100MPa压力下温度和水对干酪根结构状态影响的实验研究

为了实验验证变质沉积物中的碳质物拉曼光谱地质温度计的可用性,利用冷封口式高温高压水热系统将焊封金管内的干酪根于100MPa压力和温度(250-700℃)、有水和无水条件下处理24小时,激光拉曼探针(LRM)分析表明,实验所得碳质物的一级和二级拉曼谱特征(拉曼峰的存在、峰的位置、宽度、高度和面积)随温度系统地变化,所得碳质物的D/O比值随温度升高而减小,但在D/O比-温度关系图上-500℃处有一拐点(极小)。实验条件下处理的干酪根的显微富利叶变换红外谱(micro-FTIR)分析表明,脂族C-H和芳族C-H吸收峰的相对强度在500℃左右急剧变化以及在700℃的实验产物中仍存在含氢的功能团。高温高压条件下,水的存在不利于碳质物的石墨化(有序化)。     

高温高压条件下水镁石相变的拉曼光谱研究

本文应用金刚石压腔装置结合拉曼光谱分析技术原位观测了高温高压条件下水镁石的结构变化特征。结果表明：常温升至300℃过程中,随温度升高,水镁石中表征H-O对称伸缩振动的3652 cm-1拉曼特征峰向低波数移动,拉曼特征峰波数与对应的体系温度呈现良好的线性相关关系。常温条件下体系加压过程中,当压力升高至1.19 GPa时,水镁石中表征H-O振动的3652 cm-1拉曼峰向高波数移动并逐渐消失,同时产生表征方镁石的1078 cm-1拉曼特征峰,表明水镁石脱水相变为方镁石。随后压力降低过程中,表征水镁石H-O振动的3652 cm-1拉曼特征峰没有重新出现,脱水相变过程不可逆。     

H_2O-CO_2体系融合二氧化硅毛细管样品原位显微激光拉曼光谱研究

使用配备Linkam冷热台的显微激光拉曼光谱仪,采用融合二氧化硅毛细管样品,在-120～31℃温度区间,1 200～1 500cm-1光谱区间上,原位采集H2O-CO2体系流体包裹体的拉曼光谱,并针对CO2特征拉曼光谱展开分析。结果表明,融合二氧化硅毛细管样品中的流体具有代表性。通过对毛细管样品进行拉曼光谱采集,该实验获得了流体包裹体中CO2气相、CO2液相、CO2固相、CO2水合物相和CO2水溶液相的特征光谱。光谱分析结果显示,在实验温度区间上,CO2固相和CO2水合物相特征峰的稳定性,有助于鉴别拉曼光谱;同时,CO2气相、CO2液相和CO2水溶液相费米共振峰峰位因CO2压力或密度影响而发生变化。此外,该实验在温度变化过程中,鉴定了不同相的拉曼特征光谱。结果表明,激光拉曼光谱结合显微测温技术能够有效鉴别包裹体中不同的流体相,获得相变过程,确定相变温度。     

华北奥陶系含膏角砾岩气爆成因探讨

根据华北奥陶系含膏角砾岩形态特征,对其成因进行初步分析.利用数值方法分析含膏角砾岩形成期地温特征,表明其存在粘土矿物及石膏脱水的温度条件.对加温条件下含膏泥岩孔隙气体压力进行实验研究,显示在较高温度条件下,含膏泥岩石膏脱水将产生极高的孔隙水压力.扫锚电镜和能谱分析结果反映出高温条件下石膏矿物结构发生了较大的变化.分析结果表明,华北奥陶系含膏角砾岩具备气爆成因条件.     

不同压力下Ⅰ型甲烷水合物拉曼光谱

本文描述了合成的Ⅰ型甲烷水合物高压下拉曼光谱测定结果。甲烷水合物用细粒冰和甲烷气在温度0℃～9℃和压力18MPa下历时2天合成,在金刚石压腔里进行了原位的显微观察和拉曼光谱测定。一组温度25℃和压力范围132～901MPa下的拉曼光谱数据显示,样品的光谱呈左高右低的双峰结构,左谱峰位置范围为2904.4～2907.2cm~(-1),右谱峰位置范围为2915～2922cm~(-1),谱峰位置随压力变化,典型光谱的左右谱峰强度比近似为3:1,系典型的Ⅰ型结构特征;这说明甲烷水合物在较高压力下也能保持Ⅰ型结构。作为比较,甲烷气和溶解水中的甲烷的拉曼光谱也进行了测定,它们的拉曼光谱特征与Ⅰ型甲烷水合物的明显不同。     

C-H-O-N体系挥发分的拉曼定量分析:压力、温度和流体组成的影响

拉曼光谱是定量分析流体包裹体中挥发分组成和压力的重要手段,而这又是恢复流体捕获温度、压力的前提。本文收集了CH_4-N_2、CH_4-N_2-H_2O和CH_4-N_2-CO_2-CO体系在21～350℃和1～60 MPa条件下的原位拉曼光谱,获取了CH_4、N_2、CO_2和CO特征拉曼光谱的峰位和峰面积等光谱参数,并以上述体系为例,探讨了应用拉曼光谱定量分析C-H-O-N体系挥发分组成的关键技术问题,即压力、温度和流体组成对分析结果的影响。首先,在温度恒定的条件下,v_1-CH_4、v_1-N_2、(v_1-2v_2)-CO_2高频峰和v_1-CO峰位随着压力的升高而发生负向偏移。在压力恒定的条件下,v_1-CH_4、(v_1-2v_2)-CO_2峰位随温度升高向高频偏移,但v_1-N_2和v_1-CO峰位随温度变化未发生明显偏移,因而可以应用这些组分的特征峰位来反映流体压力。其次,CH_4、CO_2和CO相对于N_2的拉曼定量因子随压力升高而增大,分别在大于10 MPa、10 MPa和2.5 MPa以上达到稳定值。温度对CH_4和CO的定量因子影响不显著,但CO_2的定量因子随温度升高明显降低。水对CH_4定量因子影响仅在低压条件下显著,在200℃以下的高压条件下影响较弱。最后,以含未知CH_4/N_2比例的CH_4-N_2混合气体的熔融毛细硅管合成包裹体为例,提出了应用拉曼光谱定量分析流体包裹体中复杂挥发分比例和内压的一般方法。受实验条件和仪器设置的影响,各个实验室测定的拉曼定量因子存在较大差异,在应用拉曼光谱定量分析包裹体挥发分组成时应予以注意。     

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。     

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。     

斜长石的碎裂流与半脆性变形

在温度为25～700℃、压力为500～1500MPa和应变率10~(-5)S~(-1)的条件下,对布什维尔德斜长石(An_(75),粒度350μm,5％其它物质)展开了一系列实验。在所施加的P—T范围内布什维尔德杂岩的强度都保持对压力敏感,而弱化则出现在给定压力条件下增温的情况。由粘滑向稳定滑移的转变出现在200～300℃和≥500MPa条件下。在200～300℃时强度的降低,局部出现的碎裂流及缺少晶内塑性变形的微观证据都有利地说明一种可能性,即这种转变对应于一定量随机分布的热破裂的扩展。均匀韧性流动仅出现在600℃和700℃温度,1000～1500MPa压力条件下,它与机械双晶,不均匀和带状波状消光的发育对应,这可能是由半脆性变形引起的。在这些条件下,变形持续至应变高达44％。     

CH4-H2O体系流体包裹体均一过程激光拉曼光谱定量分析

对南黄海盆地二叠纪地层中某石英脉中的CH4-H2O体系流体包裹体均一过程进行了激光拉曼光谱定量分析。利用甲烷与水的拉曼峰面积比值计算不同温度下流体包裹体中水溶液相中甲烷的浓度,除了在100℃附近出现最小值,随温度增加甲烷浓度呈指数增大。包裹体在214℃完全均一,均一时甲烷的浓度为0·1347mol/L。同时利用甲烷的拉曼特征对流体包裹体均一过程的内压变化作了分析。压力变化可以分为三个区间:19~100℃,随温度升高压力增大;100~150℃压力随温度升高减小;150℃之后压力迅速增大。均一温度下的内压为21·92MPa。流体包裹体内压的变化主要是由甲烷溶解行为和封闭体系的热力学特征决定的。实验表明激光拉曼光技术可以作为定量分析含甲烷流体包裹体的一种有效方法。     

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     

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.     

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.     

The Electrical Conductivity of Gabbro at High Temperature and High Pressure

The electric conductivity of gabbro has been measured at 1.0 - 2.0 GPa and 320-700℃, and the conduction mechanism has been analyzed in terms of the impedance spectra.Experimental results indicated that the electric conductivity depends on the frequency of alternative current. Impedance arcs representing the conduction mechanism of grain interiors are displayed in the complex impedance plane, and the mechanism is dominated at high pressure.These arcs occur over the range of 102 - k× 105 Hz (k is the positive integer from 1 to 9). On the basis of our results and previous work, it is concluded that gabbro cannot form any high conductivity layer (HCL) in the middle-lower crust.     

耐高温高压复合保温管研究

耐高温高压复合保温管主要解决超高温高压环境下钻孔测量问题。为攻克超高温高压环境下真空绝热保温、高压密封等关键技术,研究的耐高温高压复合保温管为“超高温钻孔测量仪”提供一种耐高温承压管,使用环境温度可达270 ℃,压力120 MPa。通过室内测试与现场应用,说明其满足超高温高压要求,可应用于高温地热能钻探工程、干热岩钻探工程、科学钻探工程、深部矿产资源勘探和深部油气资源勘探等工程中,为超高温大深度钻井测量提供技术支撑。     

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     

玄武岩的高温高压实验研究

玄武岩及其高温高压相—榴辉岩的相组合,经历了长期的地质作用,反映出一定的时空条件。从高温高压实验矿物学,实验岩石学入手,对于以相组合出现的某些化学体系进行平衡条件研究,可揭示此类岩石形成的物理化学环境,并有助于阐明地球内部的物理状态、组成成分以及活动过程。     

存储式高温高压钻孔测温仪的研制与应用

为解决大于200 ℃高温环境下的测温难题,为高温地热和干热岩资源勘查提供技术支撑,利用铂电阻测温技术和真空绝热保温技术研发了存储式高温高压钻孔测温仪。该仪器设计适用工作环境温度为300 ℃,耐水压100 MPa,主要用于高温高压环境下的钻孔测温。在广东惠州惠热1井和青海共和GH-01井进行了实测应用,满足目前钻遇到的孔底温度的测温要求。     

Phonon density of states in iron at high pressures and high temperatures

The phonon density of states (DOS) in iron has been measured in situ by nuclear resonance inelastic X-ray scattering (NRIXS) at high pressures and high temperatures in a resistively heated diamond anvil cell. The DOS data provide a variety of thermodynamic and elastic parameters essential for characterizing iron at depth in the Earth interior, such as average sound velocity, Debye temperature, atomic mean square displacement, average kinetic energy, vibrational entropy and specific heat. The NRIXS data were collected at 6, 20, and 29 GPa and at temperatures up to 920 K. Temperatures were directly determined from the measured spectra by the ratio of intensities of the phonon creation/annihilation side bands that are determined only by the Boltzmann factor. The change of the DOS caused by the structural transition from -Fe to -Fe is small and not resolvable within the experimental precision. However, the phonon energies in -Fe are clearly shifted to lower values with respect to - and -Fe. The temperature dependence of derived thermodynamic parameters is presented and compared with those obtained by Debyes model. The Debye temperatures that best describe the data decrease slightly with increasing temperature.     

超高温高压流变仪的研发及应用

随着我国能源勘探及地球深部探测等向深部发展,深井越来越多,地层温度、压力越来越高。保证高温高压状态下钻井液流变性能的稳定是深井安全钻进的必要前提,测定钻井液高温高压流变性是评价和优选钻井液体系最基础的工作。依托国家科技部重大仪器设备开发专项,通过对压力控制系统、温度控制系统、剪率控制系统、粘度检测系统等方面技术难题的攻关,研制成功了国内首台超高温高压流变仪。该仪器可在高温高压及低温高压条件下对钻井液、完井液、压裂液等样品的流变性进行高精度测量。