Ruby-spheres as pressure gauge for optically transparent high pressure cells

Abstract

Ruby is widely used as an in siru pressure gauge for optically transparent pressure cells up to the megabar range. Usually ruby chips cut from bulk crystals are used which are ill-characterized and inconvenient to handle and to identify visually. Here we present a systematic study on corundum samples doped with Cr³⁺ ions with concentration from 60 to 23500 ppm to determine the optimal conditions for the use as an accurate pressure marker. The influence of the excitation wavelength on the luminescence spectra was investigated. These studies led to the synthesis of small (1–50 micrometer) ruby spheres with 3000 ppm chromium concentration. After annealing and a heat treatment to avoid internal strains we find reproducible values of the position and the width of the fluorescence lines. These ruby spheres are not only well suited for a reliable and accurate pressure determination in experiments using diamond anvil cells, but can also be used as an in sihr micro-thermometer in high pressure-low temperature studies.     

超高压下红宝石荧光R线的猝灭压力与入射激发线波长的关系

 分别使用固态氩和体积比为4∶1的甲醇-乙醇混合溶液做传压介质，测量红宝石在这两种介质中的荧光光谱随压力的变化。首先发现在超高压下红宝石荧光R线的压致猝灭与入射激发线波长以及高压样品室内的静水压程度有关。实验结果表明：入射激发线的波长越长，荧光R线的猝灭压力越低；对同一激发线波长，静水压程度差，猝灭压力高。这一现象归因于红宝石吸收谱中U带和Y带随压力的蓝移。     

90 GPa（准）静水压力的产生及压力分布的测量

 本文使用固态氩做传压介质，在自制的Mao-Bell型金刚石对顶砧装置中获得了90 GPa的准静水压。通过测量样品室内不同位置上红宝石荧光R₁线的频移来确定压力分布。实验结果表明在80 GPa以下，样品室内不同位置上的压力与平均压力（p）的差Δp很小，最大的Δp/p不超过1.5%。在90 GPa时，红宝石的荧光R线与常压的很相似。这表明利用固态氩做传压介质可以获得接近100 GPa的准静水压。此外，对红宝石荧光光谱中位置在14 938 cm^-1和14 431 cm^-1两条谱线随压力的变化情况也作了讨论，并由此得出结论，14 938 cm^-1这条线也可用来标定压力。     

Hysteresis of ruby fluorescent line by pressure and annealing effect

Abstract

Accuracy of hydrostatic pressure measurement in a diamond-anvil cell (DAC) depends on the reproducibility of ruby RI fluorescent measurement. The larger scatter in R, fluorescent wavelength shift than the reproducibility of spectroscopic measurement was observed among appropriately mirror-finished ruby plates before setting up in DAC. The characteristics of the scatter changed after loading DAC up to pressure over hydrostatic limit. They vanished by annealing the ruby plates. These phenomena are presumably due to the appearance and disappearance of the residual stress in the ruby crystal. Such hysteresis of ruby fluorescent wavelength shift by pressure and its annealing effect are discussed.     

用高压显微光谱系统研究(Zn0.85Cd0.15)S:Cu,Al磷光体在流体静压力下施主-受主对的发光

用金刚石对顶砧高压显微光谱系统在室温和1bar—66kbar的流体静压力范围内研究了(Zn_0.85Cd_0.15)S:Cu,Al磷光体的发光峰位置和相对发光强度随压力而变化的规律。随着压力的增加,发射峰值波长迅速移向短波方向,而发射峰值对应的光子能量随压力增加的速率为4.7meV/kbar(38cm^-1/kbar)。这个值比该材料的吸收边随压力增加的速率要小。随着压力的增加,该磷光体的发光峰值相对强度急骤下降,当压力从常压升到66kbar时,发光峰值相对强度下降到原值的6％。这些结果可以用Al³⁺-Cu⁺的施主-受主对模型来解释。本文还估计施主(Al³⁺)和受主(Cu⁺)的激活能之和随压力增加的速率为3.7meV/kbar(30cm^-1/kbar)。 关键词：     

160 GPa压力范围内重新标定的红宝石压标

 在同一理论框架内,基于冲击Hugoniot和热力学参数计算了Al、Cu、W、 Au、Pt、Ta、Ag、Mo、Ni、Co和Zn的300 K等温压缩线,并结合现有静高压实验数据,在160 GPa压力范围内重新标定了红宝石压标。所采用的两种红宝石压标形式的标定结果分别为A=1 923.4 GPa、B=9.75和m=1 889.0 GPa、n=5.48,两者具有非常好的自洽性,200 GPa压力范围内确定的压力偏差小于2.1 GPa。基于提出的红宝石压标,重新计算了3组Au等温压缩实验的加载压力。固定等温体模量为167 GPa,重算的实验数据拟合至Vinet物态方程所得等温体模量对压力的一阶偏导为5.95,与超声实验数据非常吻合。     

红宝石能谱的理论研究

 本文用限制Hartree-Fock自洽场方法对红宝石进行了计算，得到了单电子分子轨道，在此基础上利用不可约张量方法求解红宝石价电子体系多体Schrodinger方程，得到了与实验相符的红宝石d－d跃迁能谱，标准误差为九百波数。进一步计算了在不同压力下红宝石d－d跃迁能谱。结果表明，能谱中R₁线（⁴A₁→²E）随压力增大产生红移，与实验定性一致。     

用高压显微光谱系统研究非晶态As2S3的光学折射率随流体静压力变化的规律

用金刚石对顶砧高压显微光谱系统在高达66kbar的流体静压力和光谱波段为400—900nm范围内,用透射光干涉谱法测量了非晶态As₂S₃(a-As₂S₃)的光学折射率n与压力p以及波长λ的变化关系。a-As₂S₃的折射率对压力极为敏感,在波长为650nm,压力从1bar变到66kbar时,它增加35％。在计算机上用最小二乘法对实验点进行拟合的结果得到:对某一波长λ来说,遵循n(P)=n(0)+Ap+Bp²的非线性关系。其中n(p)和n(0)是p压和常压下的折射率,A和B是与波长有关的系数,文中给出了A和B的具体参数。这个关系与Weinstein和Galkiewicz等人公布的n(p)和p之间遵循线性关系不同。 关键词：     

126.5 GPa准静水压下的光谱学实验

 本文介绍了作者利用国内加工的金刚石压砧装置及组建的微区光谱系统进行100 GPa（百万大气压）准静水压光谱学实验的概况，证明压力产生装置和微区光谱系统的多功能性是充分可靠的。实验中遇到的压力产生能力超过压力测量能力的事实，反映了高压光谱学实验在压力范围扩大时所遇到的挑战。文中对高压下的拉曼、发射、吸收及反射光谱的实验原理和实验方法也作了概略的介绍。     

Dependence of the annihilation pressure of ruby R-line fluorescence on the laser exciting wavelength

Abstract

Using solid argon as pressure medium, quasi-hydrostatic pressure was obtained at room temperature in the diamond cell up to 90 GPa. The mechanism of the disappearance of ruby R lines and the applicability of ruby pressure scale under quasi-hydrostatic pressure above 100 GPa was discussed. The deviation of every pressure measured at nine positions in the cell per mean pressure was less than 1.5% at pressure below 80 GPa.     

高压低温条件下固态氩和4∶1甲醇-乙醇混合物传压介质的传压特性

 在高压低温（77 K）条件下，利用红宝石荧光测压方法，系统地研究了金刚石对顶砧装置中固态氩和4∶1甲醇-乙醇混合物的传压特性。通过测量不同位置上红宝石荧光R₁线的频移，确定了样品室内的压力分布。实验结果表明：在0~16 GPa的压力范围内，固态氩介质中反映介质非均匀性程度的|Δp/p|<3%、σ_p/p<2%，均在室温静水压条件下所允许的范围之内。红宝石荧光R线除随压力变宽外，与常压的很相似，表明固态氩在高压低温条件下是良好的传压介质。与之相比，4∶1甲醇-乙醇介质在77 K低温下的传压特性明显差于固态氩，已不适合作传压介质。     

An opposed-anvil-type apparatus with an optical window and a wide-angle aperture for neutron diffraction

We designed new anvil assemblies for acquiring high-quality neutron diffraction data and ruby fluorescence spectra inside a sample chamber. The conical aperture of Ni-binded WC anvils was expanded by a factor of two. A hybrid gasket made of TiZr- and Al-alloy was developed to prevent outward extrusion. A small and optically transparent window of moissanite was introduced to allow for the determination of pressure and hydrostaticity by measurement of ruby fluorescence spectra. High pressure-generation tests that make use of Bi electrical conductivity and ruby pressure markers revealed that pressure could be determined over 10 GPa. In situ synchrotron X-ray diffraction experiments were also carried out using NaCl as the pressure calibrants. The maximum pressure achieved was approximately 13 GPa. The neutron diffraction intensity from the newly generated anvil assemblies was 2.5–3.0 times greater than that using the standard toroidal anvil assemblies used previously.     

Progress in pressure measurements with luminescence sensors

Abstract

Various luminescence sensors for pressure measurements are compared with the generally used ruby sensor. Typical advantages and disadvantages of different luminescence sensors based on lanthanide ions in various hosts are discussed. Emphasis is given to the sensor based on Sm^2?: MFCl (M =Sr, Ba) with respect to its sensitivity, temperature dependence and range of applicability.     

外加热型金刚石对顶压砧高压装置及高温下的压力测量

 本文报导了一种外加热型金刚石对顶压砧装置的高温高压技术，装置的压力可达20 GPa，温度可达350 ℃。采用本装置对六角结构的α-LiIO₃进行了高温高压X射线衍射实验，获得的四方结构高压相与用淬火卸压所得的ε相结构一致；建立了高温下的红宝石测试技术。发现可以根据由此法测定的Δγ_p-T曲线初步判别样品是否存在伴随有体积变化的结构相变，并可估计出该相变的压力、温度范围及相变造成的压力下降值。     

Ruby fluorescence lifetime measurements for temperature determinations at high (p,T)

The lifetime of the ruby R₁ fluorescence line was measured as a function of pressure (up to about 20 GPa) and temperature (550 K) in an externally heated diamond anvil cell (DAC). At constant temperatures, the lifetime is increasing linearly with increasing pressure. The slope of the pressure dependence is constant up to a temperature of 450 K and it is decreasing at higher temperatures. At constant pressure, the lifetime is exponentially decreasing with increasing temperature. The (p, T)-dependence can be parametrized by the combination of a linear and an exponential function. This allows an accurate p, T-determination by the combination of fluorescence spectroscopy using Sm²⁺-doped strontium tetraborate and lifetime measurements of ruby, as the energy of the Sm²⁺ fluorescence is nearly temperature-independent.     

In situ solidification of ionic liquid [EMIM][EtOSO3] from melt under high pressure

In situ solidification of 1-ethyl-3-methylimidazolium ethyl sulfate [EMIM][EtOSO₃] from melt under high pressure has been investigated by using Raman spectroscopy. The results indicate that [EMIM][EtOSO₃] might experience a phase transition at about 2.4 GPa upon compression, which could be identified as solidification to a superpressurized glass by pressure broadening of the sharp ruby R₁ fluorescence line. Upon cooling, it solidifies as a glassy state rather than crystallizes at low temperature down to 93 K. These facts are suggestive of a phase transition of liquid to a superpressurized glass induced by compression in [EMIM][EtOSO₃], which is similar to the glassy state at low temperature.     

红宝石R'、B线及U、Y带压力移位的理论计算

基于电子径向波函数在加压下扩展的概念,把B、C、Dq、ξ等参量表示成线性压缩κ\的函数,并进一步考虑三角场作用,理论计算了红宝石R''、B线及U、Y带的光谱压力移位,结果与实验数据符合很好.     

High Pressure Spectroscopy of Ti Doped Al2O3 and YAIO3 Host Crystals

We report high-pressure luminescence spectroscopy studies of Ti^3? in Al₂O₃ and YAlO₃. High-pressure luminescence spectra were measured for Al₂O₃:Ti^3? up to 90kbar and for YAlO₃:Ti^3? up to 181 kbar. In both cases, a blue shift of the luminescence peak with pressure was observed and is attributed to an increase in the octahedral crystal-field strength (10 Dq) with pressure. In the case of YAlO₃;Ti^3?, an additional luminescence peak was observed at 181 kbar and below ～ 200 K, and is attributed to a metastable state. The metastability of the ²E excited state was induced by pressure that removes the equivalency of three energy minima of the ²E state coupled to the ? mode.     

Equations of state for Cu,Ag, and Au and problems with shock wave reduced isotherms

Thermophysical data at low pressure are used to constrain a thermodynamic model for equations of state and all the other thermophysical properties in wide ranges of pressure and temperature. Comparisons with shock wave reduced isotherms show strong deficiencies in the models used in the data reductions. A revision in the evaluation of static high-pressure X-ray diffraction data for Cu and Au together with data for ruby luminescence line shifts from the literature lends further support to some recent refinements of the ruby pressure scale.