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.

A Breakthrough in Pressure Generation by a Kawai-Type Multi-Anvil Apparatus with Tungsten Carbide Anvils

Expansion of the pressure range of Kawai-type multi-anvil presses (KMAPs) with tungsten carbide (WC) anvils is called for, especially in the field of Earth science. However, no significant progress in pressure generation has been made for 40 years. Our recent studies have expanded the pressure generation of a KMAP with WC anvils to 65 GPa, which is the world record for high-pressure generation in this device and is more than 2.5 times higher than conventional pressure generation. We have also successfully generated pressures of about 50 GPa at high temperatures. This work reviews our recently developed technology for high-pressure generation. High-pressure generation at room temperature and at high temperature was attained by integration of the following techniques:① a precisely aligned guideblock system,② a high degree of hardness of the second-stage anvils,③ tapering of the second-stage anvil faces,④ a high-pressure cell consisting of materials with a high bulk modulus, and ⑤ high thermal insulation of the furnace. Our high-pressure technology will facilitate investigation of the phase stability and physical properties of materials under the conditions of the upper part of the lower mantle, and will permit the synthesis and characterization of novel materials.

Recent advances of high-pressure generation in a multianvil apparatus using sintered diamond anvils

The tried and tested multianvil apparatus has been widely used for high-pressure and hightemperature experimental studies in Earth science. As a result, many important results have been obtained for a better understanding of the components, structure and evolution of the Earth. Due to the strength limi- tation of materials, the attainable multianvil pressure is generally limited to about 30 GPa （corresponding to about 900 km of the depth in the Earth） when tungsten carbide cubes are adopted as second-stage anvils. Compared with tungsten carbide, the sintered diamond is a much harder material. The sintered diamond cubes were introduced as second-stage anvils in a 6--8 type multianvil apparatus in the 1980s, which largely enhanced the capacity of pressure generation in a large volume press. With the development of material synthesis and processing techniques, a large sintered diamond cube （14 ram） is now available. Recently, maximum attainable pressures reaching higher than 90 GPa （corresponding to about 2700 km of the depth in the Earth） have been generated at room temperature by adopting 14-mm sintered diamond anvils. Using this technique, a few researches have been carried out by the quenched method or combined with synchrotron radiation in situ observation. In this paper we review the properties of sintered diamond and the evolu- tion of pressure generation using sintered diamond anvils. As-yet unsolved problems and perspectives for uses in Earth Science are also discussed.

Numerical Si mulation of Inner Stress Fields for Stretching Block With Rectangular Section Between Flat Anvils

The stretch of blocks with rectangular section using flat anvils was simulated by using ANSYS software. The inner stress distribution for different tool width ratio w/h and blank width ratio b/h was studied. Consequent- ly, critical anvil width ratio （w/h）c and critical blank width ratio （b/h）c are obtained, which provide a sound basis for designing reasonable stretching technology.

金川收购Metorex与五矿资源收购Anvil案例比较

为缓解我国铜资源供需严重失衡的矛盾,我国矿业企业在海外并购日益加强,非洲已经成为重要的目标地区。本文对近年矿业界的两大具有可比性的收购案例-金川收购梅特瑞斯和五矿资源收购安维尔进行了详细比较研究,通过对目标公司概况、交易概况、资源量与储量、财务预测及估值倍数的阐述及技术分析,说明在非洲进行矿业并购要付出较大的代价,二者相比金川交易比五矿有稍好的性价比。

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.

RIGID-PLASTIC MECHANICAL MODEL FOR THE FORGING METHOD WITH HORIZONTAL V-SHAPED ANVIL

In order to decrease the anisotropy of mechanical properties, the rigid-plastic mechanical model for the forging method with horizontal V-shaped anvil is presented. The forging method, through the change of anvils shape, is able to control fibrous tissue direction, to improve the anisotropy of mechanical properties of axial forgings, to realize uniform forging. Therefore, the forging method can overcome the defect that conventional forging methods produce. The mechanism of the forging method with horizontal V-shaped anvil and the process of metal deformation are analyzed. The agreement of theoretical analysis with experimental study verifies the fact that the forging method with horizontal V-shaped anvil can control effectively the mechanical properties of axial forgings.

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.

Cubic anvil cell apparatus for high-pressure and low-temperature physical property measurements

We will build a cubic anvil cell （CAC） apparatus for high-pressure and low-temperature physical property measurements in the synergic extreme condition user facility （SECUF）. In this article, we first introduce the operating principle, the development history, and the current status of the CAC apparatus, and subsequently describe the design plan and technical targets for the CAC in SECUF. We will demonstrate the unique advantages of CAC, i.e., excellent pressure homogeneity and large hydrostatic pressure capacity, by summarizing our recent research progresses using CAC. Finally, we conclude by providing some perspectives on the applications of CAC in the related research fields.

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.

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.

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.

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.

Quantitative Analysis of Meso-β-scale Convective Cells and Anvil Clouds over North China

This paper proposes several quantitative characteristics to study convective systems using observations from Doppler weather radars and geostationary satellites. Specifically, in order to measure the convective intensity of each system, a new index, named the ＂Convective Intensity Ratio＂ （CIR）, is defined as the ratio between the area of strong radar echoes at the upper level and the size of the convective cell itself. Based on these quantitative characteristics, the evolution of convective cells, surface rainfall intensity, rainfall area and convectively generated anvil clouds can be studied, and the relationships between them can also be analyzed. After testing nine meso-β-scale convective systems over North China during 2006–2007, the results were as follows： （1） the CIR was highly correlated with surface rainfall intensity, and the correlation reached a maximum when the CIR led rainfall intensity by 6–30 mins. The maximum CIR could be at most ～30 mins before the maximum rainfall intensity. （2） Convective systems with larger maximum CIRs usually had colder cloud-tops. （3） The maximum area of anvil cloud appeared 0.5–1.5 h after rainfall intensity began to weaken. The maximum area of anvil cloud and the time lag between maximum rainfall intensity and the maximum area of anvil cloud both increased with the CIR.

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.

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.

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.

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.

In-situ control of oxygen fugacity for laboratory measurements of electrical conductivity of minerals and rocks in a multi-anvil press

In this paper, a new of oxygen fugaeity controltechnique that can be widely applied to in-situ measurement of the grain interior electrical conductivities of minerals and rocks is presented for high temperature and high pressure. Inside the sample assembly, a metal and corresponding metal oxide form a solid oxygen buffer. The principle of this technique is to randomly monitor and adjust oxygen fugacity in the large-volume multi-anvil press by changing the types of solid oxygen buffer, metal shielding case and electrodes. At a pressure of up to 5.0 GPa and a temperature of up to 1423 K, the electrical conductivities of the dry peridotite are tested under the conditions of different oxygen fugacities. By virtue of this new technique, more and more reasonable and accurate laboratory electrical property data will be successfully obtained under controlled thermodynamic conditions.