Performance calculations of new propellant systems

The purpose of this thesis is to investigate the effect on performance and chamber temperature of adding hydrogen to a propellant system. The systems investigated are:

(1) RFNA-Aniline

(2) Nitromethane

(3) Anhydrous hydrazene-liquid oxygen

Since a systematic investigation of the performance parameters of the RFNA-Aniline system over a wide range of mixture ratios has never been made, it was decided to make these calculations, in addition to the investigations stated above.

The results of the calculations can best be summarized by a study of the figures at the end of the thesis. A few generalizations can be made. The effect of adding hydrogen in small quantities to a high temperature system is to increase the performance considerably without too much change in the chamber temperature. As more hydrogen is added, the percentage increase in performance. If hydrogen is added in large quantities, both the performance curve (effective exhaust velocity) and the chamber temperature curve flatten out.

The behavior discussed above is characteristic of hot propellant systems such as RFNA-Aniline and anhydrous hydrazene. In a low temperature system, such as nitromethane, the effect is quite different. The addition of hydrogen in small quantities causes a rapid decrease in chamber temperature, but the increase in performance is considerably less on a percentage basis. As more hydrogen is added the changes in performance and chamber temperature are almost linear.

The hydro-kinetic theory of liquid helium II

In Part I the kinetic theory of excitations in flowing liquid He II is developed to a higher order than that carried out previously, by Landau and Khalatnikov, in order to demonstrate the existence of non-equilibrium terms of a new nature in the hydrodynamic equations. It is then shown that these terms can lead to spontaneous destabilization in counter currents when the relative velocity of the normal and super fluids exceeds a critical value that depends on the temperature, but not on geometry. There are no adjustable parameters in the theory. The critical velocities are estimated to be in the 14-20 m/sec range for T ≤ 2.0° K, but tend to zero as T → T_λ. The possibility that these critical velocities may be related to the experimentally observed "intrinsic" critical velocities is discussed.

Part II consists of a semi-classical investigation of rotonquantized vortex line interactions. An essentially classical model is used for the collision and the behavior of the roton in the vortex field is investigated in detail. From this model it is possible to derive the HVBK mutual friction terms that appear in the phenomenalogical equations of motion for rotating liquid He II. Estimates of the Hall and Vinen B and B' coefficients are in good agreement with experiments. The claim is made that the theory does not contain any arbitrary adjustable parameters.

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.

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.

Investigations of charge-carrier dynamics at semiconductor/liquid interfaces

Theoretical and experimental investigations of charge-carrier dynamics at semiconductor/liquid interfaces, specifically with respect to interfacial electron transfer and surface recombination, are presented.

Fermi's golden rule has been used to formulate rate expressions for charge transfer of delocalized carriers in a nondegenerately doped semiconducting electrode to localized, outer-sphere redox acceptors in an electrolyte phase. The treatment allows comparison between charge-transfer kinetic data at metallic, semimetallic, and semiconducting electrodes in terms of parameters such as the electronic coupling to the electrode, the attenuation of coupling with distance into the electrolyte, and the reorganization energy of the charge-transfer event. Within this framework, rate constant values expected at representative semiconducting electrodes have been determined from experimental data for charge transfer at metallic electrodes. The maximum rate constant (i.e., at optimal exoergicity) for outer-sphere processes at semiconducting electrodes is computed to be in the range 10^-17-10^-16 cm⁴ s^-1, which is in excellent agreement with prior theoretical models and experimental results for charge-transfer kinetics at semiconductor/liquid interfaces.

Double-layer corrections have been evaluated for semiconductor electrodes in both depletion and accumulation conditions. In conjuction with the Gouy-Chapman-Stern model, a finite difference approach has been used to calculate potential drops at a representative solid/liquid interface. Under all conditions that were simulated, the correction to the driving force used to evaluate the interfacial rate constant was determined to be less than 2% of the uncorrected interfacial rate constant.

Photoconductivity decay lifetimes have been obtained for Si(111) in contact with solutions of CH₃OH or tetrahydrofuran containing one-electron oxidants. Silicon surfaces in contact with electrolyte solutions having Nernstian redox potentials > 0 V vs. SCE exhibited low effective surface recombination velocities regardless of the different surface chemistries. The formation of an inversion layer, and not a reduced density of electrical trap sites on the surface, is shown to be responsible for the long charge-carrier lifetimes observed for these systems. In addition, a method for preparing an air-stable, low surface recombination velocity Si surface through a two-step, chlorination/alkylation reaction is described.

I. Spectroscopic observation of discrete sites in simple liquids. II. Infrared intensity perturbations of hydrogen halide fundamentals in liquid xenon. III. Rotation of HCl in solid rare gases.

Part I

The spectrum of dissolved mercury atoms in simple liquids has been shown to be capable of revealing information concerning local structures in these liquids.

Part II

Infrared intensity perturbations in simple solutions have been shown to involve more detailed interaction than just dielectric polarization. No correlation has been found between frequency shifts and intensity enhancements.

Part III

Evidence for perturbed rotation of HCl in rare gas matrices has been found. The magnitude of the barrier to rotation is concluded to be of order of 30 cm^(-1).

Experimental study on inertial effects in liquid-solid flows

This thesis presents experimental measurements of the rheological behavior of liquid-solid mixtures at moderate Reynolds (defined by the shear rate and particle diameter) and Stokes numbers, ranging from 3 ≤ Re ≤ 1.6 × 10³ and 0.4 ≤ St ≤ 195. The experiments use a specifically designed Couette cylindrical rheometer that allows for probing the transition from transporting a pure liquid to transporting a dense suspension of particles. Measurements of the shear stress are presented for a wide range of particle concentration (10 to 60% in volume) and for particle to fluid density ratio between 1 and 1.05. The effective relative viscosity exhibits a strong dependence on the solid fraction for all density ratios tested. For density ratio of 1 the effective viscosity increases with Stokes number (St) for volume fractions (φ) lower than 40% and becomes constant for higher φ. When the particles are denser than the liquid, the effective viscosity shows a stronger dependance on St. An analysis of the particle resuspension for the case with a density ratio of 1.05 is presented and used to predict the local volume fraction where the shear stress measurements take place. When the local volume fraction is considered, the effective viscosity for settling and no settling particles is consistent, indicating that the effective viscosity is independent of differences in density between the solid and liquid phase. Shear stress measurements of pure fluids (no particles) were performed using the same rheometer, and a deviation from laminar behavior is observed for gap Reynolds numbers above 4× 10³, indicating the presence of hydrodynamic instabilities associated with the rotation of the outer cylinder. The increase on the effective viscosity with Stokes numbers observed for mixtures with φ ≤ 30% appears to be affected by such hydrodynamic instabilities. The effective viscosity for the current experiments is considerably higher than the one reported in non-inertial suspensions.

Photoelectrochemistry of GaAs and Si liquid junctions

A quantitative study has been performed on the stability of GaAs surfaces in a 0.10 M K₂Se-0.01 M K₂Se₂ aqueous solution. In this electrolyte, n-type GaAs electrodes displayed significant photocorrosion in competition with faradaic charge transfer to Se^2-. Chemisorption of group VIIIB metal ions onto the GaAs surfaces yielded improved current-voltage behavior of the GaAs photoanodes, and also resulted in a significant reduction in photocorrosion. This behavior implies that the chemisorbed metal ions act to increase the rate of hole transfer to the Se^2- species. Related experiments on n-GaAs, pGaAs, and Sn-doped In₂O₃ electrodes in Te^2-/- aqueous solutions have also been performed.

The majority carrier (electrons) transfer rate constant at a highly doped n⁺-Si/Co(Cp)₂Cl-methanol junction has been measured directly using the chronoamperometry electrochemical technique. The reduction reaction rate of Co(Cp)₂+ was 0.03 cm-s^-1 at the Si electrode, and was more than 100 times slower than at a hanging mercury electrode. The slower rate was attributed to the smaller optical and static dielectric constants, and the lower density of electrons of the semiconductor. The experimental results were compared to the Marcus theory of charge transfer.

The unique properties of high purity Si/liquid junctions have been investigated under illumination conditions in which the photogenerated carrier concentration exceeds the dopant concentration. Under these high injection conditions, negligible electric fields exist at the semiconductor/liquid interface, and carrier motion is driven by diffusion. Studies of the current-voltage properties of the Si in methanol solutions containing various redox couples suggested that high efficiency photoelectrochemical cells could be established through selective collection of carriers at the semiconductor/liquid junction. The quasi-Fermi levels of electrons and holes were measured directly against the solution potential. Steady-state and transient photovoltage measurements, and theoretical modeliug of the carrier transport, generation, and recombination dynamics indicated that the quasi-Fermi levels were flat across the semiconductor sample. The recombination velocities at the Si/liquid junctions have also been measured, and were shown to vary with the solution potential following the Shockley-Read-Hall theory on recombination.

Equilibration of a liquid droplet-vapor-gas mixture downstream of a shock wave

The equations of motion for the flow of a mixture of liquid droplets, their vapor, and an inert gas through a normal shock wave are derived. A set of equations is obtained which is solved numerically for the equilibrium conditions far downstream of the shock. The equations describing the process of reaching equilibrium are also obtained. This is a set of first-order nonlinear differential equations and must also be solved numerically. The detailed equilibration process is obtained for several cases and the results are discussed.

Sputtering of the gallium-indium eutectic alloy in the liquid phase

We have measured sputtering yields and angular distributions of sputtered atoms from both the solid and liquid phases of gallium, indium, and the gallium-indium eutectic alloy. This was done by Rutherford backscattering analysis of graphite collector foils. The solid eutectic target shows a predominance of indium crystallites on its surface which have to be sputtered away before the composition of the sputtered atoms equals the bulk target composition. The size of the crystallites depends upon the conditions under which the alloy is frozen. The sputtering of the liquid eutectic alloy by 15 keV Ar⁺ results in a ratio of indium to gallium sputtering yields which is 28 times greater than would be expected from the target stoichiometry. Furthermore, the angular distribution of gallium is much more sharply peaked about the normal to the target surface than the indium distribution. When the incident Ar⁺ energy is increased to 25 keV, the gallium distribution broadens to the same shape as the indium distribution. With the exception of the sharp gallium distribution taken from the liquid eutectic at 15 keV, all angular distributions from liquid targets fit a cos² θ function. An ion-scattering-spectroscopy analysis of the liquid eutectic alloy reveals a surface layer of almost pure indium. A thermodynamic explanation for this highly segregated layer is discussed. The liquid eutectic alloy provides us with a unique target system which allows us to estimate the fraction of sputtered material which comes from the first monolayer of the surface.

1. Ultrasonic studies of binary liquid structure in the critical region. Theory and experiment for the 2,6-lutidine/water system. 2. Hartree-Fock calculations of electric polarizabilities of some simple atoms and molecules, and their practicality. 3. Calculation of vibrational transition probabilities in collinear atom-diatom and diatom-diatom collisions with Lennard-Jones interaction

Part 1. Many interesting visual and mechanical phenomena occur in the critical region of fluids, both for the gas-liquid and liquid-liquid transitions. The precise thermodynamic and transport behavior here has some broad consequences for the molecular theory of liquids. Previous studies in this laboratory on a liquid-liquid critical mixture via ultrasonics supported a basically classical analysis of fluid behavior by M. Fixman (e. g., the free energy is assumed analytic in intensive variables in the thermodynamics)--at least when the fluid is not too close to critical. A breakdown in classical concepts is evidenced close to critical, in some well-defined ways. We have studied herein a liquid-liquid critical system of complementary nature (possessing a lower critical mixing or consolute temperature) to all previous mixtures, to look for new qualitative critical behavior. We did not find such new behavior in the ultrasonic absorption ascribable to the critical fluctuations, but we did find extra absorption due to chemical processes (yet these are related to the mixing behavior generating the lower consolute point). We rederived, corrected, and extended Fixman's analysis to interpret our experimental results in these more complex circumstances. The entire account of theory and experiment is prefaced by an extensive introduction recounting the general status of liquid state theory. The introduction provides a context for our present work, and also points out problems deserving attention. Interest in these problems was stimulated by this work but also by work in Part 3.

Part 2. Among variational theories of electronic structure, the Hartree-Fock theory has proved particularly valuable for a practical understanding of such properties as chemical binding, electric multipole moments, and X-ray scattering intensity. It also provides the most tractable method of calculating first-order properties under external or internal one-electron perturbations, either developed explicitly in orders of perturbation theory or in the fully self-consistent method. The accuracy and consistency of first-order properties are poorer than those of zero-order properties, but this is most often due to the use of explicit approximations in solving the perturbed equations, or to inadequacy of the variational basis in size or composition. We have calculated the electric polarizabilities of H₂, He, Li, Be, LiH, and N₂ by Hartree-Fock theory, using exact perturbation theory or the fully self-consistent method, as dictated by convenience. By careful studies on total basis set composition, we obtained good approximations to limiting Hartree-Fock values of polarizabilities with bases of reasonable size. The values for all species, and for each direction in the molecular cases, are within 8% of experiment, or of best theoretical values in the absence of the former. Our results support the use of unadorned Hartree-Pock theory for static polarizabilities needed in interpreting electron-molecule scattering data, collision-induced light scattering experiments, and other phenomena involving experimentally inaccessible polarizabilities.

Part 3. Numerical integration of the close-coupled scattering equations has been carried out to obtain vibrational transition probabilities for some models of the electronically adiabatic H₂-H₂ collision. All the models use a Lennard-Jones interaction potential between nearest atoms in the collision partners. We have analyzed the results for some insight into the vibrational excitation process in its dependence on the energy of collision, the nature of the vibrational binding potential, and other factors. We conclude also that replacement of earlier, simpler models of the interaction potential by the Lennard-Jones form adds very little realism for all the complication it introduces. A brief introduction precedes the presentation of our work and places it in the context of attempts to understand the collisional activation process in chemical reactions as well as some other chemical dynamics.

The structure of liquid argon as determined by x-ray diffraction

X-ray diffraction measurements and subsequent data analyses have been carried out on liquid argon at five states in the density range of 0.91 to 1.135 gm/cc and temperature range of 127 to 143°K. Duplicate measurements were made on all states. These data yielded radial distribution and direct correlation functions which were then used to compute the pair potential using the Percus-Yevick equation. The potential minima are in the range of -105 to -120°K and appear to substantiate current theoretical estimates of the effective pair potential in the presence of a weak three-body force.

The data analysis procedure used was new and does not distinguish between the coherent and incoherent absorption factors for the cell scattering which were essentially equal. With this simplification, the argon scattering estimate was compared to the gas scattering estimate on the laboratory frame of reference and the two estimates coincided, indicating the data normalized. The argon scattering on the laboratory frame of reference was examined for the existence of the peaks in the structure factor and the existence of an observable third peak was considered doubtful.

Numerical studies of the effect of truncation, normalization, the subsidiary peak phenomenon in the radial distribution function, uncertainties in the low angle data relative to errors in the direct correlation function and the distortion phenomenon are presented.

The distortion phenomenon for this experiment explains why the Mikolaj-Pings argon data yielded pair potential well depths from the Percus-Yevick equation that were too shallow and an apparent slope with respect to density that was too steep compared to theoretical estimates.

The data presented for each measurement are: empty cell and cell plus argon intensity, absorption factors, argon intensity, smoothed argon intensity, smoothed argon intensity corrected for distortion, structure factor, radial distribution function, direct correlation function and the pair potential from the Percus-Yevick equation.