Equation of state of cubic boron nitride at high pressures and temperatures

We report accurate measurements of the equation of state (EOS) of cubic boron nitride by x-ray diffraction up to 160 GPa at 295 K and 80 GPa in the range 500-900 K. Experiments were performed on single-crystals embedded in a quasi-hydrostatic pressure medium (helium or neon). Comparison between the present EOS data at 295 K and literature allows us to critically review the recent calibrations of the ruby standard. The full P-V-T data set can be represented by a Mie-Gr\"{u}neisen model, which enables us to extract all relevant thermodynamic parameters: bulk modulus and its first pressure-derivative, thermal expansion coefficient, thermal Gr\"{u}neisen parameter and its volume dependence. This equation of state is used to determine the isothermal Gr\"{u}neisen mode parameter of the Raman TO band. A new formulation of the pressure scale based on this Raman mode, using physically-constrained parameters, is deduced.Comment: 8 pages, 7 figure

Effect of nanostructuration on compressibility of cubic BN

Compressibility of high-purity nanostructured cBN has been studied under quasi-hydrostatic conditions at 300 K up to 35 GPa using diamond anvil cell and angle-dispersive synchrotron powder X-ray diffraction. It has been found that the data fit to the Vinet equation of state yields the values of the bulk modulus B₀ of 375(4) GPa with its first pressure derivative B₀´ of 2.3(3), thus, the nanometer grain size (≈ 20 nm) results in a decrease of the bulk modulus by ≈ 9‰.Сжимаемость высокочистого наноструктурированного cBN была изучена в квазигидростатических условиях при 300 K до 35 GPa в алмазных наковальнях с помощью угловой дисперсионной рентгеновской дифракции синхротронного излучения. Описание полученных данных уравнением состояния Винэ дает значение модуля сжимаемости B₀ = 375(4) ГПа и его первой производной по давлению B₀' = 2.3(3). Наноразмер зерна (~ 20 нм) приводит к уменьшению модуля сжимаемости на ~ 9 %.Стисливість високочистого наноструктурованого cBN була вивчена в квазігідростатичних умовах при 300 K до 35 ГПa в алмазних наковальнях за допомогою кутової дисперсійної рентгенівської дифракції синхротронного випромінювання. Опис одержаних даних рівнянням стану Віне дає значення модуля стисливості B₀ = 375(4) ГПа і його першої похідної по тиску B₀' = 2.3(3). Нанорозмір зерна (~ 20 нм) приводить до зменшення модуля стисливості на ~ 9 %

Equation of state of single-crystal cubic boron phosphide

The 300 K equation of state of cubic (zinc-blende) boron phosphide BP has been studied by in situ single-crystal X-ray diffraction with synchrotron radiation up to 55 GPa. The measurements have been performed under quasi-hydrostatic conditions using a Ne pressure medium in a diamond anvil cell. A fit of the experimental p-V data to the Vinet equation of state yields the bulk modulus B0 of 179(1) GPa with its pressure derivative of 3.3(1). These values are in a good agreement with previous elastic measurements, as well as with semiempirical estimations.Уравнение состояния кубического (цинковая обманка) фосфида бора BP при 300 К изучено in situ до давления 55 ГПа с применением монокристаллической дифракции рентгеновских лучей с синхротронным излучением. Измерения проводили в алмазных наковальнях в квазигидростатических условиях с использованием Ne в качестве среды, передающей давление. Соответствие экспериментальных p-V данных уравнению состояния Винета (Vinet) дает объемный модуль упругости B0 = 179(1) ГПа и его производную по давлению 3,3(1). Эти величины хорошо согласуются с прежними измерениями упругости, а также с полуэмпирическими оценками.Рівняння стану кубічного (цинкова обманка) фосфіду бору BP при 300 К вивчено in situ до тиску 55 ГПа зі застосуванням монокристалічної дифракції рентгенівських променів із синхротронним випромінюванням. Вимірювання проводили в алмазних ковадлах у квазігідростатичних умовах з використанням Ne в якості середовища, що передає тиск. Відповідність експериментальних p-V даних рівнянню стану Вінета (Vinet) дає об’ємний модуль пружності B0 = 179(1) ГПа і його похідну по тиску 3,3(1). Ці величини добре узгоджуються з попередніми вимірюваннями пружності, а також із напівемпіричними оцінками

The effect of cation disorder on magnetic properties of new double perovskites La2NixCo1-xMnO6 (x = 0.2 - 0.8)

Solid solutions of new double perovskite oxides La2NixCo1-xMnO6 (x = 0.2, 0.25, 0.5, 0.75, 0.8) were synthesized by solid-state reaction method. The X-ray powder diffraction data show that all the compounds crystallize in the monoclinic structure with space group P21/n at room temperature. The elementary composition of the powders was determined by the electron Probe Microanalysis. Raman and IR spectra show strong bands at (520, 650 cm?1) and (426, 600 cm?1) respectively, attributed to the stretching vibration of Ni/Co-O and Mn-O bonds in the structure. The magnetic studies for all the compounds have been performed in both DC and AC magnetic fields in the temperature range from 2 to 300 K. All samples exhibit a main paramagnetic to ferromagnetic (PM-FM) transition between 232 K and 260 K, and their Curie temperature increases rapidly with increasing x values. Three samples with x = 0.2, 0.25 and 0.5 respectively display also a secondary PM-FM transition between 200 K and 208 K. The thermal variation of out of phase component of AC susceptibility presents also frequency-dependent transitions between 65 K and 110 K unfolding the existence of super-paramagnetic mono-domains in all samples. The band gap energy has been calculated and revealing semiconductor behavior for all samples

The high-pressure phase of boron, {\gamma}-B28: disputes and conclusions of 5 years after discovery

{\gamma}-B28 is a recently established high-pressure phase of boron. Its structure consists of icosahedral B12 clusters and B2 dumbbells in a NaCl-type arrangement (B2){\delta}+(B12){\delta}- and displays a significant charge transfer {\delta}~0.5- 0.6. The discovery of this phase proved essential for the understanding and construction of the phase diagram of boron. {\gamma}-B28 was first experimentally obtained as a pure boron allotrope in early 2004 and its structure was discovered in 2006. This paper reviews recent results and in particular deals with the contentious issues related to the equation of state, hardness, putative isostructural phase transformation at ~40 GPa, and debates on the nature of chemical bonding in this phase. Our analysis confirms that (a) calculations based on density functional theory give an accurate description of its equation of state, (b) the reported isostructural phase transformation in {\gamma}-B28 is an artifact rather than a fact, (c) the best estimate of hardness of this phase is 50 GPa, (d) chemical bonding in this phase has a significant degree of ionicity. Apart from presenting an overview of previous results within a consistent view grounded in experiment, thermodynamics and quantum mechanics, we present new results on Bader charges in {\gamma}-B28 using different levels of quantum-mechanical theory (GGA, exact exchange, and HSE06 hybrid functional), and show that the earlier conclusion about significant degree of partial ionicity in this phase is very robust

A portable high-pressure stress cell based on the V7 Paris-Edinburgh apparatus

International audienceWe describe a newdevice, based on aV7 Paris–Edinburgh press, for torsional testing of material at pressures up to 7GPa (extendable to 15 GPa). Samples are deformed using a simple shear geometry between opposed anvils by rotating the lower anvil, via a rotational actuator, with respect to an upper, stationary, anvil. Use of conical anvil profiles greatly increases sample dimensions more than other high-pressure torsional apparatus did. Samples of polycrystalline Zr (2mm thick, 3.5mm diameter) have been sheared at strains exceeding γ∼1.5 at constant strain rate and at pressures from 1.8 to 5GPa, and textural development has been studied by electron microscopy. Use of amorphous-boron-epoxy gaskets means that nearly simple shear of samples can be routinely achieved. This apparatus allows study of the plastic and anelastic behaviour of materials under high pressure, and is particularly suited for performing in situ investigations using synchrotron or neutron radiatio

Phase boundary between Na–Si clathrates of structures I and II at high pressures and high temperatures

Understanding of the covalent clathrate formation is a crucial point for the design of new superhard materials with intrinsic coupling of superhardness and metallic conductivity. It has been found that silicon clathrates have the archetype structures, which can serve an existent model compounds for superhard clathrate frameworks Si–B, Si–C, B–C and C with intercalated atoms (e.g., alkali metals or even halogens) that can assure the metallic properties. Here we report our in situ and ex situ studies of high-pressure formation and stability of clathrates Na₈Si₄₆ (structure I) and Na₂₄₊xSi₁₃₆ (structure II). Experiments have been performed using standard Paris–Edinburgh cells (opposite anvils) up to 6 GPa and 1500 K. We have established that chemical interactions in the Na–Si system and transition between two structures of clathrates occur at temperatures below silicon melting. The strong sensitivity of crystallization products to the sodium concentration has been observed. A tentative diagram of clathrate transformations has been proposed. At least up to ~ 6 GPa, Na₂₄₊xSi₁₃₆ (structure II) is stable at lower temperatures as compared to Na₈Si₄₆ (structure I).Изучен in situ и ex situ процесс образования при высоких давлениях и стабильности клатратов Na₈Si₄₆ (структура I) и Na₂₄₊xSi₁₃₆ (структура II). Эксперименты были проведены в стандартных Париж-Эдинбургских ячейках (opposite anvils) при давлениях и температурах до 6 ГПа и 1500 K соответственно. Установлено, что химическое взаимодействие в системе Na–Si и переходы между двумя структурами клатратов происходят при температурах ниже температуры плавления кремния. Предложено первое приближение диаграммы превращений клатратов. Отмечена большая чувствительность продуктов кристаллизации к концентрации натрия. Na₂₄₊xSi₁₃₆ (структура II) является стабильной при более низких температурах по сравнению с Na₈Si₄₆ (структура I), по крайней мере до ~ 6 ГПа.Вивчено in situ і ex situ процес утворення при високих тисках і стабільності клатратів Na₈Si₄₆ (структура I) і Na₂₄₊xSi₁₃₆ (структура II). Експерименти було проведено в стандартних Париж-Единбурзький комірках (opposite anvils) при тисках і температурах до 6 ГПа і 1500 K відповідно. Встановлено, що хімічна взаємодія в системі Na–Si і переходи між двома структурами клатратов відбуваються при температурах нижче температури плавлення кремнію. Запропоновано перше наближення діаграми перетворень клатратів. Відзначено велику чутливість продуктів кристалізації до концентрації натрію. Na₂₄₊xSi₁₃₆ (структура II) є стабільною при більш низьких температурах у порівнянні з Na₈Si₄₆ (структура I), принаймні до ~ 6 ГПа

Effect of nanostructuration on compressibility of cubic BN

Compressibility of high-purity nanostructured cBN has been studied under quasi-hydrostatic conditions at 300 K up to 35 GPa using diamond anvil cell and angle-dispersive synchrotron X-ray powder diffraction. A data fit to the Vinet equation of state yields the values of the bulk modulus B0 of 375(4) GPa with its first pressure derivative B0' of 2.3(3). The nanometer grain size (\sim20 nm) results in decrease of the bulk modulus by ~9%

Rotating tomography Paris-Edinburgh cell:a novel portable press for micro-tomographic 4-D imaging at extreme pressure/temperature/stress conditions

International audienceThis paper presents details of instrumental development to extend synchrotron X-ray microtomography techniques to in situ studies under static compression (high pressure), shear stress or the both conditions at simultaneous high temperatures. To achieve this, a new rotating tomography Paris–Edinburgh cell has been developed. This ultra-compact portable device easily and successfully adapted to various multi-modal synchrotron experimental set-up at ESRF, SOLEIL and DIAMOND is explained in detail. An in-depth description of proof of concept first experiments performed on a high resolution imaging beamline is then given, which illustrate the efficiency of the set-up and the data quality that can be obtained

Deformation-aided segregation of Fe-S liquid from olivine under deep Earth conditions: Implications for core formation in the early solar system

The planets and larger rocky bodies of the inner solar system are differentiated, and consist of metallic, iron-rich cores surrounded by thick shells of silicate. Core formation in these bodies, i.e. the segregation of metal from silicate, was a key process in the early solar system, and one which left a lasting geochemical signature. It is commonly assumed that extensive silicate melting and formation of deep magma oceans was required to initiate core formation, due to the inability of iron-rich melts to segregate from a solid silicate matrix. Here we assess the role of deformation in aiding segregation of core-forming melts from solid silicate under conditions of planetary deep interiors. Low-strain rate, high-pressure/ temperature deformation experiments and high-resolution 2-D and 3-D textural analysis demonstrate that deformation fundamentally alters iron-rich melt geometry, promoting wetting of silicate grain boundaries and formation of extensive micron to sub-micron width Fe-rich melt bands. Deformation-aided Fe-S melt networks noted here contrast those observed in higher finite strain experiments conducted at lower pressure, and may reveal either an alternative mechanism for melt segregation at higher pressures, or an early stage process of melt segregation. Results suggest, however, that core-mantle chemical equilibration cannot be assumed in models of planetary formation, and that instead, the chemistry of rocky planets may record a complex, multi-stage process of core formation.This work was supported by the University Of Edinburgh (Principal’s Career Development studentship), the Natural Environment Research Council under NE/I016333/1, Science and Technology Facilities Council, European Synchrotron Radiation Facility, and the EPSRC for the Manchester X-ray Imaging Facility under EP/ F007906/1 and EP/F028431/1