8 GPa) and temperatures from room temperature to 100°C. Transition to the fcc phase of lithium has been analyzed. The hysteresis of the direct and inverse transitions is 0.3 GPa at room temperature, decreases slightly with an increase in the temperature, and is almost independent of the prehistory of the sample. The phase transition line on the P-T diagram has a positive slope of dP/dT = 0.03 GPa/K. It is assumed that the fcc phase of lithium, which is stable at a high pressure, can appear for kinetic regions from the 9R phase, which is intermediate in energy between the bcc and fcc modifications.     

Triple point on the melting curve and polymorphism of nitrogen at high pressure

Raman spectra of solid and fluid nitrogen to pressures up to 120 GPa and temperatures up to 2500 K reveal that the melting line exhibits a maximum near 70 GPa, followed by a triple point near 87 GPa, after which the melting temperature rises again. Fluid nitrogen remains molecular over the entire pressure range studied, and there is no sign of a fluid-fluid transition. Solid phases obtained on quenching from the melt above 48 GPa are identical to the recently discovered iota and zeta' phases. We find that kinetics plays a major role in the experimentally observed phase changes and account for the metastability of various crystalline molecular phases and the existence of an amorphous single bonded eta-N.     

Crystal structure and compressibility of FePt nanoparticles under high pressures and high temperatures

FePt nanoparticles with an average grain size of 4 nm and equiatomic composition of Fe and Pt was studied under high pressures in a diamond anvil cell to investigate its structural stability and compressibility under high compression. The ambient pressure disordered face-centered-cubic (fcc) phase was found to be stable to the highest pressure of 61 GPa (compression of 15%) at room temperature. The compression of Fe₅₀Pt₅₀ nanoparticles is closer to the compression curve for pure Pt and shows lower compressibility than what would be expected for a bulk Fe₅₀Pt₅₀ alloy. The nanoparticle character of Fe₅₀Pt₅₀ sample is maintained to the highest pressure without any observable grain coarsening effects at ambient temperature. Laser heating of disordered fcc phase at 32 GPa to a temperature of 2000 K resulted in a phase transformation to a microcrystalline phase with the distorted fcc structure.     

Phase transition,lattice dynamical and thermodynamic properties of yttrium antimonide with the rock salt structure under high pressure: first-principles investigations

We investigate the structural, electronic, first-order pressure-induced phase transition, lattice dynamical, and thermodynamic properties of yttrium antimonide (YSb) with the rock salt structure at high pressures and high temperatures using the projector-augmented wave method based on the density-functional theory. By the usual condition of equal enthalpy, we find that the rock salt-structured YSb is stable up to 31.10 GPa, and then transforms to the CsCl-type structure, this is consistent with the experiment result which begins transform from 26 GPa then ends at 36 GPa. The phonon dispersion curves of the rock salt-structured YSb are calculated under high pressure for the first time using a linear-response approach to density-functional perturbation theory successfully. Within the calculated phonon density of state and the quasi-harmonic approximation, we predict further the thermal physical properties of YSb under high temperature and high pressure systematically.     

Electrical and mechanical properties of C70 fullerene and graphite under high pressures studied using designer diamond anvils

We compare electrical and mechanical properties of C70 fullerene with high purity graphite to 48 GPa at room temperature using designer diamond anvils with embedded electrical microprobes. The electrical resistance of C70 shows a minimum at 20 GPa with transformation to an amorphous insulating phase complete above 35 GPa, while graphite remains conducting. Nanoindentation shows hardness values 220 times larger for the pressure quenched amorphous phase than for similarly treated graphite. Our studies establish that the amorphous carbon phase produced from C70 has unique properties not attainable from graphite.     

Phase transformations in amorphous fullerite C60 under high pressure and high temperature

First phase transformations of amorphous fullerite C₆₀ at high temperatures (up to 1800 K) and high pressures (up to 8 GPa) have been investigated and compared with the previous studies on the crystalline fullerite. The study was conducted using neutron diffraction and Raman spectroscopy. The amorphous fullerite was obtained by ball-milling. We have shown that under thermobaric treatment no crystallization of amorphous fullerite into С₆₀ molecular modification is observed, and it transforms into amorphous-like or crystalline graphite. A kinetic diagram of phase transformation of amorphous fullerite in temperature–pressure coordinates was constructed for the first time. Unlike in crystalline fullerite, no crystalline polymerized phases were formed under thermobaric treatment on amorphous fullerite. We found that amorphous fullerite turned out to be less resistant to thermobaric treatment, and amorphous-like or crystalline graphite were formed at lower temperatures than in crystalline fullerite.     

Density measurements of non-crystalline materials under high pressure and high temperature

Abstract

We have developed a new method for density measurements by means of X-ray absorption under high pressure and high temperature using a multi-anvil apparatus combined with a synchrotron-radiation source. To overcome the effect of the variation of the sample thickness under pressure, a sapphire ball was put in the sample capsule as a calibrant of the thickness, and the intensity of the transmitted X-ray beam was measured as a function of the sample position. The densities of crystalline and liquid tellurium were measured up to 5 GPa and up to 700°C. Discontinuous changes in the density at the Te I-Te 11 transition and at the melting were clearly observed.     

Electrical transport and high pressure studies on bulk Ge20Te80 glass

The electrical resistivity of bulk Ge₂₀Te₈₀ has been measured as a function of pressure and temperature. At 5 GPa, an amorphous semiconductor-to-crystalline metal transition has been observed. The sample recovered from the high pressure cell, after the application of 7 GPa, has a face-centred cubic structure with a lattice constant of 6·42 A. In crystalline sample, the semiconductor-to-metal transition occurs at 7 GPa. The thermoelectric power has also been measured for glassy samples in the temperature range 300–240 K.     

Phase transformation of Ni/Si thin films induced by nanoindentation and annealing

Thin Ni/Si films are prepared by depositing a Ni layer with a thickness of 100 nm on a Si (100) substrate. The as-deposited thin-film specimens are indented to a maximum depth of 500 nm using a nanoindentation technique and are then annealed at temperatures of 200°C, 300°C, 500°C and 800°C for 2 min. The microstructural changes and phases induced in the various specimens are observed using transmission electron microscopy (TEM) and micro-Raman scattering spectroscopy (RSS). Based on the load-displacement data obtained in the nanoindentation tests, the hardness and Young’s modulus of the as-deposited specimens are found to be 13 GPa and 177 GPa, respectively. The microstructural observations reveal that the nanoindentation process prompts the transformation of the indentation-affected zone of the silicon substrate from a diamond cubic structure to a mixed structure comprising amorphous phase and metastable Si III and Si XII phases. Following annealing at temperatures of 200∼500°C, the indented zone contains either a mixture of amorphous phase and Si III and Si XII phases, or Si III and Si XII phases only, depending on the annealing temperature. In addition, the annealing process prompts the formation of nickel silicide phases at the Ni/Si interface or within the indentation zone. The composition of these phases depends on the annealing temperature. Specifically, Ni₂Si is formed at a temperature of 200°C, NiSi is formed at a temperature of 300°C and 500°C, and NiSi₂ is formed at 800°C.     

Magnetic ordering temperatures in rare earth metal dysprosium under ultrahigh pressures

Magnetic ordering temperatures in heavy rare earth metal dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to a pressure of 69 GPa and a temperature of 10 K. Previous studies using magnetic susceptibility measurements at high pressures were able to track magnetic ordering temperature only till 7 GPa in the hexagonal close packed (hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. This is followed by a rapid increase in the magnetic ordering temperatures in the double hcp phase and finally leveling off in the distorted face centered cubic phase of Dy. Our studies reaffirm that 4f-shell remains localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.