Seismic structure above and below the core-mantle boundary

Seismic structure above and below the core-mantle boundary (CMB) has been studied through use of travel time and waveform analyses of several different seismic wave groups. Anomalous systematic trends in observables document mantle heterogeneity on both large and small scales. Analog and digital data has been utilized, and in many cases the analog data has been optically scanned and digitized prior to analysis.

Differential travel times of S - SKS are shown to be an excellent diagnostic of anomalous lower mantle shear velocity (V s) structure. Wavepath geometries beneath the central Pacific exhibit large S- SKS travel time residuals (up to 10 sec), and are consistent with a large scale 0(1000 km) slower than average V_s region (≥3%). S - SKS times for paths traversing this region exhibit smaller scale patterns and trends 0(100 km) indicating V_s perturbations on many scale lengths. These times are compared to predictions of three tomographically derived aspherical models: MDLSH of Tanimoto [1990], model SH12_WM13 of Suet al. [1992], and model SH.10c.17 of Masters et al. [1992]. Qualitative agreement between the tomographic model predictions and observations is encouraging, varying from fair to good. However, inconsistencies are present and suggest anomalies in the lower mantle of scale length smaller than the present 2000+ km scale resolution of tomographic models. 2-D wave propagation experiments show the importance of inhomogeneous raypaths when considering lateral heterogeneities in the lowermost mantle.

A dataset of waveforms and differential travel times of S, ScS, and the arrival from the D" layer, Scd, provides evidence for a laterally varying V_s velocity discontinuity at the base of the mantle. Two different localized D" regions beneath the central Pacific have been investigated. Predictions from a model having a V_s discontinuity 180 km above the CMB agree well with observations for an eastern mid-Pacific CMB region. This thickness differs from V_s discontinuity thicknesses found in other regions, such as a localized region beneath the western Pacific, which average near 280 km. The "sharpness" of the V_s jump at the top of D", i.e., the depth range over which the V_s increase occurs, is not resolved by our data, and our data can in fact may be modeled equally well by a lower mantle with the increase in V_s at the top of D" occurring over a 100 krn depth range. It is difficult at present to correlate D" thicknesses from this study to overall lower mantle heterogeneity, due to uncertainties in the 3-D models, as well as poor coverage in maps of D" discontinuity thicknesses.

P-wave velocity structure (V_p) at the base of the mantle is explored using the seismic phases SKS and SPdKS. SPdKS is formed when SKS waves at distances around 107° are incident upon the CMB with a slowness that allows for coupling with diffracted P-waves at the base of the mantle. The P-wave diffraction occurs at both the SKS entrance and exit locations of the outer core. SP_dKS arrives slightly later in time than SKS, having a wave path through the mantle and core very close to SKS. The difference time between SKS and SP_dKS strongly depends on V_p at the base of the mantle near SK Score entrance and exit points. Observations from deep focus Fiji-Tonga events recorded by North American stations, and South American events recorded by European and Eurasian stations exhibit anomalously large SP_dKS - SKS difference times. SKS and the later arriving SP_dKS phase are separated by several seconds more than predictions made by 1-D reference models, such as the global average PREM [Dziewonski and Anderson, 1981] model. Models having a pronounced low-velocity zone (5%) in V_p in the bottom 50-100 km of the mantle predict the size of the observed SP_dK S-SKS anomalies. Raypath perturbations from lower mantle V_s structure may also be contributing to the observed anomalies.

Outer core structure is investigated using the family of SmKS (m=2,3,4) seismic waves. SmKS are waves that travel as S-waves in the mantle, P-waves in the core, and reflect (m-1) times on the underside of the CMB, and are well-suited for constraining outermost core V_p structure. This is due to closeness of the mantle paths and also the shallow depth range these waves travel in the outermost core. S3KS - S2KS and S4KS - S3KS differential travel times were measured using the cross-correlation method and compared to those from reflectivity synthetics created from core models of past studies. High quality recordings from a deep focus Java Sea event which sample the outer core beneath the northern Pacific, the Arctic, and northwestern North America (spanning 1/8th of the core's surface area), have SmKS wavepaths that traverse regions where lower mantle heterogeneity is pre- dieted small, and are well-modeled by the PREM core model, with possibly a small V_p decrease (1.5%) in the outermost 50 km of the core. Such a reduction implies chemical stratification in this 50 km zone, though this model feature is not uniquely resolved. Data having wave paths through areas of known D" heterogeneity (±2% and greater), such as the source-side of SmKS lower mantle paths from Fiji-Tonga to Eurasia and Africa, exhibit systematic SmKS differential time anomalies of up to several seconds. 2-D wave propagation experiments demonstrate how large scale lower mantle velocity perturbations can explain long wavelength behavior of such anomalous SmKS times. When improperly accounted for, lower mantle heterogeneity maps directly into core structure. Raypaths departing from homogeneity play an important role in producing SmKS anomalies. The existence of outermost core heterogeneity is difficult to resolve at present due to uncertainties in global lower mantle structure. Resolving a one-dimensional chemically stratified outermost core also remains difficult due to the same uncertainties. Restricting study to higher multiples of SmKS (m=2,3,4) can help reduce the affect of mantle heterogeneity due to the closeness of the mantle legs of the wavepaths. SmKS waves are ideal in providing additional information on the details of lower mantle heterogeneity.

Synthesis and potency of long end-associative polymers for mist control

Long linear polymers that are end-functionalized with associative groups were studied as additives to hydrocarbon fluids to mitigate the fire hazard associated with the presence of mist in a crash scenario. These polymers were molecularly designed to overcome both the shear-degradation of long polymer chains in turbulent flows, and the chain collapse induced by the random placement of associative groups along polymer backbones. Architectures of associative groups on the polymer chain ends that were tested included clusters of self-associative carboxyl groups and pairs of hetero-complementary associative units.

Linear polymers with clusters of discrete numbers of carboxyl groups on their chain ends were investigated first: an innovative synthetic strategy was devised to achieve unprecedented backbone lengths and precise control of the number of carboxyl groups on chain ends (N). We found that a very narrow range of N allows the co-existence of sufficient end-association strength and polymer solubility in apolar media. Subsequent steady-flow rheological study on solution behavior of such soluble polymers in apolar media revealed that the end-association of very long chains in apolar media leads to the formation of flower-like micelles interconnected by bridging chains, which trap significant fraction of polymer chains into looped structures with low contribution to mist-control. The efficacy of very long 1,4-polybutadiene chains end-functionalized with clusters of four carboxyl groups as mist-control additives for jet fuel was further tested. In addition to being shear-resistant, the polymer was found capable of providing fire-protection to jet fuel at concentrations as low as 0.3wt%. We also found that this polymer has excellent solubility in jet fuel over a wide range of temperature (-30 to +70°C) and negligible interference with dewatering of jet fuel. It does not cause an adverse increase in viscosity at concentrations where mist-control efficacy exists.

Four pairs of hetero-complementary associative end-groups of varying strengths were subsequently investigated, in the hopes of achieving supramolecular aggregates with both mist-control ability and better utilization of polymer building blocks. Rheological study of solutions of the corresponding complementary associative polymer pairs in apolar media revealed the strength of complementary end-association required to achieve supramolecular aggregates capable of modulating rheological properties of the solution.

Both self-associating and complementary associating polymers have therefore been found to resist shear degradation. The successful strategy of building soluble, end-associative polymers with either self-associative or complementary associative groups will guide the next generation of mist-control technology.

The theory of long distance electron transfer reactions

The rate of electron transport between distant sites was studied. The rate depends crucially on the chemical details of the donor, acceptor, and surrounding medium. These reactions involve electron tunneling through the intervening medium and are, therefore, profoundly influenced by the geometry and energetics of the intervening molecules. The dependence of rate on distance was considered for several rigid donor-acceptor "linkers" of experimental importance. Interpretation of existing experiments and predictions for new experiments were made.

The electronic and nuclear motion in molecules is correlated. A Born-Oppenheimer separation is usually employed in quantum chemistry to separate this motion. Long distance electron transfer rate calculations require the total donor wave function when the electron is very far from its binding nuclei. The Born-Oppenheimer wave functions at large electronic distance are shown to be qualitatively wrong. A model which correctly treats the coupling was proposed. The distance and energy dependence of the electron transfer rate was determined for such a model.

Effects of self energy of the ions on the double layer structure and properties at the dielectric interface

Although numerous theoretical efforts have been put forth, a systematic, unified and predictive theoretical framework that is able to capture all the essential physics of the interfacial behaviors of ions, such as the Hofmeister series effect, Jones-Ray effect and the salt effect on the bubble coalescence remain an outstanding challenge. The most common approach to treating electrostatic interactions in the presence of salt ions is the Poisson-Boltzmann (PB) theory. However, there are many systems for which the PB theory fails to offer even a qualitative explanation of the behavior, especially for ions distributed in the vicinity of an interface with dielectric contrast between the two media (like the water-vapor/oil interface). A key factor missing in the PB theory is the self energy of the ion.

In this thesis, we develop a self-consistent theory that treats the electrostatic self energy (including both the short-range Born solvation energy and the long-range image charge interactions), the nonelectrostatic contribution of the self energy, the ion-ion correlation and the screening effect systematically in a single framework. By assuming a finite charge spread of the ion instead of using the point-charge model, the self energy obtained by our theory is free of the divergence problems and gives a continuous self energy across the interface. This continuous feature allows ions on the water side and the vapor/oil side of the interface to be treated in a unified framework. The theory involves a minimum set of parameters of the ion, such as the valency, radius, polarizability of the ions, and the dielectric constants of the medium, that are both intrinsic and readily available. The general theory is first applied to study the thermodynamic property of the bulk electrolyte solution, which shows good agreement with the experiment result for predicting the activity coefficient and osmotic coefficient.

Next, we address the effect of local Born solvation energy on the bulk thermodynamics and interfacial properties of electrolyte solution mixtures. We show that difference in the solvation energy between the cations and anions naturally gives rise to local charge separation near the interface, and a finite Galvani potential between two coexisting solutions. The miscibility of the mixture can either increases or decreases depending on the competition between the solvation energy and translation entropy of the ions. The interfacial tension shows a non-monotonic dependence on the salt concentration: it increases linearly with the salt concentration at higher concentrations, and decreases approximately as the square root of the salt concentration for dilute solutions, which is in agreement with the Jones-Ray effect observed in experiment.

Next, we investigate the image effects on the double layer structure and interfacial properties near a single charged plate. We show that the image charge repulsion creates a depletion boundary layer that cannot be captured by a regular perturbation approach. The correct weak-coupling theory must include the self-energy of the ion due to the image charge interaction. The image force qualitatively alters the double layer structure and properties, and gives rise to many non-PB effects, such as nonmonotonic dependence of the surface energy on concentration and charge inversion. The image charge effect is then studied for electrolyte solutions between two plates. For two neutral plates, we show that depletion of the salt ions by the image charge repulsion results in short-range attractive and long-range repulsive forces. If cations and anions are of different valency, the asymmetric depletion leads to the formation of an induced electrical double layer. For two charged plates, the competition between the surface charge and the image charge effect can give rise to like- charge attraction.

Then, we study the inhomogeneous screening effect near the dielectric interface due to the anisotropic and nonuniform ion distribution. We show that the double layer structure and interfacial properties is drastically affected by the inhomogeneous screening if the bulk Debye screening length is comparable or smaller than the Bjerrum length. The width of the depletion layer is characterized by the Bjerrum length, independent of the salt concentration. We predict that the negative adsorption of ions at the interface increases linearly with the salt concentration, which cannot be captured by either the bulk screening approximation or the WKB approximation. For asymmetric salt, the inhomogeneous screening enhances the charge separation in the induced double layer and significantly increases the value of the surface potential.

Finally, to account for the ion specificity, we study the self energy of a single ion across the dielectric interface. The ion is considered to be polarizable: its charge distribution can be self-adjusted to the local dielectric environment to minimize the self energy. Using intrinsic parameters of the ions, such as the valency, radius, and polarizability, we predict the specific ion effect on the interfacial affinity of halogen anions at the water/air interface, and the strong adsorption of hydrophobic ions at the water/oil interface, in agreement with experiments and atomistic simulations.

The theory developed in this work represents the most systematic theoretical technique for weak-coupling electrolytes. We expect the theory to be more useful for studying a wide range of structural and dynamic properties in physicochemical, colloidal, soft-matter and biophysical systems.

Design of antenna-coupled lumped-element titanium nitride KIDs for long-wavelength multi-band continuum imaging

Many applications in cosmology and astrophysics at millimeter wavelengths including CMB polarization, studies of galaxy clusters using the Sunyaev-Zeldovich effect (SZE), and studies of star formation at high redshift and in our local universe and our galaxy, require large-format arrays of millimeter-wave detectors. Feedhorn and phased-array antenna architectures for receiving mm-wave light present numerous advantages for control of systematics, for simultaneous coverage of both polarizations and/or multiple spectral bands, and for preserving the coherent nature of the incoming light. This enables the application of many traditional "RF" structures such as hybrids, switches, and lumped-element or microstrip band-defining filters.

Simultaneously, kinetic inductance detectors (KIDs) using high-resistivity materials like titanium nitride are an attractive sensor option for large-format arrays because they are highly multiplexable and because they can have sensitivities reaching the condition of background-limited detection. A KID is a LC resonator. Its inductance includes the geometric inductance and kinetic inductance of the inductor in the superconducting phase. A photon absorbed by the superconductor breaks a Cooper pair into normal-state electrons and perturbs its kinetic inductance, rendering it a detector of light. The responsivity of KID is given by the fractional frequency shift of the LC resonator per unit optical power.

However, coupling these types of optical reception elements to KIDs is a challenge because of the impedance mismatch between the microstrip transmission line exiting these architectures and the high resistivity of titanium nitride. Mitigating direct absorption of light through free space coupling to the inductor of KID is another challenge. We present a detailed titanium nitride KID design that addresses these challenges. The KID inductor is capacitively coupled to the microstrip in such a way as to form a lossy termination without creating an impedance mismatch. A parallel plate capacitor design mitigates direct absorption, uses hydrogenated amorphous silicon, and yields acceptable noise. We show that the optimized design can yield expected sensitivities very close to the fundamental limit for a long wavelength imager (LWCam) that covers six spectral bands from 90 to 400 GHz for SZE studies.

Excess phase (frequency) noise has been observed in KID and is very likely caused by two-level systems (TLS) in dielectric materials. The TLS hypothesis is supported by the measured dependence of the noise on resonator internal power and temperature. However, there is still a lack of a unified microscopic theory which can quantitatively model the properties of the TLS noise. In this thesis we derive the noise power spectral density due to the coupling of TLS with phonon bath based on an existing model and compare the theoretical predictions about power and temperature dependences with experimental data. We discuss the limitation of such a model and propose the direction for future study.

Estimation of catalyst activity profiles and deactivation parameters from reactor operating data with applications to naphtha reforming

Techniques are developed for estimating activity profiles in fixed bed reactors and catalyst deactivation parameters from operating reactor data. These techniques are applicable, in general, to most industrial catalytic processes. The catalytic reforming of naphthas is taken as a broad example to illustrate the estimation schemes and to signify the physical meaning of the kinetic parameters of the estimation equations. The work is described in two parts. Part I deals with the modeling of kinetic rate expressions and the derivation of the working equations for estimation. Part II concentrates on developing various estimation techniques.

Part I: The reactions used to describe naphtha reforming are dehydrogenation and dehydroisomerization of cycloparaffins; isomerization, dehydrocyclization and hydrocracking of paraffins; and the catalyst deactivation reactions, namely coking on alumina sites and sintering of platinum crystallites. The rate expressions for the above reactions are formulated, and the effects of transport limitations on the overall reaction rates are discussed in the appendices. Moreover, various types of interaction between the metallic and acidic active centers of reforming catalysts are discussed as characterizing the different types of reforming reactions.

Part II: In catalytic reactor operation, the activity distribution along the reactor determines the kinetics of the main reaction and is needed for predicting the effect of changes in the feed state and the operating conditions on the reactor output. In the case of a monofunctional catalyst and of bifunctional catalysts in limiting conditions, the cumulative activity is sufficient for predicting steady reactor output. The estimation of this cumulative activity can be carried out easily from measurements at the reactor exit. For a general bifunctional catalytic system, the detailed activity distribution is needed for describing the reactor operation, and some approximation must be made to obtain practicable estimation schemes. This is accomplished by parametrization techniques using measurements at a few points along the reactor. Such parametrization techniques are illustrated numerically with a simplified model of naphtha reforming.

To determine long term catalyst utilization and regeneration policies, it is necessary to estimate catalyst deactivation parameters from the the current operating data. For a first order deactivation model with a monofunctional catalyst or with a bifunctional catalyst in special limiting circumstances, analytical techniques are presented to transform the partial differential equations to ordinary differential equations which admit more feasible estimation schemes. Numerical examples include the catalytic oxidation of butene to butadiene and a simplified model of naphtha reforming. For a general bifunctional system or in the case of a monofunctional catalyst subject to general power law deactivation, the estimation can only be accomplished approximately. The basic feature of an appropriate estimation scheme involves approximating the activity profile by certain polynomials and then estimating the deactivation parameters from the integrated form of the deactivation equation by regression techniques. Different bifunctional systems must be treated by different estimation algorithms, which are illustrated by several cases of naphtha reforming with different feed or catalyst composition.