In situ rheological measurements at extreme pressure and temperature using synchrotron X‐ray diffraction and radiography

Dramatic technical progress seen over the past decade now allows the plastic properties of materials to be investigated under extreme pressure and temperature conditions. Coupling of high‐pressure apparatuses with synchrotron radiation significantly improves the quantification of differential stress and specimen textures from X‐ray diffraction data, as well as specimen strains and strain rates by radiography. This contribution briefly reviews the recent developments in the field and describes state‐of‐the‐art extreme‐pressure deformation devices and analytical techniques available today. The focus here is on apparatuses promoting deformation at pressures largely in excess of 3 GPa, namely the diamond anvil cell, the deformation‐DIA apparatus and the rotational Drickamer apparatus, as well as on the methods used to carry out controlled deformation experiments while quantifying X‐ray data in terms of materials rheological parameters. It is shown that these new techniques open the new field of in situ investigation of materials rheology at extreme conditions, which already finds multiple fundamental applications in the understanding of the dynamics of Earth‐like planet interior.     

Reappearance of ferroelectric soft modes in the paraelectric phase of Pb(1-x)Ca(x)TiO3 at high pressures: Raman and x-ray diffraction studies

High pressure Raman spectroscopy and x-ray diffraction measurements have been carried out on Pb(1-x)Ca(x)TiO(3) (x = 0.10 and 0.30). Using high pressure Raman spectroscopic data, it is observed that the phonon instability responsible for the ferroelectric phase reappears in the paraelectric phase after a critical pressure. The observed critical pressures in the Ca(2+) doped PbTiO(3) system are much lower than the unique pressures suggested for PbTiO(3) based materials. A suitable explanation is given to explain this lowering of critical pressure. It is also shown that the ferroelectric phase which stabilizes in the paraelectric phase has a tetragonal symmetry with space group I4cm.     

大块钙钛矿MgSiO3和镁方铁矿(Mg,Fe)O的高压合成

 钙钛矿相MgSiO₃和镁方铁矿(Mg,Fe)O作为地球下地幔含量最丰富的候选矿物，其高温高压实验数据通常用来与地震学探测数据做对比，对限定下地幔的真实矿物学组分具有决定性的作用。但天然的钙钛矿相MgSiO₃和镁方铁矿(Mg,Fe)O很难得到，给这两种矿物的高温高压实验研究工作带来不便。介绍了应用活塞圆筒（Piston-Cylinder）压机和大腔体二级压砧（Mutli-Anvil）压机高温高压合成大块钙钛矿相MgSiO₃和不同Fe/Mg比的镁方铁矿(Mg,Fe)O样品的实验技术和实验方法，对所得到的样品进行了微区电子探针、拉曼光谱和X射线衍射分析。所得样品可以作为高压实验特别是冲击压缩实验的初始样品。     

Zr-based bulk metallic glass as a cylinder material for high pressure apparatuses

Zirconium-based bulk metallic glass (Zr-based BMG) has outstanding properties as a cylinder material for piston-cylinder high pressure apparatuses and is especially useful for neutron scattering. The piston-cylinder consisting of a Zr-based BMG cylinder with outer/inner diameters of 8.8/2.5?mm sustains pressures up to 1.81?GPa and ruptured at 2.0?GPa, with pressure values determined by the superconducting temperature of lead. The neutron attenuation of Zr-based BMG is similar to that of TiZr null-scattering alloy and more transparent than that of CuBe alloy. No contamination of sharp Bragg reflections is observed in the neutron diffraction pattern for Zr-based BMG. The magnetic susceptibility of Zr-based BMG is similar to that of CuBe alloy; this leads to a potential application for measurements of magnetic properties under pressure.     

聚龙一号装置准等熵压缩实验负载优化研究

准等熵压缩实验技术已用来研究材料在高压下的状态方程。基于聚龙一号装置平台,实现对样品的准等熵压缩和超高速飞片发射,进行了一系列实验来加深对负载构型的理解。通过对负载结构的设计,研究了构设电极尺寸与电极间隙对磁应力的大小与分布的影响。基于模拟和实验结果,带状线负载结构可以很好地提高磁压和提升装置的运行水平,其电极表面磁压分布也具有良好的均匀性和平面性。目前为止,已经可以用带状线负载在聚龙一号装置上获得峰值压力高达约100 GPa的准等熵压缩,并获得速度超过10 km/s的超高速飞片。     

聚龙一号装置准等熵压缩实验负载优化研究

准等熵压缩实验技术已用来研究材料在高压下的状态方程。基于聚龙一号装置平台,实现对样品的准等熵压缩和超高速飞片发射,进行了一系列实验来加深对负载构型的理解。通过对负载结构的设计,研究了构设电极尺寸与电极间隙对磁应力的大小与分布的影响。基于模拟和实验结果,带状线负载结构可以很好地提高磁压和提升装置的运行水平,其电极表面磁压分布也具有良好的均匀性和平面性。目前为止,已经可以用带状线负载在聚龙一号装置上获得峰值压力高达约100 GPa的准等熵压缩,并获得速度超过10 km/s的超高速飞片。     

Pressure induced resistivity changes in diluted magnetic semiconductors of (Hg,Fe)Se and (Hg,Mn)Te

Abstract

Electrical resistance measurements have been performed on samples of Hg_1-xFe_xSe and Hg_1-xMn_xTe for × ≤ 0.30 as a function of pressure to 7.0 GPa. Both materials crystallize in the B3 structure at atmospheric pressure and room temperature and belong to the class of materials known as diluted magnetic semiconductors. At elevated pressures, HgTe undergoes a phase change from the B3 to B9 phase which is accompanied by an increase in the electrical resistivity of several orders of magnitude. The results reported here are that increasing × in both materials serves to increase the B3-B9 transition pressure. The implication being that partial replacement of the Hg-bonds by Fe-Se and Mn-Te, respectively, increases the stability range of the B3 phase     

A Brief Overview of the Effect of High Pressures on the Vibrational Spectra of Biomaterials

Abstract

The application of high pressures to biomaterials can often result in significant structural modifications and, in some cases, also lead to changes in the rates and the equilibria of any associated biological activities. Pressure-induced changes can conveniently be monitored by molecular spectroscopy. We present here a brief overview of the effects of high pressures on the IR and Raman spectra of biomaterials that have been reported over the past 25 years. Examples of the biomaterials that have been examined are model antithyroid drugs, proteins, amino acids, dental materials, human bones, and bioorganometallic compounds. In addition, some recent investigations on the effect of pressure on microbial activity and the conversion of biomass into molecular hydrogen under supercritical water conditions are discussed. Two typical diamond-anvil cells (DACs), which are used for high-pressure vibrational spectroscopic measurements, are also described here.     

EDXD studies above 400 GPa (and prospects for obtaining pressures near 1 TPa and doing EDXD studies at such pressures)

Abstract

We have now taken two materials (W, Mo) to pressures greater than the pressure at the center of the earth for the first time, with all pressures based on x-ray diffraction and shock-based equations of state. The present paper describes x-ray diffraction studies of a sample in which pressure equals or exceeds 438 GPa. It is noted that as a result of the process of pressure strengthening, pressures of 1 TPa may be attainable.

Presented at the IUCr Workshop on ‘Synchrotron Radiation Instrumenration for HighPressure Crystallography’. Daresbury Laboratory 20-21 July 1991     

Pressure-induced structural transformations and the anomalous behavior of the viscosity in network chalcogenide and oxide melts

It is known that a number of compressed melts undergo structural phase transitions. Data on the structural changes at high pressures in chalcogenides (AsS, As₂S₃) and oxide (B₂O₃) melts with a network structure have been reviewed. Viscosity is one of the fundamental physical properties of a liquid. For various melts, it varies in a very wide range. Structural transformations in melts induce the corresponding changes in all physical properties, in particular viscosity. The measurements of the viscosity of a number of melts at high pressures and temperatures by the radiographic method have been reported. Changes in the viscosity by several orders of magnitude have been detected when the pressure is varied by several gigapascals. The diffusion mechanism in network-structure melts at various pressures has been analyzed. The prediction of the behavior of the viscosity of various melts at superhigh pressures is of high importance for the physics of glass transition, geophysics, and materials science.     

Review: high pressure generation techniques beyond the limit of conventional diamond anvils

ABSTRACT

Current anvil designs and problems associated with various efforts to generate static high pressures beyond the limit of conventional diamond anvil cells (DACs) (～400?GPa) are reviewed. Pressures of up to 1?TPa have been reported by one research group using the double-stage DAC (ds-DAC) technique, but no other research group has successfully reproduced this high pressure result. Some research groups have used toroidal anvils, achieving pressures of >400?GPa. We have conducted numerous ds-DAC experiments and investigated the problems associated with such experiments. They include problems associated with various pressure scales in the multi-megabar region, difficulties in obtaining reliable X-ray diffraction patterns from micron-sized samples, and physical property measurements of tiny materials that may be harder than diamond. Each of these problems is discussed, following the summary of various experiments.     

High pressure studies at the photon factory

Abstract

The Photon Factory has unique features from the point of view of high pressure research. Six beamlines have been used for high pressure experiments, two of which were constructed as dedicated beamlines for large high pressure devices. Various kinds of high pressure studies, such as powder and single crystal x-ray diffraction and absorption experiments, have been carried out on these beamlines by more than 30 user groups, including foreign visitors. Two types of high pressure apparatuses are most frequently used. One is the large volume high pressure devices (MAX80 and MAX90) combined with high energy and/or high brightness synchrotron radiation. The other is a system combining the diamond anvil cell with a 2-dimensional detector, the IMAGE PLATE. Many improvements have been made both in the high pressure techniques and the diffraction measurement methods.

Presented at the IUCr Workshop on ‘Synchrotron Radiation Instrumentation for High Pressure Crystallography’. Daresbury Laboratory 20-21 July 1991     

Effect of interstitial air pressure and particle size on the heat storage coefficient of a two phase system

An expression for the heat storage coefficient (HSC) of loose granular systems at interstitial air pressures is developed in terms of the characteristic pressure. The dependence of the HSC on pore and particle sizes and characteristic pressure is also discussed. To test the validity of the derived expression, the experiments are performed on a number of materials with various particle sizes and interstitial air pressures. The other reported data on the HSC are also compared with predicted values. A good agreement is found between them. This study suggests that the selection of proper particle size and partial evacuation of the pore improves the insulation characteristics of the materials.     

CuCl nanocrystals in alkali-halide matrices under hydrostatic pressure

CuCl nanocrystals in crystalline alkali-halide matrices have been investigated under hydrostatic pressures up to 18 GPa. The pressures of structural phase transitions in CuCl have been determined both for different nanocrystal sizes and for different matrices (NaCl, LiCl, KCl). For CuCl nanocrystals in NaCl an increase of the transition pressure with decreasing nanocrystal size is observed, which is explained by the increasing importance of surface pressure for small nanocrystals. We found higher transition pressures for the LiCl matrix than for the NaCl matrix. The reason for this is that the pressure which acts on the nanocrystal differs from the external pressure. A simple elastic model describes the effective pressure transmitted from the matrix to the nanocrystal. With CuCl nanocrystals embedded in KCl we have studied the behavior of nanocrystals during a phase transition of the matrix. Additionally we have determined the pressure coefficients of the exciton energies of the CuCl nanocrystals, which depend on the elastic properties of the matrix. Received 4 March 1999     

Temperature and pressure behaviour of narrow-gap semiconductors including galena

The structural high pressure and temperature investigation of narrow-gap semiconductors (lead chalcogenides) has been performed in the present article. A realistic approach for room temperature and high temperature study of narrow-gap semiconductors has been used. It is examined that the present compounds are more stable in NaCl-phase and they transform to CsCl-phase at high pressure. In the present article, the phase transition pressures and volume collapses of lead chalcogenides have been investigated at room and high temperatures. Phase transition pressures have been reported at high temperature range from 0 to 1200 K. Elastic and anharmonic constants have also been reported at room temperature. A structural study of the narrow-gap semiconductors have been carried out using the realistic model including temperature effect. The temperature and pressure behaviour of elastic constants for the present compounds have also been discussed. Furthermore, various mechanical and thermo dynamical properties like modulus of elasticity, Debye temperatures etc. are also presented.     

Low gas pressures obtained by means of sorbents

The paper describes the use of active charcoal and a 13X molecular sieve at 78°K to pump all-glass apparatuses with a small volume (up to 5000 cm³) from atmospheric pressure to a pressure region of 10^–2 mm Hg. At this pressure an outgassed second pumping stage (also sorbent) permits pressures from 10^–6 to 10^–7 mm Hg to be obtained. Active charcoal was also used as a two-stage fore pump (p=10^–6 mm Hg) for a one-stage mercury diffusion pump and in this system pressures of 5 to 10×10^–10 mm Hg were achieved.     

Analysis of relative pressure range influence on the identification quality during computer identification of adsorption system parameters by employing the new multilayer adsorption models

The aim of this work has been to analyze the problems related to the identification of microporous structure parameters of carbonaceous materials. The new methods for microporous structure parameters identification have been explored with special focus on the influence of the analyzed relative pressure range on the reliability of parameters identification. For that purpose, the adsorption isotherm of nitrogen on active carbon for different ranges of relative pressures p/p₀ was analyzed. The conducted research was to provide for an answer to the question of whether the range of the analyzed relative pressures has any effect on the quality of adsorption system parameters identification, as well as what range of the relative pressure permits execution of the reliable identification of microporous structure parameters.     

Pressure effect on the electromotive force of the type R thermocouple

ABSTRACT

The pressure effect on the electromotive force (EMF) of a Pt13Rh–Pt (type R) thermocouple was examined to determine the temperature measurement accuracy of solid pressure medium apparatuses in high-pressure experiments. Single-wire EMFs were measured up to pressure of 13?GPa and temperature of 1173?K with a Kawai-type multi-anvil apparatus for Pt13Rh and Pt based on the single-wire method. The pressure conditions along the wires were evaluated by in situ X-ray diffraction using synchrotron X-ray radiation. The pressure effect of the Seebeck coefficients of Pt13Rh and Pt were determined by the analysis of the single-wire EMFs and pressure–temperature profiles along the wires and was virtually consistent with those determined in previous studies at lower pressures and temperatures. For type R thermocouple, the difference between the nominal and real temperatures was determined to be as large as –75?K at 13?GPa and 873?K.     

High-pressure synthesized materials: treasures and hints

This short review covers some particular aspects of the production of new materials under high pressures. Despite the fact that there is an extremely wide range of new high-pressure synthesized substances with unique properties, a commercial synthesis has been used up to date only for producing superhard materials – these are real treasures of today’s industry. At the same time, as should be underlined here, high-pressure experiments often give scientists material with helpful hints of what new intriguing substances can exist in principle. This is true both for new superhard, semiconducting, magnetic, superconducting, optical materials already synthesized under pressure and a large number of hypothetic new polymers from low-Z elements.     

超高压和酶抑制剂联合处理对荔枝果肉中过氧化物酶和果胶甲基酯酶的影响

 为了研究超高压与酶抑制剂联合处理对荔枝果肉中过氧化物酶（POD）和果胶甲基酯酶（PME）的影响,将荔枝（“淮枝”品种）果肉在两种酶抑制剂组合溶液（A：5 g/L柠檬酸+2.5 g/L L-抗坏血酸+5 g/L氯化钙;B：10 g/L柠檬酸+5 g/L L-抗坏血酸+10 g/L氯化钙）中分别浸泡10 min,并在100~400 MPa压力、10 ℃温度条件下处理30 min,采用分光光度法测定果肉中POD、PME的活性。结果表明：A、B两种组合处理能够明显钝化POD,但却显著激活了PME;超高压与A组合联合处理不能使POD、PME活性下降;超高压与B组合联合处理对POD、PME的影响与压力值有关系,100~300 MPa的超高压与B组合联合处理使POD活性下降,200~400 MPa的超高压与B组合联合处理则使PME活性升高。因此,超高压与酶抑制剂联合处理对荔枝果肉中POD的钝化存在一定的协同效应,且浓度越高,协同抑制效应越明显;而超高压与酶抑制剂联合处理对荔枝果肉中PME的钝化却表现出一定的拮抗性。