流体包裹体压力计研究之二:高温高压下碳氢化合物的拉曼光谱

在温度23～315℃、压力高达近2000MPa下用金刚石压腔下研究了正庚烷、环己烷及其混合物的拉曼光谱特征。结果表明：环己烷和正庚烷混合,只是改变了环己烷及正庚烷的平均C-H伸缩振动的拉曼位移,但是并不影响其P-△^-vp关系式。另外,经过数据拟合,得到了平均C-H伸缩振动的拉曼位移与压力的关系为：P=78．21（△^-vp）＋71．56。该公式可以用来作为流体包裹体尤其是油气包裹体的压力计。     

拉曼光谱方法测量流体包裹体的内压及其应用

通过金刚石压腔和显微激光拉曼光谱方法,获得了流体包裹体中H2O-NaCl体系的O—H、碳酸根的C—O、硫酸根的S—O和正庚烷-环己烷的C—H振动拉曼位移与温度和压力关系的表达式。该研究结果可以用于实测流体包裹体在不同温度下的内压,并可由此获得流体包裹体的p-t线或等容线。这不仅有助于精确获得流体包裹体的形成温度和形成压力,也可为研究和确定流体包裹体中流体的组成和性质提供依据。     

流体包裹体压力计研究之一:高温高压下Na2SO4溶液的拉曼光谱

用金刚石压腔研究了Na2SO4溶液在温度30~400℃、压力90~2400 MPa条件下的拉曼光谱特征。结果表明:温度相同时,SO42-的对称伸缩振动随压力增大向高频方向偏移;而在压力基本相同时,随温度升高则向低频方向偏移。经过数据拟合得到了SO42-对称伸缩振动的拉曼位移与温度、压力的关系为:ρ=190.44Δυp 0.002 7t2 2.901 9t-111.68。该公式可以用来作为流体包裹体的压力计。     

天然气和液态混合烷烃拉曼特征峰与温度、压力的关系

天然气和液态混合烷烃在不同压力和温度下的原位拉曼测试表明,天然气和液态混合烷烃的拉曼特征峰随温度增高向高波数移动,随压力增大而表现出不同的拉曼位移趋势。2917 cm^-1左右为天然气的C–H对称伸缩振动峰(ν1),随压力增大向低波数移动,甲烷占烃类的比例和C₂₊烃类含量对ν1拉曼位移有影响。<150℃时,液态混合烷烃的C–H对称伸缩振动峰和C–H不对称伸缩振动峰随压力增加向高波数移动,拉曼特征峰位移与压力相关性曲线变化趋势一致;≥150℃时,液态混合烷烃的部分拉曼特征峰随压力增大向低波数移动,拉曼特征峰位移与压力相关性曲线变化趋势不一致。     

一种潜在的地质压力计：流体包裹体子矿物的激光拉曼光谱测压法

高温高压下矿物的拉曼原位测量表明，某些拉曼活性的物质其拉曼位移与压力之间具有良好的线性关系。这一特性使我们能够通过测量矿物包裹体中含有这些子矿物的拉曼位移以确定矿物的形成压力。与目前常采用的共存矿物对压力计以及流体包裹体的CO2等容线法等压力测定方法相比，该方法具有快速、方便和准确的特点。由于包裹体中可以存在各种不同的子矿物以及不同的溶液物质，因此系统研究包裹体中一切可能存在的矿物或物质的拉曼位移与温度和压力之间的关系将可以提供一种方便、准确的地质压力测量手段。     

冷冻条件下天然包裹体中流体水分子氢键的拉曼光谱特征

水的拉曼图谱实际就是带氢键作用的OH伸缩振动峰(包括对称伸缩振动峰和反对称伸缩振动峰)和不带氢键作用的OH对称伸缩振动峰(包括对称伸缩振动峰和反对称伸缩振动峰)的叠加包络线,通过对流体中水的拉曼图谱的分析可以反映流体中氢键作用的强弱.因此,用Renishaw MK1-1000型显微激光拉曼探针原位分析了冷冻条件下天然的流体包裹体腔内流体水分子的氢键作用.研究表明,在冷冻条件下,水分子运动以带氢键作用的伸缩振动为主,同时还有微弱的非氢键作用的伸缩振动;随着温度的降低,流体中水分子的氢键作用不断地增强;在-130~-180 ℃区间氢键作用增强的趋势明显加大,暗示流体性质在此温度区间可能发生了突变.      

草酸的稳定性及CO_2包裹体压力计实验研究

应用金刚石压腔(diamond-anvil cell)实验技术,对草酸的稳定性进行了研究。草酸在高压低温条件下可以稳定存在,而在低压高温条件下将分解为CO2、H2O等气体。当成矿流体遇到破裂带或裂隙而发生减压沸腾时,可以使成矿流体中的有机络合物迅速发生分解产生大量CO2,从而造成金属元素在有利的空间沉淀、富集成矿。同时,实验研究了高温高压条件下CO2的物理化学性质,得到了CO2包裹体压力计的测定方程:P(MPa)=271.517·(Δν1381.93-0.010987·ΔT)+0.1,式中Δν1381.93(cm-1)为待测包裹体中CO2的拉曼位移相对于常温常压下CO2的拉曼位移1381.93cm-1之差,ΔT(℃)为待测包裹体的温度与常温(23℃)之差,P(MPa)为待测包裹体的内压。由上式计算拉曼位移ν的标准偏差为±0.2cm-1,压力P的误差为±54MPa。该压力标定方程适用于在高压下温度范围为23℃≤T≤390℃的压力标定。     

常温和压力0.1～1300 MPa下硬石膏的拉曼光谱研究

利用立方氧化锆压腔装置测量了高压下硬石膏中硫酸根离子内部S-O键的四个振动（对称伸缩振动、弯曲振动、反对称伸缩振动和变形弯曲振动）的拉曼位移,研究结果表明：在25℃和0．1～1300MPa压力范围内硬石膏未发生相变,所观察到的硬石膏各个拉曼峰的位移值随压力的增加而线性增加,它们与压力之间的关系可分别表达为：υ1018=0．0053p＋1016.8,υ417=0．0013p＋416．82,υ498=0．0044P＋499．25,υ1129=0．0052p＋1128．5,υ1160=0．0067p＋1159．5,υ608=0．0028p＋608．76,υ627=0．0036p＋627．01,υ675=0．0039p＋675．32,且伸缩振动受压力的影响比弯曲振动大。其1018cm^-1峰强度大,是石英464cm^-1峰的6倍,因此硬石膏也是宝石压腔良好的压力标定物质。     

利用U—1000型激光拉曼探针测定流体包裹体气体成分的研究

本文利用U－1000型激光拉曼探针成功地测量出单个流体包裹体中H2S、CH4、CO2气体成分，并讨论了包裹体中这些气体的拉曼谱峰位移与包裹体内压的关系，分析了影响激光拉曼探针定量测定包裹体气相成分的取面积和拉曼定量因子因素。     

沥青包裹体的拉曼光谱特征

对石油中的沥青质组分进行了拉曼光谱分析,发现有两种不同的拉曼光谱特征的沥青质:一是具碳质拉曼特征峰的沥青质,二是无碳质拉曼特征峰的沥青质,将前者称为碳质沥青质.对储集砂岩中的深色沥青质包裹体拉曼分析并据其拉曼光谱图特征将这类包裹体分为三种类型:含碳质沥青包裹体、碳质沥青包裹体和沥青包裹体.如果烃包裹体形成后经历了地质构造应力而破裂和地热作用而发生轻组分移出,就形成了沥青包裹体;若再经地质高温变质作用而发生了碳化,就形成碳质沥青包裹体;若只经历地质高温变质作用而发生碳化,组分热解但未移出,可能会形成含碳质沥青包裹体.     

Viscosity of albite melt at high pressure and high temperature

 The viscosity of albite (NaAlSi₃O₈) melt was measured at high pressure by the in situ falling-sphere method using a high-resolution X-ray CCD camera and a large-volume multianvil apparatus installed at SPring-8. This system enabled us to conduct in situ viscosity measurements more accurately than that using the conventional technique at pressures of up to several gigapascals and viscosity in the order of 10⁰ Pa s. The viscosity of albite melt is 5.8 Pa s at 2.6 GPa and 2.2 Pa s at 5.3 GPa and 1973 K. Experiments at 1873 and 1973 K show that the decrease in viscosity continues to 5.3 GPa. The activation energy for viscosity is estimated to be 316(8) kJ mol⁻¹ at 3.3 GPa. Molecular dynamics simulations suggest that a gradual decrease in viscosity of albite melt at high pressure may be explained by structural changes such as an increase in the coordination number of aluminum in the melt. Received: 6 January 2001 / Accepted: 27 August 2001     

高温高压岩石流变仪的围压标定方法

高温高压岩石流变仪围压标定的主要方法为氯化盐类的部分熔融法和矿物相变法。利用氯化盐类进行压力标定时,不仅可以利用单一盐类,也可以使用多种盐类的混合物;常用的压力标定矿物相变及其适用温压范围如下:石英-柯石英,500~1200℃、2.5~3.2GPa;钠长石-硬玉+石英,600~1200℃、1.6~3.2GPa;铁橄榄石+石英-铁辉石,600~1200℃、1~1.7GPa;磷镁石-Mg3(PO4)2-Ⅱ,565~825℃、0.6~0.9GPa;方解石-文石,600~1200℃、0.5~2.5GPa。不同的标定方法具有不同的特征,文中将进行详细介绍。     

Electrical conductivity of K-feldspar at high temperature and high pressure

Electrical conductivity measurements on dry polycrystalline K-feldspar were performed at 1.0 to 3.0 GPa and 873 to 1,173 K with a multi-anvil high-pressure apparatus and the Solartron-1260 Impedance/Gain Phase Analyzer in the frequency range of 10^?1 to 10⁶ Hz. At each temperature the complex impedance displays a perfect semi-circular arc that represents the grain-interior conduction. Under the experimental conditions, electrical conductivity exponentially increases with increasing temperature and slightly decreases with increasing pressure; however, the effect of pressure on the conductivity is less pronounced than that of temperature. The activation enthalpy decreases slightly from 0.99 to 1.02 eV with increasing pressure, and the activation energy and activation volume for K-feldspar are 0.98 eV and 1.46?±?0.17 cm³/mol, respectively. According to these Arrhenius parameters, ionic conduction is proposed to be the dominant conduction mechanism in K-feldspar at high temperatures and pressures, and potassium ions are the charge carriers transporting by an interstitial mechanism. The diffusion coefficient of potassium at high temperatures was calculated from our conductivity data on K-feldspar using Nernst–Einstein equation, and the results were compared with the previous experimental results.     

Strength of solid pressure media and implications for high pressure apparatus

The stress-strain properties of talc, pyrophyllite, silver chloride, sodium chloride, boron nitride and graphite have been measured under confining pressures up to 8 or 10 kb at room temperature, and, in the case of talc, also at temperatures up to 900° C. The extrapolation and application of these results to solid medium high pressure apparatus of pistoncylinder type is discussed and a calculation made of the correction to nominal pressure (friction correction), taking into account the stress gradients in the medium and the shearing between the medium and the cylinder wall. Correction to the nominal differential stress measured in solid medium stress-strain apparatus is also discussed.     

铁橄榄石高温高压流变性的实验研究

通过高温高压实验研究了铁橄榄石集合体的流变性.首先,利用高精度的Paterson气体介质变形装置对铁橄榄石集合体Fe2SiO4进行了高温三轴压缩蠕变试验.变形试验条件为:温度1273～1423K,围压300MPa,差应力10～250MPa,应变率10-7～10-4s-1,试件的最大变形量不超过20%.利用三维非线性拟合方法对蠕变试验数据进行分析,得到铁橄榄石集合体的微观变形机制为扩散域和位错域,扩散域的应力指数为1左右.位错蠕变域中,干燥铁橄榄石集合体的应力指数为5.4.活化能为781kJ/mol;含水铁橄榄石集合体的应力指数为3.4,活化能为516kJ/mol.实验结果表明,含水时铁橄榄石的流变强度比干燥时小一个数量级.将实验结果与铁橄榄石单晶的强度进行对比,发现铁橄榄石集合体的流变强度比铁橄榄石单晶的强度高.从而得到了铁橄榄石集合体高温高压流变性(强度)的初步试验结果.     

致密砂岩高围压和高孔隙水压下渗透率演化规律及微观机制

深部岩石工程具有高地应力和高水头压力的特点。为了研究岩石在高围压和高孔隙水压条件下渗透率演化规律,选取致密砂岩开展不同围压条件下变孔隙水压的渗流试验。研究结果表明:(1)在所研究的围压范围内(0~50 MPa),随孔隙压力增加,渗透率依次呈现3种不同的变化趋势,即快速增长阶段(围压为10~20 MPa)、缓慢增长阶段(围压为30~40 MPa)和保持恒定阶段(围压为50 MPa);在围压卸载时,由于高围压作用使试样内部产生不可逆变形,导致渗透率具有明显的不可恢复现象,且随围压降低,渗透率恢复存在滞后效应。(2)渗流试验过程中,体积应变和渗透率演化具有较好的一致性。(3)在围压加卸载过程中,高孔隙水压力条件下渗透率对应力的敏感程度和恢复程度均大于低孔隙水压力。(4)偏光显微镜图像从微观角度揭示了试样在围压加卸载过程中产生不可逆变形的内在机制:骨架颗粒相互挤压、错动导致原有微裂隙压缩、孔隙减小甚至坍塌,引起渗透率不可恢复。渗流试验后,纵波波速增大,说明岩石致密性提高,与试样内部微观结构变化具有较好的一致性。     

Can HHe+exist at high pressure:Exploration of high pressure induced HF–He compounds

HHe⁺is considered as the strongest acid and most powerful proton donor known to human.Whether HHe⁺exists at planetary high pressure environment is a quite important problem in physics,chemistry and planetary sciences.Here,using the ab initio evolutionary algorithm USPEX package,we searched HF–He system,which was reported as the most possible candidate to contain HHe⁺.The calculation proved HHe⁺cannot form at pressure<1000 GPa,due to a conflict between the covalent component in symmetric hydrogen bond and ionic HHe⁺.Although He atoms have no chemical bonding with other elements,they can supply a chemical pressure,leading to two new phases He2(HF)4 and He(HF).With coplanar(HF)₄rings,He₂(HF)₄have an aromaticity-like electronic behavior while He(HF)has a new type of chiral HF chain.The formation of He₂(HF)₄and He(HF)prove that the chemical pressure from He,on par with external pressure,have ability to control the structural and electronic configuration and induce some new familiars of compounds include H and He elements which are fundamental planetary materials in giant planets.     

X-ray diffraction study of magnesite at high pressure and high temperature

 P–V–T measurements on magnesite MgCO₃ have been carried out at high pressure and high temperature up to 8.6 GPa and 1285 K, using a DIA-type, cubic-anvil apparatus (SAM-85) in conjunction with in situ synchrotron X-ray powder diffraction. Precise volumes are obtained by the use of data collected above 873 K on heating and in the entire cooling cycle to minimize non-hydrostatic stress. From these data, the equation-of-state parameters are derived from various approaches based on the Birch-Murnaghan equation of state and on the relevant thermodynamic relations. With K′₀ fixed at 4, we obtain K₀=103(1) GPa, α(K⁻¹)=3.15(17)×10⁻⁵ +2.32(28)×10⁻⁸ T, (∂K_T/∂T)_P=−0.021(2) GPaK⁻¹, (dα/∂P)_T=−1.81×10⁻⁶ GPa⁻¹K⁻¹ and (∂K_T/∂T)_V= −0.007(1) GPaK⁻¹; whereas the third-order Birch-Murnaghan equation of state with K′₀ as an adjustable parameter yields the following values: K₀=108(3) GPa, K′₀=2.33(94), α(K⁻¹)=3.08(16)×10⁻⁵+2.05(27) ×10⁻⁸ T, (∂K_T/∂T)_P=−0.017(1) GPaK⁻¹, (dα/∂P)_T= −1.41×10⁻⁶ GPa⁻¹K⁻¹ and (∂K_T/∂T)_V=−0.008(1) GPaK⁻¹. Within the investigated P–T range, thermal pressure for magnesite increases linearly with temperature and is pressure (or volume) dependent. The present measurements of room-temperature bulk modulus, of its pressure derivative, and of the extrapolated zero-pressure volumes at high temperatures, are in agreement with previous single-crystal study and ultrasonic measurements, whereas (∂K_T/∂T)_P, (∂α/∂P)_T and (∂K_T/∂T)_V are determined for the first time in this compound. Using this new equation of state, thermodynamic calculations for the reactions (1) magnesite=periclase+CO₂ and (2) magnesite+enstatite=forsterite+CO₂ are consistent with existing experimental phase equilibrium data. Received September 28, 1995/Revised, accepted May 22, 1996     

Crystal structure of columbite under high pressure

The structural evolution of two columbites under pressure, one ferrocolumbite from Raode (Africa) and one manganocolumbite from Kragero (Norway), has been determined by single-crystal X-ray diffraction. Structural investigations at high pressure have been carried out on samples which were preliminarily annealed to attain the complete cation-ordered state. For each crystal, five complete datasets have been collected from room pressure up to ca. 7 GPa. Structure refinements converged to final discrepancy factors R ranging between 5.2 and 5.8% for both the crystals. Structure refinements of X-ray diffraction data at different pressures allowed characterisation of the mechanisms by which the columbite structure accommodates variations in pressure. A and B octahedral volumes in both samples decrease linearly as pressure increases, with a larger compression of the larger A site. The difference in polyhedral bulk moduli of the A sites for the two samples does not appear to relate directly to the octahedral sizes, the A site being more compressible in the Fe-rich sample than in the Mn-rich one. By far the most compressible direction in both the analysed samples is along b. The cations are in fact free to move along this direction, thus allowing the octahedral chains to slide over each other; this effect is particularly evident in the manganocolumbite sample which shows a steep shortening of interchain A–B distances along b.     

Density of peridotite melts at high pressure

Densities of ultramafic melts were determined up to 22 GPa by relative buoyancy experiments. Olivine and diamond were used as buoyancy markers. We confirmed that the density crossover of PHN 1611 melt and its equilibrium olivine (Fo94) occurs at around 13.5 GPa and 2030 °C and that olivine floats from deeper regions in the magma ocean of the primordial terrestrial mantle. The comparison of the compression curves of basic and ultrabasic melts implies that the basic melt is more compressible. This can be explained by the difference in the amount of compressible linkage of SiO_n and AlO_n polyhedra. The interstitial melt trapped by the density crossover can be the cause of the impedance anomaly of the seismic wave in the deep upper mantle.