1000－7598－(2003)增1―0001―08

随着地下工程的发展,对于埋置较深和地质环境较为复杂的隧道工程,高地温问题已经成为一个重要的工程问题并引起了国内外学者的广泛关注。研究隧道的温度场分布问题对于解决寒区隧道冻融问题、高温隧道问题、隧道火灾灾害等是十分必要的。针对高地温环境中的圆形隧道,假定其具有一定长度且承受轴对称的温度荷载和地应力作用,建立两端简支的二维稳态的热传导方程和平衡方程。利用无量纲化和微分方程级数求解的方法,得到了包含温度场、位移场及应力场的热弹性理论解。依据上述研究结果,以某包含衬砌的圆形断面隧道为例进行了热弹性分析,并得到了由于隧道开挖而引起的围岩的温度变化范围。研究所得结论可为隧道施工及运营过程中隧道的保温隔热提供重要的理论依据。     

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.     

In situ measurement of dissolved chloride in high temperature hydrothermal fluids

The ability to continuously monitor chemical properties of hydrothermal vent effluents for extended periods of time is essential to understanding dynamic processes responsible for the temporally variable nature of mid-ocean ridge hydrothermal systems. Although instruments do exist for some parameters, there has been no sensor capable of measuring the chloride concentration, an indicator of possible phase separation, on a real-time and long-term basis. In this article, we discuss the construction of a novel instrument which measures solution resistance as a proxy for chloride concentration. The sensor consists of four gold electrodes embedded in a cylindrical ZrO₂ ceramic housing. It has been successfully deployed in several high temperature vents at the Main Endeavour Field (MEF) on the Juan de Fuca ridge in the NE Pacific, and calibrated under simulated hydrothermal conditions ranging up to 380 °C and 300 bar. The in situ data clearly demonstrate a tidal influence on the effluent from some high temperature vents possibly relating to a subsurface mixing process involving non-seawater end-members. Non-tidal changes are used to constrain the sequence and type of controls operating on fluids circulating within the subsurface.     

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     

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.     

The breakdown of potassium feldspar at high water pressures

The equilibrium position of the reaction between sanidine and water to form “sanidine hydrate” has been determined by reversal experiments on well characterised synthetic starting materials in a piston cylinder apparatus. The reaction was found to lie between four reversed brackets of 2.35 and 2.50 GPa at 450 °C, 2.40 and 2.59 GPa at 550 °C, 2.67 and 2.74 GPa at 650 °C, and 2.70 and 2.72 GPa at 680 °C. Infrared spectroscopy showed that the dominant water species in sanidine hydrate was structural H₂O. The minimum quantity of this structural H₂O, measured by thermogravimetric analysis, varied between 4.42 and 5.85 wt% over the pressure range of 2.7 to 3.2 GPa and the temperature range of 450 to 680 °C. Systematic variation in water content with pressure and temperature was not clearly established. The maximum value was below 6.07 wt%, the equivalent of 1 molecule of H₂O per formula unit. The water could be removed entirely by heating at atmospheric pressure to produce a metastable, anhydrous, hexagonal KAlSi₃O₈ phase (“hexasanidine”) implying that the structural H₂O content of sanidine hydrate can vary. The unit cell parameters for sanidine hydrate, measured by powder X-ray diffraction, were a = 0.53366 (±0.00022) nm and c = 0.77141 (±0.00052) nm, and those for hexasanidine were a = 0.52893 (±0.00016) nm and c = 0.78185 (±0.00036) nm. The behaviour and properties of sanidine hydrate appear to be analogous to those of the hydrate phase cymrite in the equivalent barium system. The occurrence of sanidine hydrate in the Earth would be limited to high pressure but very low temperature conditions and hence it could be a potential reservoir for water in cold subduction zones. However, sanidine hydrate would probably be constrained to granitic rock compositions at these pressures and temperatures. Received: 6 May 1997 / Accepted: 2 October 1997     

Thermal diffusivity of garnets at high temperature

Thermal diffusivity (D) of garnets with diverse chemical compositions was measured using the laser-flash technique, which is accurate (±2%) and isolates the lattice component from direct radiative transfer. Temperatures ranged from ~290 to ~1,600 K (unless limited by melting). Seven synthetic (e.g., YAG, GGG) and 15 natural garnets with two types of ionic substitution [Ca₃(Fe,Al)₂Si₃O₁₂ and (Mg,Fe,Ca)₃Al₂Si₃O₁₂] and varying amounts of OH^- were examined. Cation substitution or hydroxyl incorporation lowers D from end-member values. Thermal diffusivity is constant once the temperature (T) exceeds a critical value (T _sat) of ~1,100 to 1,500 K. From ~290 K to T _sat, the measurements are best represented by 1/D=A+BT+CT ² where A, B, and C are constants. These constants vary little among diverse chemical compositions, suggesting that the oxygen sublattice controls heat transport. Higher order terms are needed only when T _sat is low, such as Ant Hill garnet wherein 1/D=0.049403+0.0032299T−2.3992T ²×10⁻⁶+6.0168T ³×10⁻¹⁰(1/D in s/mm²; T in K). The mean free path (λ, computed from D and sound velocities) is slightly larger than the lattice parameter above T _sat, in accord with phonon–phonon interactions requiring non-localized modes. At most temperatures, λ is nm-sized. Large values of λ are obtained by extrapolation to a few Kelvins, suggesting that boundary scattering can only be important at extremely cold temperatures. The observed behavior with T and chemical composition is consistent with the damped harmonic oscillator model. Phonon transport is best represented by inverse thermal diffusivity wherein 1/D goes as T ⁿ where n is between 1 and 3 up to ~200 K, depends on a quadratic or cubic polynomial at moderate T, but is constant above T _sat. The predicted and observed temperature response of 1/D mimics the well-known form for heat capacity, in that acoustic modes control heat transport near cryogenic temperatures, optic phonons dominate above ambient temperature, and a limit analogous to that of Dulong and Petit is reached at very high temperature, due to full population of discrete phonon states.     

Thermodynamic properties of San Carlos olivine at high temperature and high pressure

In this study, the thermal expansion and heat capacity of San Carlos olivine under high temperature and high pressure are reported. Combining accurate sound velocity data under different P–T conditions with density and heat capacity data at ambient pressure, the density, adiabatic bulk modulus, shear modulus, and most importantly, thermal expansion and heat capacity, of San Carlos are extracted to 14 GPa by a numerical procedure using classic thermodynamic relationships. These data are in agreement with published findings. To estimate the temperature gradient in the upper mantle, we also report the fitting equations of thermal expansion and heat capacity of San Carlos olivine as a function of both temperature and pressure to the P–T condition of the 410 km discontinuity, which provide the thermodynamic properties with increasing depth in the Earth’s interior.     

高温高压下石膏脱水相变的原位拉曼光谱研究

本文运用激光拉曼光谱仪,利用水热金刚石压腔装置对高温高压条件下石膏-水体系中的石膏脱水相变进行拉曼光谱研究.在压力0.1 MPa～837.9 MPa和温度16～200 ℃条件下通过系列实验对相变的过程进行了原位光谱分析.与人们已知的无水条件下石膏分两步脱水的过程不同,高压下石膏在饱和水环境下倾向于一次性的脱去所有结晶水而形成无水石膏,实验中没有观察到半水石膏的出现.通过实验数据得到石膏和无水石膏的转折温度和平衡压力间的关系式为P(MPa)=19.56·T(℃)-2926.5.     

Friction in faulted rock at high temperature and pressure

Two hundred observations of frictional behavior of seven low-porosity silicate rocks were made at temperatures to 700°C and pressures from 2.5 to 6 kbar. For all rocks except one, peridotite, stick-slip occurred at low temperature and gave way to stable sliding at some high temperature, different for each rock. These differences could be related to the presence or absence of minerals such as amphibole, mica, or serpentine. Up to some temperature, depending on rock type, the friction stress was relatively unaffected by temperature. The shear stress decreased at higher temperature, and in some cases such decrease was related to the coincidence of fracture and friction strength. While somewhat dependent on rock type, the friction stress for the seven rocks studied was about the same, within 10–15%. Up to 265°C, water had little effect on the frictional behavior of faulted granite at 3 kbar effective pressure. The frictional stresses measured in the laboratory were significantly higher than estimated for natural faults. This difference could be accounted for by high pore pressure or weak alteration materials in the natural fault zone.     

Carrara大理岩高温高压变形实验研究

利用高精度的Paterson高温高压流变仪对Carrara大理岩在高温(873~1173K)高压(~300MPa)以及约10-6~10-3s-1应变速率下进行了三轴压缩变形实验。结果表明,在等应变速率条件下,其强度随着温度的升高而降低;在等温和等压条件下,其强度随着应变速率的增加先快速增加而后缓慢增加。在应变速率对差应力的双对数投图中,我们发现随着温度的升高拟合直线的斜率减小,并且在873K和高应变速率时973K温度下Carrara大理岩的流变本构方程服从指数律变化关系;而在高温(1073K和1173K)和973K低应变速率条件下Carrara大理岩的应力指数n为5.3~7.7,且服从幂次律变化关系。因此,Carrara大理岩在本研究的实验条件下主要有两种变形机制,一种是用指数律表示的高应力变形机制;另一种是用幂次律表示的中等应力变形机制。     

Crystallographic investigation of the huttenlocher exsolution at high temperature

Three plagioclases in the composition range An_66–70 from the different geological environments were selected for investigation of the Huttenlocher exsolution by Laue and Weissenberg methods with monochromatic X-ray radiation. In order to find the characteristics of the Huttenlocher exsolution at high temperatures heating experiments were carried out. The reversible phase transition between body centered plagioclase and high plagioclase in the anorthite-rich composition of the plagioclase and the irreversible transition from intermediate plagioclase to high plagioclase in the anorthite-poor composition were observed.     

Reaction of forsterite with hydrogen molecules at high pressure and temperature

High pressure and temperature reactions of a mixture of forsterite and hydrogen molecules have been carried out using a laser heated diamond anvil cell at 9.8–13.2 GPa and ~1,000 K. In situ X-ray diffraction measurements showed no sign of decomposition or phase transitions of the forsterite under these experimental conditions, indicating that the olivine structure was maintained throughout all runs. However, a substantial expansion of the unit cell volume of the forsterite was observed for samples down to ~3 GPa upon quenching to ambient pressure at room temperature. The Raman spectroscopy measurements under pressure showed significant shifts of the Raman peaks of the Si–O vibration modes for forsterite and of the intramolecular vibration mode for H₂ molecules toward a lower frequency after heating. Additionally, no OH vibration modes were observed by Raman and FT-IR spectroscopic measurements. These lines of evidence show that the observed volume expansion in forsterite is not explained by the incorporation of hydrogen atoms as hydroxyl, but suggest the presence of hydrogen as molecules in the forsterite structure under these high pressure and temperature conditions.     

Kinetics of peptide hydrolysis and amino acid decomposition at high temperature

Dipeptide hydrolysis and amino acid decomposition appear to follow a first-order rate law. The hydrolysis rate increases exponentially with increasing temperature in aqueous solution at both 265 atm and water steam pressures over the temperature range of 100 to 220 degrees C. Dipeptide hydrolysis has a lower apparent activation energy at 265 atm (44.1 KJ/mol) than at water steam pressure (98.9 KJ/mol). At lower temperatures (<200-220 degrees C), the rate of peptide bond hydrolysis is faster at 265 atm than at water steam pressure. At higher temperatures (>200-220 degrees C), however, peptide bond hydrolysis is slower at 265 atm than at water steam pressure. In aqueous solution, amino acid decomposition rates also increase exponentially with increasing temperature. Amino acid decomposition rates are much higher at 265 atm than at water steam pressure over the entire temperature range investigated.     

Raman spectroscopy at high pressure and high temperature. Phase transitions and thermodynamic properties of minerals

An outline of recent developments in Raman spectroscopy at high pressure, high temperature and combined high pressure and high temperature is presented. The instrumental and technical aspects of Raman spectroscopy, and coupling of diamond anvil cells and miniature furnaces to Raman microspectrometers are discussed. Some potential pitfalls, such as the thermal pressure in laser heated diamond anvil cells or the thermal radiation during high-temperature measurements, are presented. Special emphasis is given on processing of high-temperature Raman data. New recently discovered phase transformations in the SiO₂ system (quartz→ quartz II, pressure-induced amorphization of quartz) and structural changes in SiO₂ glass and melt are used to infer the capability of in-situ Raman spectroscopy for determining the microscopic behaviour of minerals, melts and glasses under extreme pressure and temperature conditions. Finally, it is shown how vibrational mode anharmonicity can be obtained from the pressure- and temperature-induced shifts of Raman modes. This anharmonicity can be introduced into the vibrational modeling of the thermodynamic properties (entropy and equation of state) of minerals. The example of calcite is briefly discussed.     

高温高压下叶蜡石脱水电学性质的阻抗谱分析

在1.0、2 .0GPa和873～12 2 3K的温压条件下,借助于12 6 0阻抗增益相位分析仪测定了叶蜡石的电导率,并用阻抗谱原理分析了其微观导电机制。实验结果表明:样品的电导率对频率具有很强的依赖性;电阻率随着温度的升高而减小,电导率随着温度升高而增大,logσ与1/T之间符合Arrenhius线性关系;叶蜡石在1.0GPa和2 .0GPa的压力下脱水温度分别为10 74K和110 1K。根据本次获得的电导率实验结果并结合前人对滑石族所做的工作,得出了与前人不同的结论:滑石族矿物脱水电导率曲线出现了转折点。     

Thermal equation of state of natural tourmaline at high pressure and temperature

Synchrotron-based in situ angle-dispersive X-ray diffraction experiments were conducted on a natural uvite-dominated tourmaline sample by using an external-heating diamond anvil cell at simultaneously high pressures and temperatures up to 18 GPa and 723 K, respectively. The angle-dispersive X-ray diffraction data reveal no indication of a structural phase transition over the P–T range of the current experiment in this study. The pressure–volume–temperature data were fitted by the high-temperature Birch–Murnaghan equation of state. Isothermal bulk modulus of K ₀ = 96.6 (9) GPa, pressure derivative of the bulk modulus of \(K_{0}^{\prime } = 12.5 \;(4)\), thermal expansion coefficient of α ₀ = 4.39 (27) × 10^?5 K^?1 and temperature derivative of the bulk modulus (?K/?T) _P  = ?0.009 (6) GPa K^?1 were obtained. The axial thermoelastic properties were also obtained with K _a0 = 139 (2) GPa, \(K_{a0}^{\prime }\) = 11.5 (7) and α _a0 = 1.00 (11) × 10^?5 K^?1 for the a-axis, and K _c0 = 59 (1) GPa, \(K_{c0}^{\prime }\) = 11.4 (5) and α _c0 = 2.41 (24) × 10^?5 K^?1 for the c-axis. Both of axial compression and thermal expansion exhibit large anisotropic behavior. Thermoelastic parameters of tourmaline in this study were also compared with that of the other two ring silicates of beryl and cordierite.