Studies of the equation of state and elasticity of mantle minerals

Because the Earth’s upper mantle is inaccessible to us, in order to understand the chemical and physical processes that occur in the Earth’s interior we must rely on both experimental work and computational modeling. This thesis addresses both of these geochemical methods. In the first chapter, I develop an internally consistent comprehensive molar volume model for spinels in the oxide system FeO-MgO-Fe₂O₃-Cr₂O₃-Al₂O₃-TiO₂. The model is compared to the current MELTS spinel model with a demonstration of the impact of the model difference on the estimated spinel-garnet lherzolite transition pressure. In the second chapter, I calibrate a molar volume model for cubic garnets in the system SiO₂-Al₂O₃-TiO₂-Fe₂O₃-Cr₂O₃-FeO-MnO-MgO-CaO-Na₂O. I use the method of singular value analysis to calibrate excess volume of mixing parameters for the garnet model. The implications the model has for the density of the lithospheric mantle are explored. In the third chapter, I discuss the nuclear inelastic X-ray scattering (NRIXS) method, and present analysis of three orthopyroxene samples with different Fe contents. Longitudinal and shear wave velocities, elastic parameters, and other thermodynamic information are extracted from the raw NRIXS data.

Liquid silicate equation of state : using shock waves to understand the properties of the deep Earth

The equations of state (EOS) of several geologically important silicate liquids have been constrained via preheated shock wave techniques. Results on molten Fe₂SiO₄ (fayalite), Mg₂SiO₄ (forsterite), CaFeSi₂O₆ (hedenbergite), an equimolar mixture of CaAl₂Si₂O₈-CaFeSi₂O₆ (anorthite-hedenbergite), and an equimolar mixture of CaAl₂Si₂O₈-CaFeSi₂O₆-CaMgSi₂O₆(anorthite-hedenbergite-diopside) are presented. This work represents the first ever direct EOS measurements of an iron-bearing liquid or of a forsterite liquid at pressures relevant to the deep Earth (> 135 GPa). Additionally, revised EOS for molten CaMgSi₂O₆ (diopside), CaAl₂Si₂O₈ (anorthite), and MgSiO₃ (enstatite), which were previously determined by shock wave methods, are also presented.

The liquid EOS are incorporated into a model, which employs linear mixing of volumes to determine the density of compositionally intermediate liquids in the CaO-MgO-Al₂O₃-SiO₂-FeO major element space. Liquid volumes are calculated for temperature and pressure conditions that are currently present at the core-mantle boundary or that may have occurred during differentiation of a fully molten mantle magma ocean.

The most significant implications of our results include: (1) a magma ocean of either chondrite or peridotite composition is less dense than its first crystallizing solid, which is not conducive to the formation of a basal mantle magma ocean, (2) the ambient mantle cannot produce a partial melt and an equilibrium residue sufficiently dense to form an ultralow velocity zone mush, and (3) due to the compositional dependence of Fe2+ coordination, there is a threshold of Fe concentration (molar X_Fe ≤ 0.06) permitted in a liquid for which its density can still be approximated by linear mixing of end-member volumes.

Sound velocities and equation of state of iron-rich (Mg,Fe)O

Ultralow-velocity zones (ULVZs) are small structures at the base of the mantle characterized by sound velocities up to 30% lower than those of surrounding mantle. In this thesis, we propose that iron-rich (Mg,Fe)O plays a key role in the observed sound velocities, and argue that chemically distinct, iron-enriched structures are consistent with both the low sound velocities and the measured shapes of ULVZs.

High pressure states in condensed matter: I. High pressure behavior of the iron-sulphur system with applications to the earth's core. II. Empirical equation of state for organic compounds at high pressures

Part I:

The earth's core is generally accepted to be composed primarily of iron, with an admixture of other elements. Because the outer core is observed not to transmit shear waves at seismic frequencies, it is known to be liquid or primarily liquid. A new equation of state is presented for liquid iron, in the form of parameters for the 4th order Birch-Murnaghan and Mie-Grüneisen equations of state. The parameters were constrained by a set of values for numerous properties compiled from the literature. A detailed theoretical model is used to constrain the P-T behavior of the heat capacity, based on recent advances in the understanding of the interatomic potentials for transition metals. At the reference pressure of 10⁵ Pa and temperature of 1811 K (the normal melting point of Fe), the parameters are: ρ = 7037 kg/m³, K_S0 = 110 GPa, K_S' = 4.53, K_S" = -.0337 GPa-1, and γ = 2.8, with γ α ρ^-1.17. Comparison of the properties predicted by this model with the earth model PREM indicates that the outer core is 8 to 10 % less dense than pure liquid Fe at the same conditions. The inner core is also found to be 3 to 5% less dense than pure liquid Fe, supporting the idea of a partially molten inner core. The density deficit of the outer core implies that the elements dissolved in the liquid Fe are predominantly of lower atomic weight than Fe. Of the candidate light elements favored by researchers, only sulfur readily dissolves into Fe at low pressure, which means that this element was almost certainly concentrated in the core at early times. New melting data are presented for FeS and FeS₂ which indicate that the FeS₂ is the S-hearing liquidus solid phase at inner core pressures. Consideration of the requirement that the inner core boundary be observable by seismological means and the freezing behavior of solutions leads to the possibility that the outer core may contain a significant fraction of solid material. It is found that convection in the outer core is not hindered if the solid particles are entrained in the fluid flow. This model for a core of Fe and S admits temperatures in the range 3450K to 4200K at the top of the core. An all liquid Fe-S outer core would require a temperature of about 4900 K at the top of the core.

Part II.

The abundance of uses for organic compounds in the modern world results in many applications in which these materials are subjected to high pressures. This leads to the desire to be able to describe the behavior of these materials under such conditions. Unfortunately, the number of compounds is much greater than the number of experimental data available for many of the important properties. In the past, one approach that has worked well is the calculation of appropriate properties by summing the contributions from the organic functional groups making up molecules of the compounds in question. A new set of group contributions for the molar volume, volume thermal expansivity, heat capacity, and the Rao function is presented for functional groups containing C, H, and O. This set is, in most cases, limited in application to low molecular liquids. A new technique for the calculation of the pressure derivative of the bulk modulus is also presented. Comparison with data indicates that the presented technique works very well for most low molecular hydrocarbon liquids and somewhat less well for oxygen-bearing compounds. A similar comparison of previous results for polymers indicates that the existing tabulations of group contributions for this class of materials is in need of revision. There is also evidence that the Rao function contributions for polymers and low molecular compounds are somewhat different.

The Equation of State and Petrogenesis of Komatiite

(1) Equation of State of Komatiite

The equation of state (EOS) of a molten komatiite (27 wt% MgO) was detennined in the 5 to 36 GPa pressure range via shock wave compression from 1550°C and 0 bar. Shock wave velocity, U_S, and particle velocity, U_P, in km/s follow the linear relationship U_S = 3.13(±0.03) + 1.47(±0.03) U_P. Based on a calculated density at 1550°C, 0 bar of 2.745±0.005 glee, this U_S-U_P relationship gives the isentropic bulk modulus K_S = 27.0 ± 0.6 GPa, and its first and second isentropic pressure derivatives, K'_S = 4.9 ± 0.1 and K"_S = -0.109 ± 0.003 GPa^-1.

The calculated liquidus compression curve agrees within error with the static compression results of Agee and Walker [1988a] to 6 GPa. We detennine that olivine (FO₉₄) will be neutrally buoyant in komatiitic melt of the composition we studied near 8.2 GPa. Clinopyroxene would also be neutrally buoyant near this pressure. Liquidus garnet-majorite may be less dense than this komatiitic liquid in the 20-24 GPa interval, however pyropic-garnet and perovskite phases are denser than this komatiitic liquid in their respective liquidus pressure intervals to 36 GPa. Liquidus perovskite may be neutrally buoyant near 70 GPa.

At 40 GPa, the density of shock-compressed molten komatiite would be approximately equal to the calculated density of an equivalent mixture of dense solid oxide components. This observation supports the model of Rigden et al. [1989] for compressibilities of liquid oxide components. Using their theoretical EOS for liquid forsterite and fayalite, we calculate the densities of a spectrum of melts from basaltic through peridotitic that are related to the experimentally studied komatiitic liquid by addition or subtraction of olivine. At low pressure, olivine fractionation lowers the density of basic magmas, but above 14 GPa this trend is reversed. All of these basic to ultrabasic liquids are predicted to have similar densities at 14 GPa, and this density is approximately equal to the bulk (PREM) mantle. This suggests that melts derived from a peridotitic mantle may be inhibited from ascending from depths greater than 400 km.

The EOS of ultrabasic magmas was used to model adiabatic melting in a peridotitic mantle. If komatiites are formed by >15% partial melting of a peridotitic mantle, then komatiites generated by adiabatic melting come from source regions in the lower transition zone (≈500-670 km) or the lower mantle (>670 km). The great depth of incipient melting implied by this model, and the melt density constraint mentioned above, suggest that komatiitic volcanism may be gravitationally hindered. Although komatiitic magmas are thought to separate from their coexisting crystals at a temperature =200°C greater than that for modern MORBs, their ultimate sources are predicted to be diapirs that, if adiabatically decompressed from initially solid mantle, were more than 700°C hotter than the sources of MORBs and derived from great depth.

We considered the evolution of an initially molten mantle, i.e., a magma ocean. Our model considers the thermal structure of the magma ocean, density constraints on crystal segregation, and approximate phase relationships for a nominally chondritic mantle. Crystallization will begin at the core-mantle boundary. Perovskite buoyancy at > 70 GPa may lead to a compositionally stratified lower mantle with iron-enriched mangesiowiistite content increasing with depth. The upper mantle may be depleted in perovskite components. Olivine neutral buoyancy may lead to the formation of a dunite septum in the upper mantle, partitioning the ocean into upper and lower reservoirs, but this septum must be permeable.

(2) Viscosity Measurement with Shock Waves

We have examined in detail the analytical method for measuring shear viscosity from the decay of perturbations on a corrugated shock front The relevance of initial conditions, finite shock amplitude, bulk viscosity, and the sensitivity of the measurements to the shock boundary conditions are discussed. The validity of the viscous perturbation approach is examined by numerically solving the second-order Navier-Stokes equations. These numerical experiments indicate that shock instabilities may occur even when the Kontorovich-D'yakov stability criteria are satisfied. The experimental results for water at 15 GPa are discussed, and it is suggested that the large effective viscosity determined by this method may reflect the existence of ice VII on the Rayleigh path of the Hugoniot This interpretation reconciles the experimental results with estimates and measurements obtained by other means, and is consistent with the relationship of the Hugoniot with the phase diagram for water. Sound waves are generated at 4.8 MHz at in the water experiments at 15 GPa. The existence of anelastic absorption modes near this frequency would also lead to large effective viscosity estimates.

(3) Equation of State of Molybdenum at 1400°C

Shock compression data to 96 GPa for pure molybdenum, initially heated to 1400°C, are presented. Finite strain analysis of the data gives a bulk modulus at 1400°C, K'_S. of 244±2 GPa and its pressure derivative, K'_OS of 4. A fit of shock velocity to particle velocity gives the coefficients of U_S = C_O+S U_P to be C_O = 4.77±0.06 km/s and S = 1.43±0.05. From the zero pressure sound speed, C_O, a bulk modulus of 232±6 GPa is calculated that is consistent with extrapolation of ultrasonic elasticity measurements. The temperature derivative of the bulk modulus at zero pressure, θK_OSθT|_P, is approximately -0.012 GPa/K. A thermodynamic model is used to show that the thermodynamic Grüneisen parameter is proportional to the density and independent of temperature. The Mie-Grüneisen equation of state adequately describes the high temperature behavior of molybdenum under the present range of shock loading conditions.

The stability of traveling wave solutions of parabolic equations

A method for determining by inspection the stability or instability of any solution u(t,x) = ɸ(x-ct) of any smooth equation of the form u_t = f(u_(xx),u_x,u where ∂/∂a f(a,b,c) > 0 for all arguments a,b,c, is developed. The connection between the mean wavespeed of solutions u(t,x) and their initial conditions u(0,x) is also explored. The mean wavespeed results and some of the stability results are then extended to include equations which contain integrals and also to include some special systems of equations. The results are applied to several physical examples.

Probing the thermodynamic properties of mantle rocks in solid and liquid states

Our understanding of the structure and evolution of the deep Earth is strongly linked to knowledge of the thermodynamic properties of rocky materials at extreme temperatures and pressures. In this thesis, I present work that helps constrain the equation of state properties of iron-bearing Mg-silicate perovskite as well as oxide-silicate melts. I use a mixture of experimental, statistical, and theoretical techniques to obtain knowledge about these phases. These include laser-heated diamond anvil cell experiments, Bayesian statistical analysis of powder diffraction data, and the development of a new simplified model for understanding oxide and silicate melts at mantle conditions. By shedding light on the thermodynamic properties of such ubiquitous Earth-forming materials, I hope to aid our community’s progress toward understanding the large-scale processes operating in the Earth’s mantle, both in the modern day and early in Earth’s history.

Kinetic theory of normal quantum fluids

Close to equilibrium, a normal Bose or Fermi fluid can be described by an exact kinetic equation whose kernel is nonlocal in space and time. The general expression derived for the kernel is evaluated to second order in the interparticle potential. The result is a wavevector- and frequency-dependent generalization of the linear Uehling-Uhlenbeck kernel with the Born approximation cross section.

The theory is formulated in terms of second-quantized phase space operators whose equilibrium averages are the n-particle Wigner distribution functions. Convenient expressions for the commutators and anticommutators of the phase space operators are obtained. The two-particle equilibrium distribution function is analyzed in terms of momentum-dependent quantum generalizations of the classical pair distribution function h(k) and direct correlation function c(k). The kinetic equation is presented as the equation of motion of a two -particle correlation function, the phase space density-density anticommutator, and is derived by a formal closure of the quantum BBGKY hierarchy. An alternative derivation using a projection operator is also given. It is shown that the method used for approximating the kernel by a second order expansion preserves all the sum rules to the same order, and that the second-order kernel satisfies the appropriate positivity and symmetry conditions.

Strength of thin-walled elliptical cylinders supported at the minor axis

In this investigation it was found that the instability failure of curved sheet is nearly independent of the type of loading and is primarily a function of the maximum stress, radius-thickness ration and modulus of elasticity. A method of correlating the critical stress of thin sheet under several different types of loading is given. An explanation for the experimental critical stress of thin walled cylinders under bending being greater than that for pure compression is given. The strength of unstiffened thin walled circular nose sections under pure bending was found to be controlled by local instability of the section, rather than a large scale instability. The equation of local instability of curved sheet gives values which are in fair agreement with those found experimentally.

The strength of elliptical cylinders supported at the minor axis under bending plus shear loads is governed primarily by the bending strength, and is little effected by the sheer force unless the amount of shear is quite large with respect to the moment. The effect of increasing the amount of elliptically greatly reduces the bending and shear strength of nose sections. Under torsional loads the stress at buckling falls off as the ration of the major to minor axis increases but the failure stress decreases at a slower rate than the buckling stress. The length effect of semi-circular sections under torsion is similar to that of a circular tube, and can be obtained by Donnell's theoretical equation.

Stability of parametrically excited differential equations

Sufficient stability criteria for classes of parametrically excited differential equations are developed and applied to example problems of a dynamical nature.

Stability requirements are presented in terms of 1) the modulus of the amplitude of the parametric terms, 2) the modulus of the integral of the parametric terms and 3) the modulus of the derivative of the parametric terms.

The methods employed to show stability are Liapunov’s Direct Method and the Gronwall Lemma. The type of stability is generally referred to as asymptotic stability in the sense of Liapunov.

The results indicate that if the equation of the system with the parametric terms set equal to zero exhibits stability and possesses bounded operators, then the system will be stable under sufficiently small modulus of the parametric terms or sufficiently small modulus of the integral of the parametric terms (high frequency). On the other hand, if the equation of the system exhibits individual stability for all values that the parameter assumes in the time interval, then the actual system will be stable under sufficiently small modulus of the derivative of the parametric terms (slowly varying).

Experimental and theoretical studies of the electrothermal instability in a nonequilibrium plasma

Experimental and theoretical studies have been made of the electrothermal waves occurring in a nonequilibrium MHD plasma. These waves are caused by an instability that occurs when a plasma having a dependence of conductivity on current density is subjected to crossed electric and magnetic fields. Theoretically, these waves were studied by developing and solving the equations of a steady, one-dimensional nonuniformity in electron density. From these nonlinear equations, predictions of the maximum amplitude and of the half width of steady waves could be obtained. Experimentally, the waves were studied in a nonequilibrium discharge produced in a potassium-seeded argon plasma at 2000°K and 1 atm. pressure. The behavior of such a discharge with four different configurations of electrodes was determined from photographs, photomultiplier measurements, and voltage probes. These four configurations were chosen to produce steady waves, to check the stability of steady waves, and to observe the manifestation of the waves in a MHD generator or accelerator configuration.

Steady, one-dimensional waves were found to exist in a number of situations, and where they existed, their characteristics agreed with the predictions of the steady theory. Some extensions of this theory were necessary, however, to describe the transient phenomena occurring in the inlet region of a discharge transverse to the gas flow. It was also found that in a discharge away from the stabilizing effect of the electrodes, steady waves became unstable for large Hall parameters. Methods of prediction of the effective electrical conductivity and Hall parameter of a plasma with nonuniformities caused by the electrothermal waves were also studied. Using these methods and the values of amplitude predicted by the steady theory, it was found that the measured decrease in transverse conductivity of a MHD device, 50 per cent at a Hall parameter of 5, could be accounted for in terms of the electrothermal instability.

I. Stokes flow past a thin screen. II. Viscous flows past porous bodies of finite size

Part I

The slow, viscous flow past a thin screen is analyzed based on Stokes equations. The problem is reduced to an associated electric potential problem as introduced by Roscoe. Alternatively, the problem is formulated in terms of a Stokeslet distribution, which turns out to be equivalent to the first approach.

Special interest is directed towards the solution of the Stokes flow past a circular annulus. A "Stokeslet" formulation is used in this analysis. The problem is finally reduced to solving a Fredholm integral equation of the second kind. Numerical data for the drag coefficient and the mean velocity through the hole of the annulus are obtained.

Stokes flow past a circular screen with numerous holes is also attempted by assuming a set of approximate boundary conditions. An "electric potential" formulation is used, and the problem is also reduced to solving a Fredholm integral equation of the second kind. Drag coefficient and mean velocity through the screen are computed.

Part II

The purpose of this investigation is to formulate correctly a set of boundary conditions to be prescribed at the interface between a viscous flow region and a porous medium so that the problem of a viscous flow past a porous body can be solved.

General macroscopic equations of motion for flow through porous media are first derived by averaging Stokes equations over a volume element of the medium. These equations, including viscous stresses for the description, are more general than Darcy's law. They reduce to Darcy's law when the Darcy number becomes extremely small.

The interface boundary conditions of the first kind are then formulated with respect to the general macroscopic equations applied within the porous region. An application of such equations and boundary conditions to a Poiseuille shear flow problem demonstrates that there usually exists a thin interface layer immediately inside the porous medium in which the tangential velocity varies exponentially and Darcy's law does not apply.

With Darcy's law assumed within the porous region, interface boundary conditions of the second kind are established which relate the flow variables across the interface layer. The primary feature is a jump condition on the tangential velocity, which is found to be directly proportional to the normal gradient of the tangential velocity immediately outside the porous medium. This is in agreement with the experimental results of Beavers, et al.

The derived boundary conditions are applied in the solutions of two other problems: (1) Viscous flow between a rotating solid cylinder and a stationary porous cylinder, and (2) Stokes flow past a porous sphere.

Thermodynamic and kinetic behavior of an argon plasma jet. Decomposition of nitric oxide between 1300 - 1750 degrees K in an argon plasma

In the first part of the study, an RF coupled, atmospheric pressure, laminar plasma jet of argon was investigated for thermodynamic equilibrium and some rate processes.

Improved values of transition probabilities for 17 lines of argon I were developed from known values for 7 lines. The effect of inhomogeneity of the source was pointed out.

The temperatures, T, and the electron densities, n_e , were determined spectroscopically from the population densities of the higher excited states assuming the Saha-Boltzmann relationship to be valid for these states. The axial velocities, v_z, were measured by tracing the paths of particles of boron nitride using a three-dimentional mapping technique. The above quantities varied in the following ranges: 10¹² ˂ n_e ˂ 10¹⁵ particles/cm³, 3500 ˂ T ˂ 11000 °K, and 200 ˂ v_z ˂ 1200 cm/sec.

The absence of excitation equilibrium for the lower excitation population including the ground state under certain conditions of T and n_e was established and the departure from equilibrium was examined quantitatively. The ground state was shown to be highly underpopulated for the decaying plasma.

Rates of recombination between electrons and ions were obtained by solving the steady-state equation of continuity for electrons. The observed rates were consistent with a dissociative-molecular ion mechanism with a steady-state assumption for the molecular ions.

In the second part of the study, decomposition of NO was studied in the plasma at lower temperatures. The mole fractions of NO denoted by x_NO were determined gas-chromatographically and varied between 0.0012 ˂ x_NO ˂ 0.0055. The temperatures were measured pyrometrically and varied between 1300 ˂ T ˂ 1750°K. The observed rates of decomposition were orders of magnitude greater than those obtained by the previous workers under purely thermal reaction conditions. The overall activation energy was about 9 kcal/g mol which was considerably lower than the value under thermal conditions. The effect of excess nitrogen was to reduce the rate of decomposition of NO and to increase the order of the reaction with respect to NO from 1.33 to 1.85. The observed rates were consistent with a chain mechanism in which atomic nitrogen and oxygen act as chain carriers. The increased rates of decomposition and the reduced activation energy in the presence of the plasma could be explained on the basis of the observed large amount of atomic nitrogen which was probably formed as the result of reactions between excited atoms and ions of argon and the molecular nitrogen.

Boundary value problems for stochastic differential equations

A theory of two-point boundary value problems analogous to the theory of initial value problems for stochastic ordinary differential equations whose solutions form Markov processes is developed. The theory of initial value problems consists of three main parts: the proof that the solution process is markovian and diffusive; the construction of the Kolmogorov or Fokker-Planck equation of the process; and the proof that the transistion probability density of the process is a unique solution of the Fokker-Planck equation.

It is assumed here that the stochastic differential equation under consideration has, as an initial value problem, a diffusive markovian solution process. When a given boundary value problem for this stochastic equation almost surely has unique solutions, we show that the solution process of the boundary value problem is also a diffusive Markov process. Since a boundary value problem, unlike an initial value problem, has no preferred direction for the parameter set, we find that there are two Fokker-Planck equations, one for each direction. It is shown that the density of the solution process of the boundary value problem is the unique simultaneous solution of this pair of Fokker-Planck equations.

This theory is then applied to the problem of a vibrating string with stochastic density.

Where Tori fear to tread : hypermassive neutron star remnants and absolute event horizons Or topics in computational general relativity

Computational general relativity is a field of study which has reached maturity only within the last decade. This thesis details several studies that elucidate phenomena related to the coalescence of compact object binaries. Chapters 2 and 3 recounts work towards developing new analytical tools for visualizing and reasoning about dynamics in strongly curved spacetimes. In both studies, the results employ analogies with the classical theory of electricity and magnitism, first (Ch. 2) in the post-Newtonian approximation to general relativity and then (Ch. 3) in full general relativity though in the absence of matter sources. In Chapter 4, we examine the topological structure of absolute event horizons during binary black hole merger simulations conducted with the SpEC code. Chapter 6 reports on the progress of the SpEC code in simulating the coalescence of neutron star-neutron star binaries, while Chapter 7 tests the effects of various numerical gauge conditions on the robustness of black hole formation from stellar collapse in SpEC. In Chapter 5, we examine the nature of pseudospectral expansions of non-smooth functions motivated by the need to simulate the stellar surface in Chapters 6 and 7. In Chapter 8, we study how thermal effects in the nuclear equation of state effect the equilibria and stability of hypermassive neutron stars. Chapter 9 presents supplements to the work in Chapter 8, including an examination of the stability question raised in Chapter 8 in greater mathematical detail.