Anti-Stokes/Stokes temperature calibration and its application in laser-heating diamond anvil cells

Anti-Stokes/Stokes Raman peak intensity ratio was used to infer sample temperatures,but the influence factors of system correction factors were not clear.Non-contact in-situ anti-Stokes/Stokes temperature calibration was carried out for up to 1500 K based on six different samples under two excitation light sources(±50 K within 1000 K,±100 K above1000 K),and the system correction factorγwas systematically investigated.The results show that the correction factorγof anti-Stokes/Stokes thermometry is affected by the wavelength of the excitation light source,Raman mode peak position,temperature measurement region and other factors.The anti-Stokes/Stokes thermometry was applied to the laser-heating diamond anvil cell(LHDAC)experiment to investigate the anharmonic effect of h BN under high temperature and high pressure.It is concluded that the strong anharmonic effect caused by phonon scattering at low pressure gradually changes into the predominance of localized molecular lattice thermal expansion at high pressure.

Laser-Heated Diamond-Anvil Cell (LHDAC) in Materials Science Research

Laser-heated diamond-anvil cell (LHDAC) is emerging as the most suitable, economical and versatile tool for the measurement of a large spectrum of physical properties of materials under extreme pressure and temperature conditions. In this review, the recent developments in the instrumentation, pressure and temperature measurement techniques, results of experimental investigations from the literature were discussed. Also, the future scope of the technique in various avenues of science was explored.

Application of Hydrothermal Diamond Anvil Cell to Homogenization Experiments of Silicate Melt Inclusions

The homogenization of silicate melt inclusions （SMIs）,small droplets of silicate melt trapped in magmatic minerals,is an important component of petrogenetic and magmatic research.Conventional homogenization experiments on SMIs use microscope-mounted heating stages capable of producing high temperatures at 1 atm and cold-seal high-pressure vessels.Heating stages are generally used for SMIs with low internal pressures and allow in situ observations of the homogenization processes.In contrast,cold-seal high-pressure vessels are generally used to heat SMIs that have high internal pressures,although the homogenized SMIs can only be observed after quenching in this approach.Here we outline an alternative approach that uses a hydrothermal diamond anvil cell （HDAC） apparatus to homogenize SMIs.This is the only current method wherein phase changes in high-internal-pressure SMIs can be observed in situ during homogenization experiments,which represents an advantage over other conventional methods.Using an HDAC apparatus prevents high-internal-pressure SMIs from decrepitating during heating by elevating their external pressure,in addition to allowing in situ observations of SMIs.The type-V HDAC that is currently being used has a shorter distance between the sample chamber and the observation window than earlier types,potentially enabling continuous observation of the processes involved in heating and SMI homogenization through an objective lens with a long working distance.Homogenization experiments using HDAC require that a number of steps,including HDAC preparation,sample preparation,sample loading,preheating,and formal heating,be carefully followed.Homogenization experiments on SMIs within granite samples from the Jiajika pegmatite deposit （Sichuan,China） are best performed using an HDAC-based approach,because the elevated proper external pressure of these SMIs,combined with a short heating duration,helps to suppress material leakage and any reactions within the SMIs,in addition to allowing in situ observations during homogenization experiments.Furthermore,using the HDAC approach has other benefits：heating rates can be precisely controlled,wafer oxidization can be prevented,and samples can be subjected to in situ microbeam analysis.In summary,homogenization using HDAC provides more reliable results than those obtained using conventional heating equipment.Future developments will include improvements to the quenching method and temperature controls for the HDAC apparatus,thereby improving the utility of this approach for SMI homogenization experiments.

A Study of Near-and Super-Critical Fluids Using Diamond Anvil Cell and in-Situ FT-IR Spectroscopy

The phase relation and solution structure of water and NaCl aqueous solution have been observed and examined by using the hydrothermal diamond anvil cell (HDAC) at elevated temperatures and pressures and the in situ FT-IR spectroscopy. The temperature of observations ranges from 25 to 850°C and the pressure up to 10 or 30 kb. At first, we observed the phase transition process from halite+liquid+vapour (H+L+V) to L+H, then to L (or supercritical fluid, SCF), and another path: H+L+V→L+V→L (or SCF) in heating process. By means of the visual microscope, the authors found that in the L+V immiscibility field L+V exhibits an ordered structure, i.e. a large visual cluster of solvent around ions. The liquid phase is manifested by vapour bubbles. When phase transitions are observed, the authors examined their infrared spectra by using the FT-IR microscopy simultaneously. In the case of the phase transition from liquid (L) to liquid + vapor (L+V) immisciblity field of NaCl solutions, a sudden change (strong frequency shift) of infrared spectra of the aqueous solution is observed near the critical temperature of water as the temperature is raised from 25 to 650°C. The frequency of the maximum intensity of OH symmetric and asymmetric vibration varies with respect to temperature. The sharp peak of the OH stretching vibration of the maximum intensity appears in an interval from 300 to 400°C. It is indicated that the hydrogen bonding network is weakened and broken at last near the critical point of water, which causes the aqueous solution to become more associated. Besides, a pressure indicator (a mineral or compound) was introduced to the HDAC.

Origin of deep carbonate reservoir in northeastern Sichuan Basin:New insights from in-situ hydrothermal diamond anvil cell experiments

In situ Raman analysis on the segregated near-equilibrium carbonate-fluid interaction at elevated temperatures(room temperature-260 °C) and pressures(13-812 MPa) in a hydrothermal diamond anvil cell(HDAC) reveals the preservation mechanism of porosity in deep carbonate reservoirs in the northeastern Sichuan Basin. The carbonate-fluid interaction was investigated by separately heating carbonate minerals and rocks with four different acid solutions(saturated CO2 and H2 S solutions, HCl, CH3COOH) in a sealed sample chamber. A minor continuous precipitation with increasing temperatures and pressures was observed during the experiments which caused minor sample volume change. The closed system is a preservation of pores and burial dissolution may not be the dominant diagenesis in the origin of porosity. Thin section photomicrographs observations in Changxing and Feixianguan Formations demonstrate that eogenetic pores such as moldic or intragranular pores with late small euhedral minerals, intergranular, intercrystal and biological cavity pores are the main pore types for the reservoirs. Early fast deep burial makes the porous carbonate sediments get into the closed system as soon as possible and preserves the pores created in the early diagenetic stage to make significant contribution to the deep reservoir quality. The anomalous high porosity at a given depth may come from the inheritance of primary pores and eogenetic porosity is fundamental to carbonate reservoir development. The favorable factors for deep reservoir origin include durable meteoric leaching, early fast deep burial, early dolomitization, etc. This deep pores preservation mechanism may be of great importance to the further exploration in deep carbonate reservoirs in the northeastern Sichuan Basin.

Magnetic field analysis in a diamond anvil cell for Meissner effect measurement by using the diamond NV^- center

Diamond negatively charged nitrogen-vacancy(NV-) centers provide an opportunity for the measurement of the Meissner effect on extremely small samples in a diamond anvil cell(DAC) due to their high sensitivity in detecting the tiny change of magnetic field. We report on the variation of magnetic field distribution in a DAC as a sample transforms from normal to superconducting state by using finite element analysis. The results show that the magnetic flux density has the largest change on the sidewall of the sample, where NV-centers can detect the strongest signal variation of the magnetic field. In addition, we study the effect of magnetic coil placement on the magnetic field variation. It is found that the optimal position for the coil to generate the greatest change in magnetic field strength is at the place as close to the sample as possible.

Thermal conductivity of dense hcp iron:Direct measurements using laser heated diamond anvil cell

Thermal conductivity(k)of iron is measured up to about 134 GPa.The measurements are carried out using the single sided laser heated diamond anvil cell,where the power absorbed by a Fe metal foil at hotspot is calculated using a novel thermodynamical method.Thermal conductivity of fee(γ)-Fe increases up to a pressure of about46 GPa.We find thermal conductivity values in the range of 70-80 Wm-1K-1(with an uncertainty of 40%),almost constant with pressure,in the hcp(e)phase of Fe.We attribute the pressure independent k above 46 GPa to the strong electronic correlation effects driven by the electronic topological transition(ETT).We predict a value of thermal conductivity ofε-Fe of about 40±16 Wm-1K-1 at the outer core of Earth.

Effect of deformation of diamond anvil and sample in diamond anvil cell on the thermal conductivity measurement

Studies show that the sample thickness is an important parameter in investigating the thermal transport properties of materials under high-temperature and high-pressure(HTHP)in the diamond anvil cell(DAC)device.However,it is an enormous challenge to measure the sample thickness accurately in the DAC under severe working conditions.In conventional methods,the influence of diamond anvil deformation on the measuring accuracy is ignored.For a hightemperature anvil,the mechanical state of the diamond anvil becomes complex and is different from that under the static condition.At high temperature,the deformation of anvil and sample would be aggravated.In the present study,the finite volume method is applied to simulate the heat transfer mechanism of stable heating DAC through coupling three radiativeconductive heat transfer mechanisms in a high-pressure environment.When the temperature field of the main components is known in DAC,the thermal stress field can be analyzed numerically by the finite element method.The obtained results show that the deformation of anvil will lead to the obvious radial gradient distribution of the sample thickness.If the top and bottom surfaces of the sample are approximated to be flat,it will be fatal to the study of the heat transport properties of the material.Therefore,we study the temperature distribution and thermal conductivity of the sample in the DAC by thermal-solid coupling method under high pressure and stable heating condition.

Investigating the thermal conductivity of materials by analyzing the temperature distribution in diamond anvils cell under high pressure

Investigating the thermal transport properties of materials is of great importance in the field of earth science and for the development of materials under extremely high temperatures and pressures.However,it is an enormous challenge to characterize the thermal and physical properties of materials using the diamond anvil cell(DAC)platform.In the present study,a steady-state method is used with a DAC and a combination of thermocouple temperature measurement and numerical analysis is performed to calculate the thermal conductivity of the material.To this end,temperature distributions in the DAC under high pressure are analyzed.We propose a three-dimensional radiative-conductive coupled heat transfer model to simulate the temperature field in the main components of the DAC and calculate in situ thermal conductivity under high-temperature and high-pressure conditions.The proposed model is based on the finite volume method.The obtained results show that heat radiation has a great impact on the temperature field of the DAC,so that ignoring the radiation effect leads to large errors in calculating the heat transport properties of materials.Furthermore,the feasibility of studying the thermal conductivity of different materials is discussed through a numerical model combined with locally measured temperature in the DAC.This article is expected to become a reference for accurate measurement of in situ thermal conductivity in DACs at high-temperature and high-pressure conditions.

In situ study of calcite-Ⅲ dimorphism using dynamic diamond anvil cell

The phase transitions among the high-pressure polymorphic forms of CaCO_(3)(cc-Ⅰ,cc-Ⅱ,cc-Ⅲ,and cc-Ⅲb)are investigated by dynamic diamond anvil cell(dDAC)and in situ Raman spectroscopy.Experiments are carried out at room temperature and high pressures up to 12.8 GPa with the pressurizing rate varying from 0.006 GPa/s to 0.056 GPa/s.In situ observation shows that with the increase of pressure,calcite transforms from cc-Ⅰto cc-Ⅱat~1.5 GPa and from cc-Ⅱto cc-Ⅲat~2.5 GPa,and transitions are independent of the pressurizing rate.Further,as the pressure continues to increase,the cc-Ⅲb begins to appear and coexists with cc-Ⅲwithin a pressure range that is inversely proportional to the pressurizing rate.At the pressurizing rates of 0.006,0.012,0.021,and 0.056 GPa/s,the coexistence pressure ranges of cc-Ⅲand cc-Ⅲb are 2.8 GPa-9.8 GPa,3.1 GPa-6.9 GPa,2.7 GPa-6.0 GPa,and 2.8 GPa-4.5 GPa,respectively.The dependence of the coexistence on the pressurizing rate may result from the influence of pressurizing rate on the activation process of transition by reducing the energy barrier.The higher the pressurizing rate,the lower the energy barrier is,and the easier it is to pull the system out of the coexistence state.The results of this in situ study provide new insights into the understanding of the phase transition of calcite.

How far away are accurate equations of state determinations? Some issues on pressure scales and non-hydrostaticity in diamond anvil cells

The equations of state(EOSs)of materials are the cornerstone of condensed matter physics,material science,and geophysics.However,acquiring an accurate EOS in diamond anvil cell(DAC)experiments continues to prove problematic because the current lack of an accurate pressure scale with clarified sources of uncertainty makes it difficult to determine a precise pressure value at high pressure,and nonhydrostaticity affects both the volume and pressure determination.This study will discuss the advantages and drawbacks of various pressure scales,and propose an absolute pressure scale and correction methods for the effects of non-hydrostaticity.At the end of this paper,we analyze the accuracy of the determined EOS in the DAC experiments we can achieve to date.

How to detect melting in laser heating diamond anvil cell

Research on the melting phenomenon is the most challenging work in the high pressure/temperature field. Until now,large discrepancies still exist in the melting curve of iron, the most interesting and extensively studied element in geoscience research. Here we present a summary about techniques detecting melting in the laser heating diamond anvil cell.

Raman scattering from highly-stressed anvil diamond

The high-frequency edge of the first-order Raman mode of diamond reflects the stress state at the culet of anvil, and is often used for the pressure calibration in diamond anvil cell(DAC) experiments. Here we point out that the high-frequency edge of the diamond Raman phonon corresponds to the Brillouin zone(BZ) center Γ point as a function of pressure. The diamond Raman pressure gauge relies on the stability of crystal lattice of diamond under high stress. Upon the diamond anvil occurs failure under the uniaxial stress(197 GPa), the loss of intensity of the first-order Raman phonon and a stressdependent broad Raman band centered at 600 cm^(-1) are observed, which is associated with a strain-induced local mode corresponding to the BZ edge phonon of the L1 transverse acoustic phonon branch.

花岗岩类锂矿床中锂辉石和锂云母共生性的实验模拟研究

锂是一种稀有金属元素,锂辉石和锂云母是最重要的硬岩型锂矿矿石矿物,探究二者的共生性及条件,对揭示锂元素在不同锂矿石矿物中的赋存机制以及花岗岩类锂矿床的形成机制具有重要意义。本文应用热液金刚石压腔开展了锂辉石-锂云母-H_(2)O体系的原位观测结晶实验,10组实验产物均为锂辉石和白云母,锂辉石结晶集中在500~780℃、350~1300MPa的温压条件下,白云母结晶集中在440~710℃、180~1100MPa的温压条件下。结合前人实验得到的锂云母结晶条件(500~650℃、100~450MPa),以及实验产物云母的激光拉曼线扫结果,可以得到以下认识:锂辉石与白云母结晶温压条件具有较高的重叠度,与二者可在伟晶岩中广泛共生的现象一致;锂辉石和锂云母的结晶主要受到压力影响,温度和体系F含量的影响居于次要地位;透锂长石和锂云母形成于相似的温压条件,但体系F含量的高低分别促进锂云母和透锂长石的产出;在富Li体系中,随着压力的降低可以发生白云母到锂云母的转化,指示出自然界中白云母的锂云母边可能形成于熔体或热液结晶过程中,不一定是热液蚀变的结果。

金刚石压腔(DAC)实验技术

金刚石压腔实验技术自20世纪50年代发明以来就被广泛应用于高压领域的研究,特别是近年来,随着温度、压力标定技术及各种测试方法的发展,现在已经被广泛应用于物理、化学、地球科学和生物学研究领域。文章通过Mao Bell压腔说明金刚石压腔实验装置的结构及原理。此外,根据温度和压力测定原理,将金刚石压腔的加热装置分为外加热和激光加热,并将压力测量方法划分为三种:(1)矿物谱学压力测定;(2)状态方程压力测量;(3)矿物相变法压力标定。

高压下二元富氢超导体的实验研究进展

自从1911年著名物理学家Onnes发现超导电性以来,人们不断努力提高超导转变温度,室温超导体是人类追逐的百年梦想。在近百年的研究历程中,铜基超导体、铁基超导体及麦克米兰极限MgB_(2)超导体的发现不断刷新了人们对超导领域的认知,也增强了人们进一步提高超导转变温度和挖掘高温超导机制的信心。最近,理论预测并被实验验证的新型富氢化合物显示了高温乃至室温超导电性的巨大潜力,成为室温超导体的最佳候选体系之一。值得注意的是,高压下硫氢化物和镧氢化物均具有超过200 K的超导转变温度,引领了富氢化合物的研究热潮,涌现了一些重要的理论和实验成果。本文聚焦于目前富氢化合物超导体的实验研究进展,从不同氢结构单元及氢成键特征的角度总结和归纳新型富氢化合物的晶体结构性质及超导性能。主要介绍了5种在实验上成功获得的富氢化合物超导体:间隙型、离子型、共价型、笼型及分子型。通过对比分析不同类型的富氢化合物超导体,总结出一些影响超导转变温度的普适规律,并提出目前实验上亟待解决的问题和未来主攻的实验方向。

金刚石压腔(DAC)技术及其在地球科学中的应用

近几十年来金刚石压腔(DAC)技术被广泛应用于高温高压实验研究领域,它可以达到550GPa的压力和6 000K的温度。与其他静高压实验技术(大压力机、高压釜等)相比,金刚石压腔具有独特的优势,它不仅可以进行极端温压条件下物质的结构性质、相变及状态方程等研究,而且可以原位观测整个实验过程。文中简述了金刚石压腔装置的结构及温压测量方法,然后分别从物质相变、矿物溶解度、流体性质和组成、油气成因、稳定同位素分馏系数和布里渊声学测量等方面简要介绍了金刚石压腔技术在地球科学中的研究进展。随着实验技术的不断发展和更新,金刚石压腔技术将具有更广阔的应用前景。

动态压力加载/卸载装置dDAC及原位表征技术研究进展

动态压力加载/卸载装置dDAC(Dynamic diamond anvil cell)是近年来备受高压界关注的研究装置之一,可以用来开展亚稳态材料制备、相变动力学、超高压化学等方面研究,在材料学、凝聚态物理学、化学、地学等领域具有重要的应用前景。综述了近年来国内外动态压力加载/卸载装置及原位表征技术的研究进展,详细介绍了一套新型与原位时间分辨光谱测试系统及原位加热/冷却系统相结合的、具有较大加载/卸载速度和较宽压力范围的动态压力加载/卸载装置。该动态压力加载/卸载装置及原位光谱表征系统的建立,将成为新的高压实验研究平台,从而促进高压极端条件下材料新结构和新性能等方面的研究。

热液金刚石压腔 (HDAC)在地质上的应用及甲烷水合物合成实验研究

热液金刚石压腔 (HDAC)是 2 0世纪末发展起来的一种高温高压及低温高压实验技术。它可在 - 180～ 12 0 0℃ ,10 0～ 10 0 0 0MPa水热体系进行实验 ,并具直观实验全过程的特点。文中首次运用HDAC在水体系中对哀牢山花岗岩进行了熔融实验 ,在显微镜下观察到花岗岩熔融过程 ,其初熔温度为 712 88～ 714 87℃ ,压力为 2 2 5MPa ,熔融温度为 759 54～76 0 0 0℃ ,压力为 30 0MPa。重点介绍了国外运用HDAC进行冰的高压相、水体系中伟晶岩矿物溶解、可燃有机岩、石油及岩石热解、高压下矿物包裹体均一温度测定及甲烷水合物合成实验研究新成果。甲烷水合物在永久冻土带及大陆坡、海底高原、海底沉积物等地质环境广泛分布 ,储量大 ,可成为 2 1世纪人类使用的新能源。目前世界主要国家的科学家除致力于该资源勘探外 ,还运用不同方法进行甲烷水合物的合成研究 ,以了解其形成条件及性质。开发和应用甲烷水合物具有重大意义 ,为促进我国此项工作开展 ,文中作了重点介绍。

DAC垫片孔侧壁绝缘程度对电导率测量结果的影响

通过有限元方法,计算了DAC内垫片孔侧壁与样品发生不同程度短路的情况下,范德堡法测量样品电阻率的相对误差.发现垫片孔侧壁与样品短路面积小于20%时,相对误差可以控制在10%以内.而当短路面积超过25%时,相对误差迅速增大.研究中还发现,电极越靠近样品边缘,相对误差越小.