高压下的同步辐射能量色散粉末衍射

 同步辐射已经成为高压研究的一个非常理想的光源。在北京同步辐射装置（BSRF）上、结合金刚石对顶砧超高压实验技术建立起来的能量色散X射线粉末衍射系统,已用于物质状态方程和结构相变的研究。介绍了能量色散衍射方法,以及同步辐射原位测试过程。     

非静水压下材料强度对压力标定的影响

采用金刚石对顶砧压腔和同步辐射X射线衍射技术研究了非静水压下材料强度对压力标定的影响。实验中,在同一个高压腔中用Pt和Au作为压标进行压力标定比较。Pt标定腔内压力,分别将Au与β-SiC和NaCl粉末混合,压力均加载到50GPa。结果表明:当使用β-SiC作为样品材料时,Pt标定的压力和Au标定的压力出现了比较大的差别;当使用NaCl作为样品材料时,Pt标定的压力和Au标定的压力十分接近。说明在非静水压下,样品材料强度对于压力标定有很大的影响。     

铝的等温状态方程

 采用原位高压同步辐射X射线衍射技术,利用金刚石对顶砧（DAC）装置产生高压,选用高纯NaCl粉末作为传压介质与标压物质,在室温下、21.5 GPa的压力范围内,测定了铝的等温状态方程。利用Murnaghan方程对实验结果进行了数值拟合,得到铝的零压体弹模量及其一级压力导数分别为B₀=(77±2) GPa,B₀′=4.8±0.3。该结果同相关文献资料报导的值在误差范围内符合得很好,略显得较大,这是由于传压介质NaCl的非静水压效应所致。在实验所达到的压力范围内,未发现明显的相变迹象。     

CsBr高压X光研究

 采用同步辐射X光源和能散法，对CsBr粉末样品进行高压原位X光衍射实验。由金刚石对顶压砧高压装置（DAC）产生高压，用已知状态方程的Pt粉末作内标，由Pt的衍射数据确定样品压力，最高压力达64.4 GPa。实验结果表明：室温常压下原始CsBr样品是具有简单立方结构的晶体，其晶格常数α＝0.428 5 nm。高压下CsBr的结构有所变化，在51.3~58.4 GPa的压力范围内，(110)线和(211)线发生劈裂，从而形成了四方相。     

C60高压X射线衍射研究

 采用同步辐射X光源和能量色散法对高纯C₆₀粉末样品进行高压原位X光衍射实验。由金刚石对顶压砧高压装置（DAC）产生高压,用已知状态方程的Pt粉末作内标,由Pt的衍射数据确定样品压力,最高压力达30 GPa。实验结果表明：室温常压下原始C₆₀样品为面心立方结构,晶格常数a=1.420 86 nm。高压下C₆₀的结构有所变化：从p=13.7 GPa开始,(311)线发生劈裂,形成低对称相;随着压力增加,衍射线逐渐变宽,强度逐渐变弱,压力超过25 GPa,衍射背底隆起,C₆₀开始转化成非晶相;在30 GPa左右,衍射线条完全消失,标志着向非晶相转化过程的完成。人们也对C₆₀样品不同压力的高压“淬火”相进行了X光衍射实验。采用非静水压的装样方式,最高压力达44 GPa,结果在30 GPa以上,C₆₀也转变为非晶相。最后我们对C₆₀晶体的压致非晶化现象进行了初步的讨论。     

高压对钴酸锂的晶体结构和离子导电率的影响

采用金刚石对顶砧(DAC)高压产生装置,结合同步辐射X射线衍射(XRD),对钴酸锂(LiCoO2)粉末样品进行室温下原位高压X射线衍射实验,最高压强达到20.3GPa。研究结果表明:在20.3GPa下,LiCoO2的晶体结构非常稳定,并没有发生结构相变;在20.3GPa范围内测量了晶体沿不同晶轴a、c方向的压缩比,发现LiCoO2沿c轴方向的压缩率是沿a轴方向的4.5倍;使用二阶Birch-Murnagha方程拟合出钴酸锂样品的等温状态方程。另外还采用高压原位交流阻抗谱技术(EIS),测量了不同压强下钴酸锂中锂离子导电率,最高压强达到16.8GPa时,发现在实验的压强范围内,随着压强的增加,离子导电率减小。最后将高压下锂离子的电导率与钴酸锂的晶体结构进行联系,进一步阐述了高压下钴酸锂的微观结构和电学性能之间的关系。     

杠杆式金刚石对顶砧高压装置的压力校正

一、前 言 早在三十年代,已经有人开始进行高压下X射线衍射技术的研究[1].随着高压技术的不断发展,实验方法也不断更新,压力范围不断扩大.六十年代初,人们开始应用金刚石对顶砧进行X射线衍射实验[2,3].到了七十年代,这方面的技术有很大的发展,压力可达几十万大气压[4,5]。 对金刚石对顶砧超高压装置进行压力标定,是个普遍关心的问题.在这方面,国际上已进行了许多工作.Decker[6]研究的 NaCl状态方程,作为一种校压基准,已普遍应用于高压下的X射线衍射实验中;七十年代,Barnett[7]等人发现红宝石荧光光谱随着压力升高有线性红移现象,这种现象…     

γ－Fe_2SiO_4在静水压下的压缩行为的测定

采用同步辐射高压原位Ｘ光衍射技术及金刚石对顶压砧高压装置，对γ－Ｆｅ＿２ＳｉＯ＿４进行了静水压条件下等温压缩行为的测定，最高压力达２３ＧＰａ。γ－Ｆｅ＿２ｓｉＯ＿４在０～２３ＧＰａ压力范围内的ｐ、Ｖ数据表明，其等温压缩可分为两个阶段：若设Ｋ＇＿０＝４，在０～１８Ｇｐａ，Ｋ＿０＝１８９±２ＧＰａ；而在１８～２３０Ｐａ，Ｋ＿０＝２１３±２ＧＰａ。我们认为，样品在１８ＧＰａ以下处于较好的静水压状态，压力超过１８ＧＰａ，传压介质的静水压性质变坏，所以Ｋ＿０值偏高。在整个实验过程中并未发现样品有任何发生相变的迹象。最后，对一些虽然使用了液体介质但得不到静水压条件的实验现象进行了讨论。     

锗dc到β-Sn结构的压致相变动力学研究

室温常压下锗是一种具有高载流子迁移率和窄带隙的半导体材料。在高压下,锗具有多种与硅相似的晶相,其有趣的高压行为如压致金属化和超导电性转变引起了高压研究领域的广泛关注。然而,其核心的高压相变动力学机制却鲜有深入研究。利用先进同步辐射光源的高通量X射线衍射结构诊断手段,结合基于金刚石压砧的快速动态压缩技术,研究了锗在高压相变过程中的结构演化机理。采用气膜与压电陶瓷相结合的快速加载方法,实现了数十太帕每秒的压缩速率。采用第三代同步辐射高通量粉光X射线衍射技术,实现了数十微秒时间分辨的结构解析。在相变过程中,新旧相中不同晶面的衍射强度变化存在一定的先后顺序,证实了锗的半导体相(金刚石立方结构)到金属相(β-Sn结构)的转变是位移型相变。此外,通过与静态压缩X射线衍射数据的对比,证实了在此相变过程中不同晶面消失/出现存在先后顺序的行为只能通过动态压缩和动态探测手段观察。     

绿柱石的原位高压X射线研究

 采用同步辐射光源和金刚石对顶砧（DAC）技术,对绿柱石进行了室温下的原位高压能散X射线衍射（EDXD）研究,实验的最高压力为19.2 GPa。在实验压力范围内,未观察到绿柱石发生相变,轴压缩率c大于a;在小于9.3 GPa的压力范围内,其体积压缩率符合二阶Murnaghan状态方程,而压力在9.3～19.2 GPa范围内时,其体积压缩率有所增加,且体积-压力关系近乎线性变化。     

Strength and equation of state of molybdenum triboride under 80 GPa pressure,using radial X-ray diffraction

The strength and equation of state of molybdenum triboride have been determined under nonhydrostatic compression up to 80?GPa, using an angle-dispersive radial X-ray diffraction technique in a diamond anvil cell (DAC). The RXD data yield a bulk modulus and its pressure derivative as K_0?=?342(6)?GPa with K₀′?=?2.11(17) at ψ?=?54.7°. Analysis of diffraction data using the strain theory indicates that the ratio of differential stress to shear modulus (t/G) ranges from 0.002 to 0.050 at pressures of 4–80?GPa. Together with theoretical results on the high pressure shear modulus, our results here show that molybdenum triboride sample under uniaxial compression can support a differential stress of ～10?GPa when it started to yield with plastic deformation at ～30?GPa. In addition, we draw a conclusion that MoB₃ is not a superhard material but a hard material.     

Elastic and plastic deformation of NaCl and Ni3Al polycrystals during compression in a multi-anvil apparatus

Abstract

The compression behaviour in a multi-anvil apparatus of pure NaCl and of a foil of Ni₃Al embedded in a pressure medium of NaCl has been studied by energy-dispersive X-ray diffraction. At ambient temperature, the pressure and stresses, determined from line positions of NaCl, were constant throughout the sample chamber. Line positions and line widths of NaCl reflections were reversible on pressure release. A saturation of microstrains observed in NaCl at 2 GPa is thus attributed to brittle fracture setting in at uniaxial stresses of around 0.3 GPa. Ni₃Al polycrystals, in contrast, undergo extensive (ductile) plastic deformation above 4 GPa. The compression behaviour of both Ni₃Al and NaCl is identical to that previously determined in a diamond anvil cell. While a multi-anvil device thus has the advantage, compared with a diamond anvil cell, of constant pressure and stress throughout the sample chamber, microstrains in poly-crystalline samples arise in both devices. Samples in a multi-anvil apparatus thus need to be mixed with a pressure medium and to consist of essentially single crystals just as in a diamond anvil cell. Annealing experiments at high pressures confirm that the release of the uniaxial stress component in the pressure medium does not cause a release of microstrains in the embedded sample if the latter has been plastically deformed. Annealing for the purpose of attaining hydrostatic conditions in compression studies thus has to be carried out with care.     

Compression behavior of NiO in a diamond cell

Abstract

The compressibility of synthetic polycrystalline NiO was studied in a diamond anvil cell at room temperature utilizing two different X-ray sources. A standard film with a conventional X-ray source and the energy dispersive X-ray diffraction (EDXRD) method with synchrotron radiation were used for data acquisition. In the film method, the sample was compressed in a 4:1 methanol to ethanol solution up to 7 GPa with ruby fluorescence as a pressure calibrant. In the energy dispersive method, NiO powder was mixed with gold and compressed in two different conditions: gasketed and ungasketed up to 30 GPa. In the gasketed run, water was used as the pressure transmitting medium while gold was used as pressure calibrant in both runs.

Hydrostatic compression of NiO in both diffraction methods yields a bulk modulus (K _o) of 187 ± 7 GPa assuming K′ = 4. The compression of gasketed NiO of the synchrotron experiment, however, showed an obvious break at pressure exceeding 4 GPa due to the loss of hydrostaticity. NiO in a nonhydrostatic condition behaves with less compressibility than the hydrostatic results with a nominal K _o of 238 ± 10 GPa. The lower compressibility of NiO in synchrotron runs is attributed to the uniaxial loading effect which was more easily detected by the EDXRD geometry. The discrepancy in the bulk modulus can be attributed to the contrast in the shear strength between the sample and pressure medium and the Poisson effect of the sample under uniaxial loading.     

A CCD based detector for quick detection of pressure induced phase transitions

Abstract

A high sensitivity CCD based two dimensional angle dispersive X-ray are a detector has been developed for quick detection of pressure induced phase transitions for a laboratory X-ray source such as a rotating anode generator. The performance of this detector was tested by successfully carrying out powder X-ray diffraction measurements on element Pd, intermetallics AuIn², AuGa² and low Z scatterer adamantane (C₁₀H_l6) at ambient conditions. Its utility for quick detection of phase transitions at high pressures with diamond anvil cell (DAC) is demonstrated by reproducing the known pressure induced structural phase transitions in RbI and KI. The importance of this detector system in search of unknown phase transitions has been established by observing new structural phase transitions in In_0.25Sn_0.75 and AuGa₂. Various softwares have also been developed such as interactive location of centre of diffraction rings, radial integration and image enhancement to analyze data from this detector.     

Amorphous boron composite gaskets for in situ high-pressure and high-temperature studies

The diamond anvil cell (DAC) is a fundamental device used to explore the properties of materials under extreme pressure and temperature (P/T) conditions. In the past years, simultaneous high P/T DAC experiments using the resistively heated DAC (RH-DAC) techniques have been developed for studying materials properties in a wide P/T range. However, the mechanical instability of metallic gaskets used for sample confinement at high P/T conditions remains a limiting factor for exploiting the accessible P/T range of the RH-DAC. In this study, we present a new gasket configuration that overcomes these limitations. It is based on an amorphous boron–epoxy mixture inserted in a rhenium gasket. We show how these gasket inserts stabilize the sample chamber over a wide P/T range, allowing monitoring sample properties using X-ray diffraction and absorption spectroscopy up to 50?GPa and 1620?K.     

Preparation of a macrocrystalline pressure calibrant SrB4O7:Sm 2+ suitable for the HP-HT powder diffraction

A new simplified synthesis of monocrystalline chips of SrB₄O₇: Sm²⁺ pressure calibrant, well-suited for the diamond anvil cell (DAC) powder diffraction experiments, is proposed. It consists of ordinary solid-state synthesis of fine-grained SrB₄O₇: Sm²⁺ and subsequent annealing near melting temperature. The obtained material was characterized and tested in HP-HT DAC experiment.     

纤锌矿氮化硼及其应用的研究（Ⅱ）——纤锌矿型氮化硼的等温状态方程

 使用两种不同的高压在位X光衍射法，研究了用爆炸法合成的纤锌矿型氮化硼（wBN）在室温下的等温状态方程。一种方法是用转靶X光角色散粉末衍射法，研究了它在0~40 GPa压力范围内的等温压缩行为。结果表明，wBN在0~40 GPa的压力范围内是稳定的，没有发生结构相变。通过p-V数据对Murnaghan方程拟合，得到wBN在p=0时的等温体模量B₀=(335±34) GPa及其对压力的一阶导数B₀'=4.21；另一种是用同步辐射X光能量色散衍射法，研究了它在0~25 GPa压力范围内的等温状态方程。实验中，使用了改进的自动加压的DAC高压装置，此装置保证了实验中衍射角θ₀固定不变。将获得的p-V数据仍用Murnaghan方程拟合，得到wBN在p=0时等温体模量B₀=(280±56) GPa，及其B₀'=4.39。     

High pressure generation using double-stage diamond anvil technique: problems and equations of state of rhenium

We have developed a double stage diamond anvil cell (ds-DAC) technique for reproducible pressure by precisely fabricating 2nd stage anvils using a focused ion beam system. We used 2nd stage micro-anvils made of ultra-fine (V/V₀?=?0.633 for the smallest d-spacing. The calculated pressure for this minimum volume varies from 430 to 630?GPa, depending on the choice of the equation of state of rhenium. We conclude that the most likely pressure achieved for the minimum volume of rhenium is in a range of 430–460?GPa based on a calibration using the platinum pressure scale to 280?GPa and the latter value of 630?GPa is unreasonably high, suggesting that the pressures in an earlier study for the equation of state of rhenium would have been significantly overestimated.     

高压下天然顽火辉石能量色散X射线粉末衍射研究

 在北京同步辐射装置（BSRF）高压站对采自于河北大麻坪的天然顽火辉石,在室温高压（0~31.64 GPa）下,利用金刚石压腔装置（DAC）,进行了能量色散X射线粉末衍射（EDXD）原位测量,得到了顽火辉石在不同压力下的衍射图谱,并利用UnitCell软件进行解谱,获得了其晶胞参数a、b、c和晶胞体积V及其随压力的变化,最后利用Murnaghan等温方程得到了天然顽火辉石的体积模量K_T(0)=172 GPa、压缩系数及p-V状态方程,发现沿a、b、c三方向的压缩系数存在明显的各向异性,结果与斜方辉石的弹性波速各向异性完全一致。     

White-beam X-ray diffraction and radiography studies on high-boron-containing borosilicate glass at high pressures

ABSTRACT

Multi-angle energy-dispersive X-ray diffraction studies and white-beam X-ray radiography were conducted with a cylindrically shaped (1?mm diameter and 0.7?mm high) high-boron-content borosilicate glass sample (17.6% B₂O₃) to a pressure of 13.7?GPa using a Paris-Edinburgh (PE) press at Beamline 16-BM-B, HPCAT of the Advanced Photon Source. The measured structure factor S(q) to large q?=?19 Å^?1 is used to determine information about the internuclear bond distances between various species of atoms within the glass sample. Sample pressure was determined with gold as a pressure standard. The sample height as measured by radiography showed an overall uniaxial compression of 22.5% at 13.7?GPa with 10.6% permanent compaction after decompression to ambient conditions. The reduced pair distribution function G(r) was extracted and Si–O, O–O and Si–Si bond distances were measured as a function of pressure. Raman spectroscopy of the pressure recovered sample as compared to starting material showed blue-shift and changes in intensity and widths of Raman bands associated with silicate and four-coordinated boron.