Planar reflection of gaseous detonations

Pipes containing flammable gaseous mixtures may be subjected to internal detonation. When the detonation normally impinges on a closed end, a reflected shock wave is created to bring the flow back to rest. This study built on the work of Karnesky (2010) and examined deformation of thin-walled stainless steel tubes subjected to internal reflected gaseous detonations. A ripple pattern was observed in the tube wall for certain fill pressures, and a criterion was developed that predicted when the ripple pattern would form. A two-dimensional finite element analysis was performed using Johnson-Cook material properties; the pressure loading created by reflected gaseous detonations was accounted for with a previously developed pressure model. The residual plastic strain between experiments and computations was in good agreement.

During the examination of detonation-driven deformation, discrepancies were discovered in our understanding of reflected gaseous detonation behavior. Previous models did not accurately describe the nature of the reflected shock wave, which motivated further experiments in a detonation tube with optical access. Pressure sensors and schlieren images were used to examine reflected shock behavior, and it was determined that the discrepancies were related to the reaction zone thickness extant behind the detonation front. During these experiments reflected shock bifurcation did not appear to occur, but the unfocused visualization system made certainty impossible. This prompted construction of a focused schlieren system that investigated possible shock wave-boundary layer interaction, and heat-flux gauges analyzed the boundary layer behind the detonation front. Using these data with an analytical boundary layer solution, it was determined that the strong thermal boundary layer present behind the detonation front inhibits the development of reflected shock wave bifurcation.

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.

Seismic reflection experiments imaging the physical nature of crustal structures in southern California

Seismic reflection methods have been extensively used to probe the Earth's crust and suggest the nature of its formative processes. The analysis of multi-offset seismic reflection data extends the technique from a reconnaissance method to a powerful scientific tool that can be applied to test specific hypotheses. The treatment of reflections at multiple offsets becomes tractable if the assumptions of high-frequency rays are valid for the problem being considered. Their validity can be tested by applying the methods of analysis to full wave synthetics.

Three studies illustrate the application of these principles to investigations of the nature of the crust in southern California. A survey shot by the COCORP consortium in 1977 across the San Andreas fault near Parkfield revealed events in the record sections whose arrival time decreased with offset. The reflectors generating these events are imaged using a multi-offset three-dimensional Kirchhoff migration. Migrations of full wave acoustic synthetics having the same limitations in geometric coverage as the field survey demonstrate the utility of this back projection process for imaging. The migrated depth sections show the locations of the major physical boundaries of the San Andreas fault zone. The zone is bounded on the southwest by a near-vertical fault juxtaposing a Tertiary sedimentary section against uplifted crystalline rocks of the fault zone block. On the northeast, the fault zone is bounded by a fault dipping into the San Andreas, which includes slices of serpentinized ultramafics, intersecting it at 3 km depth. These interpretations can be made despite complications introduced by lateral heterogeneities.

In 1985 the Calcrust consortium designed a survey in the eastern Mojave desert to image structures in both the shallow and the deep crust. Preliminary field experiments showed that the major geophysical acquisition problem to be solved was the poor penetration of seismic energy through a low-velocity surface layer. Its effects could be mitigated through special acquisition and processing techniques. Data obtained from industry showed that quality data could be obtained from areas having a deeper, older sedimentary cover, causing a re-definition of the geologic objectives. Long offset stationary arrays were designed to provide reversed, wider angle coverage of the deep crust over parts of the survey. The preliminary field tests and constant monitoring of data quality and parameter adjustment allowed 108 km of excellent crustal data to be obtained.

This dataset, along with two others from the central and western Mojave, was used to constrain rock properties and the physical condition of the crust. The multi-offset analysis proceeded in two steps. First, an increase in reflection peak frequency with offset is indicative of a thinly layered reflector. The thickness and velocity contrast of the layering can be calculated from the spectral dispersion, to discriminate between structures resulting from broad scale or local effects. Second, the amplitude effects at different offsets of P-P scattering from weak elastic heterogeneities indicate whether the signs of the changes in density, rigidity, and Lame's parameter at the reflector agree or are opposed. The effects of reflection generation and propagation in a heterogeneous, anisotropic crust were contained by the design of the experiment and the simplicity of the observed amplitude and frequency trends. Multi-offset spectra and amplitude trend stacks of the three Mojave Desert datasets suggest that the most reflective structures in the middle crust are strong Poisson's ratio (σ) contrasts. Porous zones or the juxtaposition of units of mutually distant origin are indicated. Heterogeneities in σ increase towards the top of a basal crustal zone at ~22 km depth. The transition to the basal zone and to the mantle include increases in σ. The Moho itself includes ~400 m layering having a velocity higher than that of the uppermost mantle. The Moho maintains the same configuration across the Mojave despite 5 km of crustal thinning near the Colorado River. This indicates that Miocene extension there either thinned just the basal zone, or that the basal zone developed regionally after the extensional event.

I. A seismotectonic study of the Middle America Subduction Zone. II. Lithosphere and upper mantle structure of the Canadian Shield and Eastern North America

This thesis consists of two separate parts. Part I (Chapter 1) is concerned with seismotectonics of the Middle America subduction zone. In this chapter, stress distribution and Benioff zone geometry are investigated along almost 2000 km of this subduction zone, from the Rivera Fracture Zone in the north to Guatemala in the south. Particular emphasis is placed on the effects on stress distribution of two aseismic ridges, the Tehuantepec Ridge and the Orozco Fracture Zone, which subduct at seismic gaps. Stress distribution is determined by studying seismicity distribution, and by analysis of 190 focal mechanisms, both new and previously published, which are collected here. In addition, two recent large earthquakes that have occurred near the Tehuantepec Ridge and the Orozco Fracture Zone are discussed in more detail. A consistent stress release pattern is found along most of the Middle America subduction zone: thrust events at shallow depths, followed down-dip by an area of low seismic activity, followed by a zone of normal events at over 175 km from the trench and 60 km depth. The zone of low activity is interpreted as showing decoupling of the plates, and the zone of normal activity as showing the breakup of the descending plate. The portion of subducted lithosphere containing the Orozco Fracture Zone does not differ significantly, in Benioff zone geometry or in stress distribution, from adjoining segments. The Playa Azul earthquake of October 25, 1981, M_s=7.3, occurred in this area. Body and surface wave analysis of this event shows a simple source with a shallow thrust mechanism and gives M_o=1.3x10²⁷ dyne-cm. A stress drop of about 45 bars is calculated; this is slightly higher than that of other thrust events in this subduction zone. In the Tehuantepec Ridge area, only minor differences in stress distribution are seen relative to adjoining segments. For both ridges, the only major difference from adjoining areas is the infrequency or lack of occurrence of large interplate thrust events.

Part II involves upper mantle P wave structure studies, for the Canadian shield and eastern North America. In Chapter 2, the P wave structure of the Canadian shield is determined through forward waveform modeling of the phases P_nl, P, and PP. Effects of lateral heterogeneity are kept to a minimum by using earthquakes just outside the shield as sources, with propagation paths largely within the shield. Previous mantle structure studies have used recordings of P waves in the upper mantle triplication range of 15-30°; however, the lack of large earthquakes in the shield region makes compilation of a complete P wave dataset difficult. By using the phase PP, which undergoes triplications at 30-60°, much more information becomes available. The WKBJ technique is used to calculate synthetic seismograms for PP, and these records are modeled almost as well as the P. A new velocity model, designated S25, is proposed for the Canadian shield. This model contains a thick, high-Q, high-velocity lid to 165 km and a deep low-velocity zone. These features combine to produce seismograms that are markedly different from those generated by other shield structure models. The upper mantle discontinuities in S25 are placed at 405 and 660 km, with a simple linear gradient in velocity between them. Details of the shape of the discontinuities are not well constrained. Below 405 km, this model is not very different from many proposed P wave models for both shield and tectonic regions.

Chapter 3 looks in more detail at recordings of P_nl in eastern North America. First, seismograms from four eastern North American earthquakes are analyzed, and seismic moments for the events are calculated. These earthquakes are important in that they are among the largest to have occurred in eastern North America in the last thirty years, yet in some cases were not large enough to produce many good long-period teleseismic records. A simple layer-over-a-halfspace model is used for the initial modeling, and is found to provide an excellent fit for many features of the observed waveforms. The effects on P_nl of varying lid structure are then investigated. A thick lid with a positive gradient in velocity, such as that proposed for the Canadian shield in Chapter 2, will have a pronounced effect on the waveforms, beginning at distances of 800 or 900 km. P_nl records from the same eastern North American events are recalculated for several lid structure models, to survey what kinds of variations might be seen. For several records it is possible to see likely effects of lid structure in the data. However, the dataset is too sparse to make any general observations about variations in lid structure. This type of modeling is expected to be important in the future, as the analysis is extended to more recent eastern North American events, and as broadband instruments make more high-quality regional recordings available.

Characterization and modeling of premixed turbulent n-heptane flames in the thin reaction zone regime

n-heptane/air premixed turbulent flames in the high-Karlovitz portion of the thin reaction zone regime are characterized and modeled in this thesis using Direct Numerical Simulations (DNS) with detailed chemistry. In order to perform these simulations, a time-integration scheme that can efficiently handle the stiffness of the equations solved is developed first. A first simulation with unity Lewis number is considered in order to assess the effect of turbulence on the flame in the absence of differential diffusion. A second simulation with non-unity Lewis numbers is considered to study how turbulence affects differential diffusion. In the absence of differential diffusion, minimal departure from the 1D unstretched flame structure (species vs. temperature profiles) is observed. In the non-unity Lewis number case, the flame structure lies between that of 1D unstretched flames with "laminar" non-unity Lewis numbers and unity Lewis number. This is attributed to effective Lewis numbers resulting from intense turbulent mixing and a first model is proposed. The reaction zone is shown to be thin for both flames, yet large chemical source term fluctuations are observed. The fuel consumption rate is found to be only weakly correlated with stretch, although local extinctions in the non-unity Lewis number case are well correlated with high curvature. These results explain the apparent turbulent flame speeds. Other variables that better correlate with this fuel burning rate are identified through a coordinate transformation. It is shown that the unity Lewis number turbulent flames can be accurately described by a set of 1D (in progress variable space) flamelet equations parameterized by the dissipation rate of the progress variable. In the non-unity Lewis number flames, the flamelet equations suggest a dependence on a second parameter, the diffusion of the progress variable. A new tabulation approach is proposed for the simulation of such flames with these dimensionally-reduced manifolds.

Electrocatalytic reduction of dioxygen at chemically modified electrodes

The kinetics of the reduction of O₂ by Ru(NH₃)₆⁺² as catalyzed by cobalt(II) tetrakis(4-N-methylpyridyl)porphyrin are described both in homogeneous solution and when the reactants are confined to Nafion coatings on graphite electrodes. The catalytic mechanism is determined and the factors that can control the total reduction currents at Nafion-coated electrodes are specified. A kinetic zone diagram for analyzing the behavior of catalyst-mediator-substrate systems at polymer coated electrodes is presented and utilized in identifying the current-limiting processes. Good agreement is demonstrated between calculated and measured reduction currents at rotating disk electrodes. The experimental conditions that will yield the optimum performance of coated electrodes are discussed, and a relationship is derived for the optimal coating thickness.

The relation between the reduction potentials of adsorbed and unadsorbed cobalt(III) tetrakis(4-N-methylpyridyl)porphyrin and those where it catalyzes the electroreduction of dioxygen is described. There is an unusually large change in the formal potential of the Co(III) couple upon the adsorption of the porphyrin on the graphite electrode surface. The mechanism in which the (inevitably) adsorbed porphyrin catalyzes the reduction of O₂ is in accord with a general mechanistic scheme proposed for most monomeric cobalt porphyrins.

Four new dimeric metalloporphyrins (prepared in the laboratory of Professor C. K. Chang) have the two porphyrin rings linked by an anthracene bridge attached to meso positions. The electrocatalytic behavior of the diporphyrins towards the reduction of O₂ at graphite electrodes has been examined for the following combination of metal centers: Co-Cu, Co-Fe, Fe-Fe, Fe-H₂. The Co-Cu diporphyrin catalyzes the reduction of O₂ to H₂O₂ but no further. The other three catalysts all exhibit mixed reduction pathways leading to both H₂O₂ and H₂O. However, the pathways that lead to H₂O do not involve H₂O₂ as an intermediate. A possible mechanistic scheme is offered to account for the observed behavior.

I. The attenuation and dispersion of sound in a condensing medium. II. The flow of a gas-particle mixture downstream of a normal shock in a nozzle

I. The attenuation of sound due to particles suspended in a gas was first calculated by Sewell and later by Epstein in their classical works on the propagation of sound in a two-phase medium. In their work, and in more recent works which include calculations of sound dispersion, the calculations were made for systems in which there was no mass transfer between the two phases. In the present work, mass transfer between phases is included in the calculations.

The attenuation and dispersion of sound in a two-phase condensing medium are calculated as functions of frequency. The medium in which the sound propagates consists of a gaseous phase, a mixture of inert gas and condensable vapor, which contains condensable liquid droplets. The droplets, which interact with the gaseous phase through the interchange of momentum, energy, and mass (through evaporation and condensation), are treated from the continuum viewpoint. Limiting cases, for flow either frozen or in equilibrium with respect to the various exchange processes, help demonstrate the effects of mass transfer between phases. Included in the calculation is the effect of thermal relaxation within droplets. Pressure relaxation between the two phases is examined, but is not included as a contributing factor because it is of interest only at much higher frequencies than the other relaxation processes. The results for a system typical of sodium droplets in sodium vapor are compared to calculations in which there is no mass exchange between phases. It is found that the maximum attenuation is about 25 per cent greater and occurs at about one-half the frequency for the case which includes mass transfer, and that the dispersion at low frequencies is about 35 per cent greater. Results for different values of latent heat are compared.

II. In the flow of a gas-particle mixture through a nozzle, a normal shock may exist in the diverging section of the nozzle. In Marble’s calculation for a shock in a constant area duct, the shock was described as a usual gas-dynamic shock followed by a relaxation zone in which the gas and particles return to equilibrium. The thickness of this zone, which is the total shock thickness in the gas-particle mixture, is of the order of the relaxation distance for a particle in the gas. In a nozzle, the area may change significantly over this relaxation zone so that the solution for a constant area duct is no longer adequate to describe the flow. In the present work, an asymptotic solution, which accounts for the area change, is obtained for the flow of a gas-particle mixture downstream of the shock in a nozzle, under the assumption of small slip between the particles and gas. This amounts to the assumption that the shock thickness is small compared with the length of the nozzle. The shock solution, valid in the region near the shock, is matched to the well known small-slip solution, which is valid in the flow downstream of the shock, to obtain a composite solution valid for the entire flow region. The solution is applied to a conical nozzle. A discussion of methods of finding the location of a shock in a nozzle is included.

Particle fluid mechanics in shear flows, acoustic waves, and shock waves

Three different categories of flow problems of a fluid containing small particles are being considered here. They are: (i) a fluid containing small, non-reacting particles (Parts I and II); (ii) a fluid containing reacting particles (Parts III and IV); and (iii) a fluid containing particles of two distinct sizes with collisions between two groups of particles (Part V).

Part I

A numerical solution is obtained for a fluid containing small particles flowing over an infinite disc rotating at a constant angular velocity. It is a boundary layer type flow, and the boundary layer thickness for the mixture is estimated. For large Reynolds number, the solution suggests the boundary layer approximation of a fluid-particle mixture by assuming W = W_p. The error introduced is consistent with the Prandtl’s boundary layer approximation. Outside the boundary layer, the flow field has to satisfy the “inviscid equation” in which the viscous stress terms are absent while the drag force between the particle cloud and the fluid is still important. Increase of particle concentration reduces the boundary layer thickness and the amount of mixture being transported outwardly is reduced. A new parameter, β = 1/Ω τ_v, is introduced which is also proportional to μ. The secondary flow of the particle cloud depends very much on β. For small values of β, the particle cloud velocity attains its maximum value on the surface of the disc, and for infinitely large values of β, both the radial and axial particle velocity components vanish on the surface of the disc.

Part II

The “inviscid” equation for a gas-particle mixture is linearized to describe the flow over a wavy wall. Corresponding to the Prandtl-Glauert equation for pure gas, a fourth order partial differential equation in terms of the velocity potential ϕ is obtained for the mixture. The solution is obtained for the flow over a periodic wavy wall. For equilibrium flows where λ_v and λ_T approach zero and frozen flows in which λ_v and λ_T become infinitely large, the flow problem is basically similar to that obtained by Ackeret for a pure gas. For finite values of λ_v and λ_T, all quantities except v are not in phase with the wavy wall. Thus the drag coefficient C_D is present even in the subsonic case, and similarly, all quantities decay exponentially for supersonic flows. The phase shift and the attenuation factor increase for increasing particle concentration.

Part III

Using the boundary layer approximation, the initial development of the combustion zone between the laminar mixing of two parallel streams of oxidizing agent and small, solid, combustible particles suspended in an inert gas is investigated. For the special case when the two streams are moving at the same speed, a Green’s function exists for the differential equations describing first order gas temperature and oxidizer concentration. Solutions in terms of error functions and exponential integrals are obtained. Reactions occur within a relatively thin region of the order of λ_D. Thus, it seems advantageous in the general study of two-dimensional laminar flame problems to introduce a chemical boundary layer of thickness λ_D within which reactions take place. Outside this chemical boundary layer, the flow field corresponds to the ordinary fluid dynamics without chemical reaction.

Part IV

The shock wave structure in a condensing medium of small liquid droplets suspended in a homogeneous gas-vapor mixture consists of the conventional compressive wave followed by a relaxation region in which the particle cloud and gas mixture attain momentum and thermal equilibrium. Immediately following the compressive wave, the partial pressure corresponding to the vapor concentration in the gas mixture is higher than the vapor pressure of the liquid droplets and condensation sets in. Farther downstream of the shock, evaporation appears when the particle temperature is raised by the hot surrounding gas mixture. The thickness of the condensation region depends very much on the latent heat. For relatively high latent heat, the condensation zone is small compared with Ʌ_D.

For solid particles suspended initially in an inert gas, the relaxation zone immediately following the compression wave consists of a region where the particle temperature is first being raised to its melting point. When the particles are totally melted as the particle temperature is further increased, evaporation of the particles also plays a role.

The equilibrium condition downstream of the shock can be calculated and is independent of the model of the particle-gas mixture interaction.

Part V

For a gas containing particles of two distinct sizes and satisfying certain conditions, momentum transfer due to collisions between the two groups of particles can be taken into consideration using the classical elastic spherical ball model. Both in the relatively simple problem of normal shock wave and the perturbation solutions for the nozzle flow, the transfer of momentum due to collisions which decreases the velocity difference between the two groups of particles is clearly demonstrated. The difference in temperature as compared with the collisionless case is quite negligible.