High-temperature elasticity of the fluorite-structure compounds CaF2, SrF2 and BaF2

The elastic moduli of single-crystal CaF₂, SrF₂ and BaF₂ have been determined by the ultrasonic pulse superposition technique as a function of temperature from T = 298 to T = 650°K. These new data are consistent with other data obtained by ultrasonic pulse techniques in the region of room temperature and are superior to previous high-temperature data from resonance experiments. The elastic moduli (c) are represented by quadratic functions in T over the experimental temperature range with the curvature in the same sense for all the moduli. Evaluation of the temperature derivatives of the elastic moduli at constant volume indicates that the dominant temperature effect is extrinsic for (?K_S/?T)_P and intrinsic for (?μ/?T)_P, where K_S and μ are the isotropic bulk and shear moduli, respectively. For the series CaF₂SrF₂BaF₂, |(?c/?T)_p| decreases with increasing molar volume for all moduli; however there are no theoretical or empirical grounds on which to derive a simple relationship between (?c/?T)_P and crystallographic parameters.     

Phase relations in the system LiFMgF2 at elevated pressures: Implications for the proposed mixed-oxide zone of the earth's mantle

Solvi and liquidi for various LiFMgF₂ mixtures have been determined at pressures up to 40 kbar by differential-thermal-analysis in a piston-cylinder high-pressure device. The melting curves of pure LiF and MgF₂ were also studied and the initial slopes (dT_m/dP)_{P = 0} were found to be 11.2 and 8.3°C/kbar, respectively. The eutectic composition (LiF)_0.64(MgF₂)_0.36 is independent of pressure to 35 kbar and the eutectic temperature rises approximately 6.3°C per kbar. Initial slopes of 11°C/kbar and 35°C/kbar are inferred for the melting curves of MgO and SiO₂ (stishovite) respectively, on the basis of data for their structural analogue compounds. The observed solid solution of LiF in MgF₂ and other evidence suggest the possibility of solid solution in the system (Mg,Fe)OSiO₂ (stishovite) under mantle conditions which may have important consequences for the elastic properties of a “mixed-oxide” zone of the earth's mantle.     

Thermal regime of the Earth's core

The outer core is assumed to consist of iron and sulfur, with a small amount of potassium that generates heat by radioactive decay of sim||pre|40 K. Two cases are considered, corresponding respectively to a high rate of heat production (Q = 2 · 10¹² cal./sec, about 0.1% K), and to a low rate (Q = 2 · 10¹¹ cal./sec). The temperature at a depth of 2800 km in the mantle is taken to be 3300°K (Wang, 1972). The temperature T_c at the core-mantle boundary depends on whether or not a density gradient in the lowermost layer D″ of the mantle prevents convection in that layer. In the first case, and for high Q, T_c = 4500–5000°K. In the second case, or for low Q, T_c ≈ 3500°K.The heat-conduction equation is used to calculate the temperature T_i at the inner-core boundary in the absence of convection. For high Q, T_i ? T_c ≈ 1600°K; for low Q, T_i ? T_c ≈ 160°K. Corresponding temperature gradients at r = r_c and r = r_i are listed in Table I.The adiabatic gradient at the top of the core is calculated by the method of Stewart (1970). It strongly depends on the parameters (ρ₀, c₀, γ₀, etc.) that characterize core material at low pressure. Stewart has drawn graphs that allow the selection of sets of parameters that are consistent with seismic velocities and a given density distribution in the core. Some acceptable sets of parameters are listed in Table II. Many sets yield temperatures T_c in the range 3500–5000°K; some give an adiabatic gradient steeper than the conductive gradient and are compatible with convection; others do not. Since properties of FeS melts remain unknown, there is at present no way of selecting any set in preference to another.Properties of the FeS system at low pressure suggest the possible appearance of immiscibility at high temperature in liquids of low sulfur content; accordingly, the inner-core boundary is thought to represent equilibrium between a solid (FeNi) inner core and a liquid layer containing only a small amount of sulfur; layer F in turn is in equilibrium with another liquid (forming layer E) containing more sulfur, and slightly less dense, than F. The temperature T_i at the inner-core boundary is about 6000–6500°K for high Q and T_c ≈ 4500–5000°K. It is consistent with Alder's (1966) and Leppaluoto's (1972) estimates of the melting point of iron at 3.3 Mbar, but not with that of Higgins and Kennedy (1971).     

Measurement of the adiabats of quartz,forsterite, and magnesium oxide at high pressures and high temperatures and adiabatic gradient in the mantle

The geophysically-important adiabat (?T/?P)_s has been measured at pressures up to 50 kbar and temperatures up to 1000°C. A simple power law describes the relationship between (?T/?P)_s and the compression of the material. The power is independent of the material and of the temperature within the uncertainty. This consistency in the power allows the extrapolation of the adiabat to pressure and temperature conditions of the mantle of the earth. The adiabatic gradient is shown to be significantly smaller than the melting gradient.     

Ultrasonic measurements of Vp and Qp: relaxation spectrum of complex modulus on basalt melts

Ultrasonic compressional wave velocity V_p and quality factor Q_p have been measured in alkali basalt, olivine basalt and basic andesite melts in the frequency range of 3.4–22 MHz and in the temperature range of 1100–1400°C. Velocity and attenuation of the melts depend on frequency and temperature, showing that there are relaxation mechanisms in the melts. Complex moduli are calculated from the ultrasonic data. The results fit well a complex modulus of Arrhenius temperature dependence with log-normal Gaussian distribution in relaxation times of attenuation. The analysis yields average relaxation time, its activation energy, relaxed modulus, unrelaxed modulus and width of Gaussian distribution in relaxation times. Relaxed modulus is smaller (17.5 GPa) for basic andesite melt of high silica and high alumina contents than for the other two basalt melts (18.1–18.4 GPa). The most probable relaxation times decrease from ～ 3 × 10^?10 s for basic andesite to ～ 10^?11 s for alkali basalt at 1400°C. Activation energies of attenuation, ranging from 270 to 340 kJ mol^?1 in the three melts, are highest in basic andesite. Longitudinal viscosity values and their temperature dependences are also calculated from V_p and Q_p data. The volume viscosity values are estimated from the data using the shear viscosity values. Longitudinal, volume and shear viscosities and their activation energies are highest in the basic andesite melt of the most polymerized structure.     

Magnetic properties of synthetic titanomagnetites

Magnetic properties and crystal structure parameters of synthetic solid solutions Fe₃O₄Fe₃TiO₄, Fe₂O₄MgFe₂O₄ and Fe₃O₄Mg₂TiO₄ have been studied. Basic regularities in the behaviour of saturation magnetisation (I_s), Curie temperature (T_C) and cubic lattice parameter a during the substitution of Ti and Mg ions for Fe ions have been found. As the concentration of Ti ions increases, I_s reduces from 70 Gs·cm³ g^?1 to 0, T_C changes from 580 to 130°C and a from 8.391 to 8.520 Å. Growth of the Mg concentration leads to changes in I_s to 19.8 Gs·cm³, g^?1, T_C, to 440°C and a, to 8.360 Å. The full Fe ions substitution gives $\text{“a”=8.440}\text{A}\text{?}$.Chemical compositions of the samples, in which the valency variation of Fe ions at oxidation leads to an increase in susceptibility and T_C, have been determined.     

Elastic and thermal properties of fluoride and oxide analogues in the rocksalt,fluorite, rutile and perovskite structures

Fluorides are considered as models for the physical properties of oxides on the basis of Goldschmidt's crystal chemical arguments. The well-established bulk modulus (K)-volume (V) relationship KV = constant is sddddhown to hold for fluorides and oxides belonging to the four isostructural series. The bulk moduli of equivolume oxides and fluorides are scaled as 4S², where S = Z^O/2Z^F is the ratio of the effective unit charges and is approximately 77% for all of the crystal structures. The fluorides have distinctly lower melting and Debye temperatures which offers the possibility of using these compounds as models for the high-temperature elastic behaviour of their oxide analogues.     

In situ measurements of sound velocities and densities across the orthopyroxene → high-pressure clinopyroxene transition in MgSiO3 at high pressure

Using acoustic measurement interfaced with a large volume multi-anvil apparatus in conjunction with in situ X-radiation techniques, we are able to measure the density and elastic wave velocities (V_P and V_S) for both ortho- and high-pressure clino-MgSiO₃ polymorphs in the same experimental run. The elastic bulk and shear moduli of the unquenchable high-pressure clinoenstatite phase were measured within its stability field for the first time. The measured density contrast associated with the phase transition OEN → HP-CEN is 2.6-2.9% in the pressure of 7-9 GPa, and the corresponding velocity jumps are 3-4% for P waves and 5-6% for S waves. The elastic moduli of the HP-CEN phase are K_S=156.7(8) GPa, G = 98.5(4) GPa and their pressure derivatives are K_S′=5.5(3) and G′ = 1.5(1) at a pressure of 6.5 GPa, room temperature. In addition, we observed anomalous elastic behavior in orthoenstatite at pressure above 9 GPa at room temperature. Both elastic wave velocities exhibited softening between 9 and 13-14 GPa, which we suggest is associated with a transition to a metastable phase intermediate between OEN and HP-CEN.     

General relationships among sound speeds: II. Theory and discussion

The dependence of bulk sound speed V_φ upon mean atomic weight $\text{m}$ and density ρ can be expressed in a single equation:

$\text{V}{}_{\mathrm{\phi }}\text{=Bρ}{}^{\mathrm{\lambda }}\text{(}\text{m}{}_0\text{m}{}^{\mathrm{<mtext>[</mtext><mtext>1</mtext><mtext>2</mtext><mtext>+\lambda (1?c)]</mtext>}}\text{(}\text{km/sec}\text{)}$

Here B is an empirically determined “universal” parameter equal to 1.42, $\text{m}{}_0\text{= 20.2}$, a reference mean atomic weight for which well-determined elastic properties exist, and λ = 1.25 is a semi empirical parameter equal to $\text{γ ?}\text{1}\text{3}$ where γ is a Grüneisen parameter. The constant c = (? ln V_M/? ln $\text{m}\text{)}{}_{\mathrm{X}}$, where V_M is molar volume, is in general different for different crystal structure series and different cation substitutions. However, it is possible to use c_Fe = 0.14 for Fe²⁺Mg²⁺ and GeSi substitutions and c_Ca ? 1.3 for CaMg substitutional series. With these values it is pos to deduce from the above equation Birch's law, its modifications introduced by Simmons to account for Ca-bearing minerals, variations in the seismic equation of state observed by D.L. Anderson, and the apparent proportionality of bulk modulus K to V_M^?4.     

Methods for estimating Curie temperatures of titanomaghemites from experimentalJs-T data

Methods for determining the Curie temperature (T_c) of titanomaghemites from experimental saturation magnetization-temperature (J_s-T) data are reviewed.J_s-T curves for many submarine basalts and synthetic titanomaghemites are irreversible and determining Curie temperatures from these curves is not a straightforward procedure. Subsequently, differences of sometimes over 100°C in the values ofT_c may result just from the method of calculation. Two methods for determiningT_c will be discussed: (1) the graphical method, and (2) the extrapolation method. The graphical method is the most common method employed for determining Curie temperatures of submarine basalts and synthetic titanomaghemites. The extrapolation method based on the quantum mechanical and thermodynamic aspects of the temperature variation of saturation magnetization nearT_c, although not new to solid state physics, has not been used for estimating Curie temperatures of submarine basalts. The extrapolation method is more objective than the graphical method and uses the actual magnetization data in estimatingT_c.     

Thermal equation of state of magnesiowüstite (Mg0.6Fe0.4)O

Volume measurements for magnesiowüstite (Mg_0.6Fe_0.4)O, were carried out up to pressures of 10.1 GPa in the temperature range 300–1273 K, using energy-dispersive synchrotron X-ray diffraction. These data allow reliable determination of the temperature dependence of the bulk modulus and good constraint on the thermal expansitivity at ambient pressure which was previously not known for magnesiowüstite. From these data, thermal and elastic parameters were derived from various approaches based on the Birch–Murnaghan equation of state (EOS) and on the relevant thermodynamic relations. The results from three different equations of state are remarkably consistent. With (∂K_T/∂P)_T fixed at 4, we obtained K₀=158(2) GPa, (∂K_T/∂T)_P=−0.029(3) GPa K⁻¹, (∂K_T/∂T)_V=−3.9(±2.3)×10⁻³ GPa K⁻¹, and α_T=3.45(18)×10⁻⁵+1.14(28)×10⁻⁸T. The K₀, (∂K_T/∂T)_P, and (∂K_T/∂T)_V values are in agreement with those of Fei et al. (1992) and are similar to previously determined values for MgO. The zero pressure thermal expansitivity of (Mg_0.6Fe_0.4)O is found to be similar to that for MgO (Suzuki, 1975). These results indicate that, for the compositional range x=0–0.4 in (Mg_1−xFe_x)O, the thermal and elastic properties of magnesiowüstite exhibit a dependence on the iron content that is negligibly small, within uncertainties of the experiments. They are consequently insensitive to the Fe–Mg partitioning between (Mg, Fe)SiO₃ perovskite and magnesiowüstite when applied to compositional models of the lower mantle. With the assumption that (Mg_0.6Fe_0.4)O is a Debye-like solid, a modified equation of heat capacity at constant pressure is proposed and thermodynamic properties of geophysically importance are calculated and tabulated at high temperatures.     

Elasticity of (Mg0.83,Fe0.17)O ferropericlase at high pressure: ultrasonic measurements in conjunction with X-radiation techniques

The elasticity of ferropericlase with a potential mantle composition of (Mg_0.83,Fe_0.17)O is determined using ultrasonic interferometry in conjunction with in situ X-radiation techniques (X-ray diffraction and X-radiography) in a DIA-type cubic anvil high-pressure apparatus to pressures of 9 GPa (NaCl pressure scale) at room temperature. In this study, we demonstrate that it is possible to directly monitor the specimen length using an X-ray image technique and show that these lengths are consistent with those derived from X-ray diffraction data when no plastic deformation of the specimen occurs during the experiment. By combining the ultrasonic and X-ray diffraction data, the adiabatic elastic bulk (K_S) and shear (G) moduli and specimen volume can be measured simultaneously. This enables pressure scale-free measurements of the equation of state of the specimen using a parameterization such as the Birch-Murnaghan equation of state. The elastic moduli determined for (Mg_0.83,Fe_0.17)O are K_S0=165.5(12) GPa, G₀=112.4(4) GPa, and their pressure derivatives are K_S0′=4.17(20) and G₀′=1.89(6). If these results are compared with those for MgO, they demonstrate that K_S0 and K_S0′ are insensitive to the addition of 17 mol% FeO, but G₀ and G₀′ are reduced by 14% and 24%, respectively. We calculate that the P and S wave velocities of a perovskite plus ferropericlase phase assemblage with a pyrolite composition at the top of the lower mantle (660 km depth) are lowered by 0.8 and 2.3%, respectively, when compared with those calculated using the elastic properties of end-member MgO. Consequently, the magnitudes of the calculated wave velocity jumps across the 660 km discontinuity are reduced by about 11% for P wave and 20% for S wave, if this discontinuity is considered as a phase transformation boundary only (ringwoodite→perovskite+ferropericlase).     

Melting temperature distribution and fractionation in the lower mantle

The melting curve of perovskite MgSiO₃ and the liquidus and solidus curves of the lower mantle were estimated from thermodynamic data and the results of experiments on phase changes and melting in silicates.The initial slope of the melting curve of perovskite MgSiO₃ was obtained as $\text{d}\text{T}{}_{\mathrm{<mtext>m</mtext>}}\text{/}\text{d}\text{P?77}\text{K}\text{GPa}{}^{\mathrm{?1}}$ at 23 GPa. The melting curve of perovskite was expressed by the Kraut-Kennedy equation as $\text{T}{}_{\mathrm{<mtext>m</mtext>}}\text{(}\text{K}\text{)=917(}\text{1+29.6ΔV}\text{V}{}_0\text{)}$, where T_m?2900 K and P?23 GPa; and by the Simon equation, $\text{P(}\text{GPa}\text{)?23=21.2[}\text{(T}{}_{\mathrm{<mtext>m</mtext>}}\text{(}\text{K}\text{)}\text{2900)}{}^{1.75}\text{?1}\text{]}$.The liquidus curve of the lower mantle was estimated as $\text{T}{}_{\mathrm{<mtext>liq</mtext>}}\text{? 0.9 T}{}_{\mathrm{<mtext>m</mtext>}}$ (perovskite) and this gives the liquidus temperature T_liq=7000 ±500 K at the mantle-core boundary. The solidus curve of the lower mantle was also estimated by extrapolating the solidus curve of dry peridotite using the slope of the solidus curve of magnesiowüstite at high pressures. The solidus temperature is ～ 5000 K at the base of the lower mantle. If the temperature distribution of the mantle was 1.5 times higher than that given by the present geotherm in the early stage of the Earth's history, partial melting would have proceeded into the deep interior of the lower mantle.Estimation of the density of melts in the MgOFeOSiO₂ system for lower mantle conditions indicates that the initial melt formed by partial fusion of the lower mantle would be denser than the residual solid because of high concentration of iron into the melt. Thus, the melt generated in the lower mantle would tend to move downward toward the mantle-core boundary. This downward transportation of the melt in the lower mantle might have affected the chemistry of the lower mantle, such as in the D″ layer, and the distribution of the radioactive elements between mantle and core.     

High-pressure X-ray diffraction studies on β- and γ-Mg2SiO4

Pressure effects on the lattice parameters of β- and γ-Mg₂SiO₄ have been measured at room temperature and at pressures up to 100 kbar using a multi-anvil high-pressure X-ray diffraction apparatus. The volume changes (ΔV/V₀) at 90 kbar are 5.4 · 10^?2 and 4.2 · 10^?2 for β- and γ-Mg₂SiO₄, respectively. Isothermal bulk moduli at zero pressure have been calculated from least-square fits of the data to straight lines. They turn out to be 1.66 ± 0.4 and 2.13 ± 0.1 Mbar for β- and γ-Mg₂SiO₄, respectively. The α → γ transition obeys Wang's linear V_φ?ρ relation but the α → β transition does not.     

Elastic properties of polycrystalline diopside (CaMgSi2O6)

A polycrystalline specimen of clinopyroxene diopside has been hot-pressed at P = 15 kbar and T = 850°C in a piston-cylinder apparatus. Compressional (ν_P) and shear (ν_S) velocities are determined as a function of pressure to 7.5 kbar at room temperature by an ultrasonic pulse transmission technique. The velocities at 7.5 kbar are ν_P = 8.06 km/sec and ν_S = 4.77 km/sec. These data are consistent with velocity-density trends for orthopyroxenes due to the compensating effects of the monoclinic structure (positive) and Ca content (negative). With the addition of the new data for diopside, it is possible to calculate directly the velocities of various upper-mantle mineral assemblages.     

Temperature dependence of the elastic moduli of ringwoodite

The elastic moduli of polycrystalline ringwoodite, (Mg_0.91Fe_0.09)₂SiO₄, were measured up to 470 K by means of the resonant sphere technique. The adiabatic bulk (K_S) and shear (μ) moduli were found to be 185.1(2) and 118.22(6) GPa at room temperature, and the average slopes of dK_S/dT and dμ/dT in the temperature range of the study were determined to be −0.0193(9) and −0.0148(3) GPa/K, respectively. Using these results, we estimate seismic wave velocity jumps for a pure olivine mantle model at 520 km depth. We find that the jump for the S-wave velocity is about 1.5 times larger than that for the P-wave velocity at this depth. This suggests that velocity jumps at the 520 km discontinuity are easier to detect using S-waves than P-waves.     

Effects of multiple scattering on coda waves in three-dimensional medium

The contribution of multiple scattering to the coda waves for three-dimensional elastic medium is investigated by extending the computational procedures developed earlier for the two-dimensional medium. It is shown that the effects of multiple scattering start to become important at a shorter lapse time,t _c = 0.65(n ₀σu)^?1, than in the two-dimensional case (t _c = 0.8(n ₀σu)^?1).     

Brief note on effects of thermal pulses on elastic moduli and Q of rock

Preliminary results of a current experimental study on relationships between elastic moduli, internal friction (Q^?1) and rock structure are compatible with lunar in situ observations which indicate that mechanisms which lower the elastic moduli of rock need not contribute significantly to the internal friction. In terrestrial rock samples which were thermally pulsed in vacuum, elastic moduli decreased andQ's increased. These results imply that the thermal pulsing induces damage such as microcracks (which lower the elastic moduli), eliminates crack surface contaminants and may destroy other possible sites of internal friction such as grain boundary mechanisms and hydrous minerals (increasingQ).     

Performance of the complete travel-time equation of state at simultaneous high pressure and temperature

The complete travel-time equation of state (CT-EOS) is presented by utilizing thermodynamics relations, such as; $$K_T = K_S (1 + \alpha \gamma T)^{ - 1} , \gamma = \frac{{\alpha K_S }}{{\rho C_P }}, \left. {\frac{{\partial C_P }}{{\partial P}}} \right)_T = - \frac{T}{\rho }\left[ {\alpha ^2 + \left. {\frac{{\partial \alpha }}{{\partial T}}} \right)_P } \right], etc.$$ The CT-EOS enables us to analyze ultrasonic experimental data under simultaneous high pressure and high temperature without introducing any assumption, as long as the density, or thermal expansivity, and heat capacity are also available as functions of temperature at zero pressure. The performance of the CT-EOS was examined by using synthesized travel-time data with random noise of 10^?5 and 10^?4 amplitude up to 4 GPa and 1500 K. Those test conditions are to be met with the newly developed GHz interferometry in a gas medium piston cylinder apparatus. The results suggest that the combination of the CT-EOS and accurate experimental data (10^?4 in travel time) can determine thermodynamic and elastic parameters, as well as their derivatives with unprecedented accuracy, yielding second-order pressure derivatives (?² M/?P ²) of the elastic moduli as well as the temperature derivatives of their first-order pressure derivatives ?² M/?P?T). The completeness of the CT-EOS provides an unambiguous criterion to evaluate the compatibility of empirical EOS with experimental data. Furthermore because of this completeness, it offers the possibility of a new and absolute pressure calibration when X-ray (i.e., volume) measurements are made simultaneously with the travel-time measurements.     

Ultrasonic velocities of North Sea chalk samples: influence of porosity, fluid content and texture

We have studied 56 unfractured chalk samples of the Upper Cretaceous Tor Formation of the Dan, South Arne and Gorm Fields, Danish North Sea. The samples have porosities of between 14% and 45% and calcite content of over 95%. The ultrasonic compressional‐ and shear‐wave velocities (V_P and V_S) for dry and water‐saturated samples were measured at up to 75 bar confining hydrostatic pressure corresponding to effective stress in the reservoir. The porosity is the main control of the ultrasonic velocities and therefore of the elastic moduli. The elastic moduli are slightly higher for samples from the South Arne Field than from the Dan Field for identical porosities. This difference may be due to textural differences between the chalk at the two locations because we observe that large grains (i.e. filled microfossils and fossil fragments) that occur more frequently in samples from the Dan Field have a porosity‐reducing effect and that samples rich in large grains have a relatively low porosity for a given P‐wave modulus. The clay content in the samples is low and is mainly represented by either kaolinite or smectite; samples with smectite have a lower P‐wave modulus than samples with kaolinite at equal porosity. We find that ultrasonic V_P and V_S of dry chalk samples can be satisfactorily estimated with Gassmann's relationships from data for water‐saturated samples. A pronounced difference between the V_P/V_S ratios for dry and water‐saturated chalk samples indicates promising results for seismic amplitude‐versus‐offset analyses.