Advancing EDL technologies for future space missions : from ground testing facilities to ablative heatshields

Motivated by recent MSL results where the ablation rate of the PICA heatshield was over-predicted, and staying true to the objectives outlined in the NASA Space Technology Roadmaps and Priorities report, this work focuses on advancing EDL technologies for future space missions.

Due to the difficulties in performing flight tests in the hypervelocity regime, a new ground testing facility called the vertical expansion tunnel is proposed. The adverse effects from secondary diaphragm rupture in an expansion tunnel may be reduced or eliminated by orienting the tunnel vertically, matching the test gas pressure and the accelerator gas pressure, and initially separating the test gas from the accelerator gas by density stratification. If some sacrifice of the reservoir conditions can be made, the VET can be utilized in hypervelocity ground testing, without the problems associated with secondary diaphragm rupture.

The performance of different constraints for the Rate-Controlled Constrained-Equilibrium (RCCE) method is investigated in the context of modeling reacting flows characteristic to ground testing facilities, and re-entry conditions. The effectiveness of different constraints are isolated, and new constraints previously unmentioned in the literature are introduced. Three main benefits from the RCCE method were determined: 1) the reduction in number of equations that need to be solved to model a reacting flow; 2) the reduction in stiffness of the system of equations needed to be solved; and 3) the ability to tabulate chemical properties as a function of a constraint once, prior to running a simulation, along with the ability to use the same table for multiple simulations.

Finally, published physical properties of PICA are compiled, and the composition of the pyrolysis gases that form at high temperatures internal to a heatshield is investigated. A necessary link between the composition of the solid resin, and the composition of the pyrolysis gases created is provided. This link, combined with a detailed investigation into a reacting pyrolysis gas mixture, allows a much needed consistent, and thorough description of many of the physical phenomena occurring in a PICA heatshield, and their implications, to be presented.

Through the use of computational fluid mechanics and computational chemistry methods, significant contributions have been made to advancing ground testing facilities, computational methods for reacting flows, and ablation modeling.

Influence of local geology on earthquake ground motion

As a simplified approach for estimating theoretically the influence of local subsoils upon the ground motion during an earthquake, the problem of an idealized layered system subjected to vertically incident plane body waves was studied. Both the technique of steady-state analysis and the technique of transient analysis have been used to analyze the problem.

In the steady-state analysis, a recursion formula has been derived for obtaining the response of a layered system to sinusoidally steady-state input. Several conclusions are drawn concerning the nature of the amplification spectrum of a nonviscous layered system having its layer stiffnesses increasing with depth. Numerical examples are given to demonstrate the effect of layer parameters on the amplification spectrum of a layered system.

In the transient analysis, two modified shear beam models have been established for obtaining approximately the response of a layered system to earthquake-like excitation. The method of continuous modal analysis was adopted for approximate analysis of the models, with energy dissipation in the layers, if any, taken into account. Numerical examples are given to demonstrate the accuracy of the models and the effect of a layered system in modifying the input motion.

Conditions are established, under which the theory is applicable to predict the influence of local subsoils on the ground motion during an earthquake. To demonstrate the applicability of the models to actual cases, three examples of actually recorded earthquake events are examined. It is concluded that significant modification of the incoming seismic waves, as predicted by the theory, is likely to occur in well defined soft subsoils during an earthquake, provided that certain conditions concerning the nature of the incoming seismic waves are satisfied.

2,4-dimethylene-1,3-cyclobutanediyl and 2,4-dimethylenebicyclobutane. Synthesis, spectroscopy, and reactivity of a triplet biradical and its covalent isomer

The preparation and direct observation of triplet 2,4-dimethylene-1,3- cyclobutanediyl (1), the non-Kekule isomer of benzene, is described. The biradical was generated by photolysis of 5,6-dimethylene-2,3- diazabicyclo[2.1.1]hex-2-ene (2) (which was synthesized in several steps from benzvalene) under cryogenic, matrix-isolation conditions. Biradical 1 was characterized by EPR spectroscopy (‌‌‌‌‌│D/hc│ =0.0204 cm^(-1), │E/hc│ =0.0028 cm^(-1)) and found to have a triplet ground state. The Δm_s= 2 transition displays hyperfine splitting attributed to a 7.3-G coupling to the ring methine and a 5.9-G coupling to the exocyclic methylene protons. Several experiments, including application of the magnetophotoselection (mps) technique in the generation of biradical 1, have allowed a determination of the zero-field triplet sublevels as x = -0.0040, y = +0.0136, and z = -0.0096 cm^(-1), where x and y are respectively the long and short in-plane axes and z the out-of-plane axis of 1.

Triplet 1 is yellow-orange and displays highly structured absorption (λ_(max)= 506 nm) and fluorescence (λ_(max) = 510 nm) spectra, with vibronic spacings of 1520 and 620 cm^(-1) for absorption and 1570 and 620 cm^(-1) for emission. The spectra were unequivocally assigned to triplet 1 by the use of a novel technique that takes advantage of the biradical's photolability. The absorption є = 7200 M^(-1) cm^(-1) and f = 0.022, establishing that the transition is spin-allowed. Further use of the mps technique has demonstrated that the transition is x-polarized, and the excited state 1s therefore of B_(1g) symmetry, in accord with theoretical predictions.

Thermolysis or direct photolysis of diazene 2 in fluid solution produces 2,4- dimethylenebicyclo[l.l.0]butane (3), whose ^(l)H NMR spectrum (-80°C, CD_(2)Cl_(2)) consists of singlets at δ 4.22 and 3.18 in a 2:1 ratio. Compound 3 is thermally unstable and dimerizes with second-order kinetics between -80 and -25°C (∆H^(‡) = 6.8 kcal mol^(-1), (∆s^(‡) = -28 eu) by a mechanism involving direct combination of two molecules of 3 in the rate-determining step. This singlet-manifold reaction ultimately produces a mixture of two dimers, 3,8,9- trimethylenetricyclo[5.1.1.0^(2,5)]non-4-ene (75) and trans-3,10-dimethylenetricyclo[6.2.0.0^(2,5)]deca-4,8-diene (76t), with the former predominating. In contrast, triplet-sensitized photolysis of 2, which leads to triplet 1, provides, in addition to 75 and 76t, a substantial amount of trans-5,10- dimethylenetricyclo[6.2.0.0^(3,6)]deca-3,8-diene (77t) and small amounts of two unidentified dimers.

In addition, triplet biradical 1 ring-closes to 3 in rigid media both thermally (77-140 K) and photochemically. In solution 3 forms triplet 1 upon energy transfer from sensitizers having relatively low triplet energies. The implications of the thermal chemistry for the energy surfaces of the system are discussed.

Studies of ambient and chamber aerosol composition using the aerosol mass spectrometer

This thesis presents composition measurements for atmospherically relevant inorganic and organic aerosol from laboratory and ambient measurements using the Aerodyne aerosol mass spectrometer. Studies include the oxidation of dodecane in the Caltech environmental chambers, and several aircraft- and ground-based field studies, which include the quantification of wildfire emissions off the coast of California, and Los Angeles urban emissions.

The oxidation of dodecane by OH under low NO conditions and the formation of secondary organic aerosol (SOA) was explored using a gas-phase chemical model, gas-phase CIMS measurements, and high molecular weight ion traces from particle- phase HR-TOF-AMS mass spectra. The combination of these measurements support the hypothesis that particle-phase chemistry leading to peroxyhemiacetal formation is important. Positive matrix factorization (PMF) was applied to the AMS mass spectra which revealed three factors representing a combination of gas-particle partitioning, chemical conversion in the aerosol, and wall deposition.

Airborne measurements of biomass burning emissions from a chaparral fire on the central Californian coast were carried out in November 2009. Physical and chemical changes were reported for smoke ages 0 – 4 h old. CO₂ normalized ammonium, nitrate, and sulfate increased, whereas the normalized OA decreased sharply in the first 1.5 - 2 h, and then slowly increased for the remaining 2 h (net decrease in normalized OA). Comparison to wildfire samples from the Yucatan revealed that factors such as relative humidity, incident UV radiation, age of smoke, and concentration of emissions are important for wildfire evolution.

Ground-based aerosol composition is reported for Pasadena, CA during the summer of 2009. The OA component, which dominated the submicron aerosol mass, was deconvolved into hydrocarbon-like organic aerosol (HOA), semi-volatile oxidized organic aerosol (SVOOA), and low-volatility oxidized organic aerosol (LVOOA). The HOA/OA was only 0.08–0.23, indicating that most of Pasadena OA in the summer months is dominated by oxidized OA resulting from transported emissions that have undergone photochemistry and/or moisture-influenced processing, as apposed to only primary organic aerosol emissions. Airborne measurements and model predictions of aerosol composition are reported for the 2010 CalNex field campaign.

Nuclear Hartree-Fock calculations on parallel computers

Hartree-Fock (HF) calculations have had remarkable success in describing large nuclei at high spin, temperature and deformation. To allow full range of possible deformations, the Skyrme HF equations can be discretized on a three-dimensional mesh. However, such calculations are currently limited by the computational resources provided by traditional supercomputers. To take advantage of recent developments in massively parallel computing technology, we have implemented the LLNL Skyrme-force static and rotational HF codes on Intel's DELTA and GAMMA systems at Caltech.

We decomposed the HF code by assigning a portion of the mesh to each node, with nearest neighbor meshes assigned to nodes connected by communication· channels. This kind of decomposition is well-suited for the DELTA and the GAMMA architecture because the only non-local operations are wave function orthogonalization and the boundary conditions of the Poisson equation for the Coulomb field.

Our first application of the HF code on parallel computers has been the study of identical superdeformed (SD) rotational bands in the Hg region. In the last ten years, many SD rotational bands have been found experimentally. One very surprising feature found in these SD rotational bands is that many pairs of bands in nuclei that differ by one or two mass units have nearly identical deexcitation gamma-ray energies. Our calculations of the five rotational bands in ^(192)Hg and ^(194)Pb show that the filling of specific orbitals can lead to bands with deexcitation gamma-ray energies differing by at most 2 keV in nuclei differing by two mass units and over a range of angular momenta comparable to that observed experimentally. Our calculations of SD rotational bands in the Dy region also show that twinning can be achieved by filling or emptying some specific orbitals.

The interpretation of future precise experiments on atomic parity nonconservation (PNC) in terms of parameters of the Standard Model could be hampered by uncertainties in the atomic and nuclear structure. As a further application of the massively parallel HF calculations, we calculated the proton and neutron densities of the Cesium isotopes from A = 125 to A = 139. Based on our good agreement with experimental charge radii, binding energies, and ground state spins, we conclude that the uncertainties in the ratios of weak charges are less than 10^(-3), comfortably smaller than the anticipated experimental error.

One-dimensional models for organic magnetic materials

In the preparation of small organic paramagnets, these structures may conceptually be divided into spin-containing units (SCs) and ferromagnetic coupling units (FCs). The synthesis and direct observation of a series of hydrocarbon tetraradicals designed to test the ferromagnetic coupling ability of m-phenylene, 1,3-cyclobutane, 1,3- cyclopentane, and 2,4-adamantane (a chair 1,3-cyclohexane) using Berson TMMs and cyclobutanediyls as SCs are described. While 1,3-cyclobutane and m-phenylene are good ferromagnetic coupling units under these conditions, the ferromagnetic coupling ability of 1,3-cyclopentane is poor, and 1,3-cyclohexane is apparently an antiferromagnetic coupling unit. In addition, this is the first report of ferromagnetic coupling between the spins of localized biradical SCs.

The poor coupling of 1,3-cyclopentane has enabled a study of the variable temperature behavior of a 1,3-cyclopentane FC-based tetraradical in its triplet state. Through fitting the observed data to the usual Boltzman statistics, we have been able to determine the separation of the ground quintet and excited triplet states. From this data, we have inferred the singlet-triplet gap in 1,3-cyclopentanediyl to be 900 cal/mol, in remarkable agreement with theoretical predictions of this number.

The ability to simulate EPR spectra has been crucial to the assignments made here. A powder EPR simulation package is described that uses the Zeeman and dipolar terms to calculate powder EPR spectra for triplet and quintet states.

Methods for characterizing paramagnetic samples by SQUID magnetometry have been developed, including robust routines for data fitting and analysis. A precursor to a potentially magnetic polymer was prepared by ring-opening metathesis polymerization (ROMP), and doped samples of this polymer were studied by magnetometry. While the present results are not positive, calculations have suggested modifications in this structure which should lead to the desired behavior.

Source listings for all computer programs are given in the appendix.

Dense, efficient chip-to-chip communication at the extremes of computing

The scalability of CMOS technology has driven computation into a diverse range of applications across the power consumption, performance and size spectra. Communication is a necessary adjunct to computation, and whether this is to push data from node-to-node in a high-performance computing cluster or from the receiver of wireless link to a neural stimulator in a biomedical implant, interconnect can take up a significant portion of the overall system power budget. Although a single interconnect methodology cannot address such a broad range of systems efficiently, there are a number of key design concepts that enable good interconnect design in the age of highly-scaled CMOS: an emphasis on highly-digital approaches to solving ‘analog’ problems, hardware sharing between links as well as between different functions (such as equalization and synchronization) in the same link, and adaptive hardware that changes its operating parameters to mitigate not only variation in the fabrication of the link, but also link conditions that change over time. These concepts are demonstrated through the use of two design examples, at the extremes of the power and performance spectra.

A novel all-digital clock and data recovery technique for high-performance, high density interconnect has been developed. Two independently adjustable clock phases are generated from a delay line calibrated to 2 UI. One clock phase is placed in the middle of the eye to recover the data, while the other is swept across the delay line. The samples produced by the two clocks are compared to generate eye information, which is used to determine the best phase for data recovery. The functions of the two clocks are swapped after the data phase is updated; this ping-pong action allows an infinite delay range without the use of a PLL or DLL. The scheme's generalized sampling and retiming architecture is used in a sharing technique that saves power and area in high-density interconnect. The eye information generated is also useful for tuning an adaptive equalizer, circumventing the need for dedicated adaptation hardware.

On the other side of the performance/power spectra, a capacitive proximity interconnect has been developed to support 3D integration of biomedical implants. In order to integrate more functionality while staying within size limits, implant electronics can be embedded onto a foldable parylene (‘origami’) substrate. Many of the ICs in an origami implant will be placed face-to-face with each other, so wireless proximity interconnect can be used to increase communication density while decreasing implant size, as well as facilitate a modular approach to implant design, where pre-fabricated parylene-and-IC modules are assembled together on-demand to make custom implants. Such an interconnect needs to be able to sense and adapt to changes in alignment. The proposed array uses a TDC-like structure to realize both communication and alignment sensing within the same set of plates, increasing communication density and eliminating the need to infer link quality from a separate alignment block. In order to distinguish the communication plates from the nearby ground plane, a stimulus is applied to the transmitter plate, which is rectified at the receiver to bias a delay generation block. This delay is in turn converted into a digital word using a TDC, providing alignment information.

On the Mumford-Tate conjecture for Abelian varieties with reduction conditions

In this thesis we study Galois representations corresponding to abelian varieties with certain reduction conditions. We show that these conditions force the image of the representations to be "big," so that the Mumford-Tate conjecture (:= MT) holds. We also prove that the set of abelian varieties satisfying these conditions is dense in a corresponding moduli space.

The main results of the thesis are the following two theorems.

Theorem A: Let A be an absolutely simple abelian variety, End° (A) = k : imaginary quadratic field, g = dim(A). Assume either dim(A) ≤ 4, or A has bad reduction at some prime ϕ, with the dimension of the toric part of the reduction equal to 2r, and gcd(r,g) = 1, and (r,g) ≠ (15,56) or (m -1, m(m+1)/2). Then MT holds.

Theorem B: Let M be the moduli space of abelian varieties with fixed polarization, level structure and a k-action. It is defined over a number field F. The subset of M(Q) corresponding to absolutely simple abelian varieties with a prescribed stable reduction at a large enough prime ϕ of F is dense in M(C) in the complex topology. In particular, the set of simple abelian varieties having bad reductions with fixed dimension of the toric parts is dense.

Besides this we also established the following results:

(1) MT holds for some other classes of abelian varieties with similar reduction conditions. For example, if A is an abelian variety with End° (A) = Q and the dimension of the toric part of its reduction is prime to dim( A), then MT holds.

(2) MT holds for Ribet-type abelian varieties.

(3) The Hodge and the Tate conjectures are equivalent for abelian 4-folds.

(4) MT holds for abelian 4-folds of type II, III, IV (Theorem 5.0(2)) and some 4-folds of type I.

(5) For some abelian varieties either MT or the Hodge conjecture holds.

Identifying and interpreting stratification in sedimentary rocks on Mars : insight from Rover and orbital observations and terrestrial field analogs

Sedimentary rocks on Mars provide insight into past aqueous and atmospheric processes, climate regimes, and potential habitability. The stratigraphic architecture of sedimentary rocks on Mars is similar to that of Earth, indicating that the processes that govern deposition and erosion on Mars can be reasonably inferred through reference to analogous terrestrial systems. This dissertation aims to understand Martian surface processes through the use of (1) ground-based observations from the Mars Exploration Rovers, (2) orbital data from the High Resolution Imaging Science Experiment onboard the Mars Reconnaissance Orbiter, and (3) the use of terrestrial field analogs to understand bedforms and sediment transport on Mars. Chapters 1 and 2 trace the history of aqueous activity at Meridiani Planum, through the reconstruction of eolian bedforms at Victoria crater, and the identification of a potential mudstone facies at Santa Maria crater. Chapter 3 uses Terrestrial Laser Scanning to study cross-bedding in pyroclastic surge deposits on Earth in order to understand sediment transport in these events and to establish criteria for their identification on Mars. The final chapter analyzes stratal geometries in the Martian North Polar Layered Deposits using tools for sequence stratigraphic analysis, to better constrain past surface processes and past climate conditions on Mars.

Multiplexed DNA-mediated electrochemistry

The aromatic core of double helical DNA possesses the unique and remarkable ability to form a conduit for electrons to travel over exceptionally long molecular distances. This core of π-stacked nucleobases creates an efficient pathway for charge transfer to proceed that is exquisitely sensitive to even subtle perturbations. Ground state electrochemistry of DNA-modified electrodes has been one of the major techniques used both to investigate and to harness the property of DNA-mediated charge transfer. DNA-modified electrodes have been an essential tool for both gaining insights into the fundamental properties of DNA and, due to the exquisite specificity of DNA-mediated charge transfer for the integrity of the π-stack, for use in next generation diagnostic sensing. Here, multiplexed DNA-modified electrodes are used to (i) gain new insights on the electrochemical coupling of metalloproteins to the DNA π-stack with relevance to the fundaments of in vivo DNA-mediated charge transfer and (ii) enhance the overall sensitivity of DNA-mediated reduction for use in the detection of low abundance diagnostic targets.

First, Methylene Blue (MB′) was covalently attached to DNA through a flexible C12 alkyl linker to yield a new redox reporter for DNA electrochemistry measurements with enhanced sensitivity. Tethered, intercalated MB′ was reduced through DNA-mediated charge transport. The redox signal intensity for MB′-dT-C12-DNA was found to be at least 3 fold larger than that of previously used Nile Blue (NB)-dT-DNA, which is coupled to the base stack via direct conjugation. The signal attenuation, due to an intervening mismatch, and therefore the degree of DNA-mediated reduction, does, however, depend on the DNA film morphology and the backfilling agent used to passivate the surface. These results highlight two possible mechanisms for the reduction of MB′ on the DNA-modified electrode that are distinguishable by their kinetics: reduction mediated by the DNA base pair stack and direct surface reduction of MB′ at the electrode. The extent of direct reduction at the surface can be minimized by overall DNA assembly conditions.

Next, a series of intercalation-based DNA-mediated electrochemical reporters were developed, using a flexible alkane linkage to validate and explore their DNA-mediated reduction. The general mechanism for the reduction of distally bound redox active species, covalently tethered to DNA through flexible alkyl linkages, was established to be an intraduplex DNA-mediated pathway. MB, NB, and anthraquinone were covalently tethered to DNA with three different covalent linkages. The extent of electronic coupling of the reporter was shown to correlate with the DNA binding affinity of the redox active species, supporting an intercalative mechanism. These electrochemical signals were shown to be exceptionally sensitive to a single intervening π-stack perturbation, an AC mismatch, in a densely packed DNA monolayer, which further supports that the reduction is DNA-mediated. Finally, this DNA-mediated reduction of MB occurs primarily via intra- rather than inter duplex intercalation, as probed through varying the proximity and integrity of the neighboring duplex DNA. Further gains to electrochemical sensitivity of our DNA-modified devices were then achieved through the application of electrocatalytic signal amplification using these solvent accessible intercalative reporters, MB-dT-C8, and hemoglobin as a novel electron sink. Electrocatalysis offers an excellent means of electrochemical signal amplification, yet in DNA based sensors, its application has been limited due to strict assembly conditions. We describe the use of hemoglobin as a robust and effective electron sink for electrocatalysis in DNA sensing on low density DNA films. Protein shielding of the heme redox center minimizes direct reduction at the electrode surface and permits assays on low density DNA films. Electrocatalysis of MB that is covalently tethered to the DNA by a flexible alkyl linkage allows for efficient interactions with both the base stack and hemoglobin. Consistent suppression of the redox signal upon incorporation of single CA mismatch in the DNA oligomer demonstrates that both the unamplified and the electrocatalytically amplified redox signals are generated through DNA-mediated charge transport. Electrocatalysis with hemoglobin is robust: it is stable to pH and temperature variations. The utility and applicability of electrocatalysis with hemoglobin is demonstrated through restriction enzyme detection, and an enhancement in sensitivity permits femtomole DNA sampling.

Finally, we expanded the application of our multiplexed DNA-modified electrodes to the electrochemical characterization of DNA-bound proteins containing [4Fe-4S] clusters. DNA-modified electrodes have become an essential tool for the characterization of the redox chemistry of DNA repair proteins that contain redox cofactors. Multiplexed analysis of EndonucleaseIII (EndoIII), a DNA repair protein containing a [4Fe-4S] cluster known to be accessible via DNA-mediated charge transport, elucidated subtle differences in the electrochemical behavior as a function of DNA morphology. DNA-bound EndoIII is seen to have two different electron transfer pathways for reduction, either through the DNA base stack or through direct surface reduction. Closely packed DNA films, where the protein has limited surface accessibility, produce electrochemical signals reflecting electron transfer that is DNA-mediated. The electrochemical comparison of EndoIII mutants, including a new family of mutations altering the electrostatics surrounding the [4Fe-4S] cluster, was able to be quantitatively performed. While little change in the midpoint potential was found for this family of mutants, significant variations in the efficiency of DNA-mediated electron transfer were apparent. Based on the stability of these proteins, examined by circular dichroism, we propose that the electron transfer pathway can be perturbed not only by the removal of aromatic residues, but also through changes in solvation near the cluster.

A new ground motion intensity measure, peak filtered acceleration (PFA), to estimate collapse vulnerability of buildings in earthquakes

In this thesis, we develop an efficient collapse prediction model, the PFA (Peak Filtered Acceleration) model, for buildings subjected to different types of ground motions.

For the structural system, the PFA model covers modern steel and reinforced concrete moment-resisting frame buildings (potentially reinforced concrete shear wall buildings). For ground motions, the PFA model covers ramp-pulse-like ground motions, long-period ground motions, and short-period ground motions.

To predict whether a building will collapse in response to a given ground motion, we first extract long-period components from the ground motion using a Butterworth low-pass filter with suggested order and cutoff frequency. The order depends on the type of ground motion, and the cutoff frequency depends on the building’s natural frequency and ductility. We then compare the filtered acceleration time history with the capacity of the building. The capacity of the building is a constant for 2-dimentional buildings and a limit domain for 3-dimentional buildings. If the filtered acceleration exceeds the building’s capacity, the building is predicted to collapse. Otherwise, it is expected to survive the ground motion.

The parameters used in PFA model, which include fundamental period, global ductility and lateral capacity, can be obtained either from numerical analysis or interpolation based on the reference building system proposed in this thesis.

The PFA collapse prediction model greatly reduces computational complexity while archiving good accuracy. It is verified by FEM simulations of 13 frame building models and 150 ground motion records.

Based on the developed collapse prediction model, we propose to use PFA (Peak Filtered Acceleration) as a new ground motion intensity measure for collapse prediction. We compare PFA with traditional intensity measures PGA, PGV, PGD, and Sa in collapse prediction and find that PFA has the best performance among all the intensity measures.

We also provide a close form in term of a vector intensity measure (PGV, PGD) of the PFA collapse prediction model for practical collapse risk assessment.

Electron energy-loss spectroscopy study of polyatomic molecular systems under pyrolytic conditions

The technique of variable-angle, electron energy-loss spectroscopy has been used to study the electronic spectroscopy of the diketene molecule. The experiment was performed using incident electron beam energies of 25 eV and 50 eV, and at scattering angles between 10° and 90°. The energy-loss region from 2 eV to 11 eV was examined. One spin-forbidden transition has been observed at 4.36 eV and three others that are spin-allowed have been located at 5.89 eV, 6.88 eV and 7.84 eV. Based on the intensity variation of these transitions with impact energy and scattering angle, and through analogy with simpler molecules, the first three transitions are tentatively assigned to an n → π* transition, a π - σ* (3s) Rydberg transition and a π → π* transition.

Thermal decomposition of chlorodifluoromethane, chloroform, dichloromethane and chloromethane under flash-vacuum pyrolysis conditions (900-1100°C) was investigated by the technique of electron energy-loss spectroscopy, using the impact energy of 50 eV and a scattering angle of 10°. The pyrolytic reaction follows a hydrogen-chloride α-elimination pathway. The difluoromethylene radical was produced from chlorodifluoromethane pyrolysis at 900°C and identified by its X^1 A_1 → A^1B_1 band at 5.04 eV.

Finally, a number of exploratory studies have been performed. The thermal decomposition of diketene was studied under flash vacuum pressures (1-10 mTorr) and temperatures ranging from 500°C to 1000°C. The complete decomposition of the diketene molecule into two ketene molecules was achieved at 900°C. The pyrolysis of trifluoromethyl iodide molecule at 1000°C produced an electron energy-loss spectrum with several iodine-atom, sharp peaks and only a small shoulder at 8.37 eV as a possible trifluoromethyl radical feature. The electron energy-loss spectrum of trichlorobromomethane at 900°C mainly showed features from bromine atom, chlorine molecule and tetrachloroethylene. Hexachloroacetone decomposed partially at 900°C, but showed well-defined features from chlorine, carbon monoxide and tetrachloroethylene molecules. Bromodichloromethane molecule was investigated at 1000°C and produced a congested, electron energy-loss spectrum with bromine-atom, hydrogen-bromide, hydrogen-chloride and tetrachloroethylene features.

^(18)O/^(16)O and D/H studies on the interactions between heated meteoric ground waters and igneous intrusions: Western San Juan Mountains, Colorado and the Isle of Skye, Scotland

Detailed oxygen, hydrogen and carbon isotope studies have been carried out on igneous and metamorphic rocks of the Stony Mountain complex, Colorado, and the Isle of Skye, Scotland, in order to better understand the problems of hydrothermal meteoric water-rock interaction.

The Tertiary Stony Mountain stock (~1.3 km in diameter), is composed of an outer diorite, a main mass of biotite gabbro, and an inner diorite. The entire complex and most of the surrounding country rocks have experienced various degrees of ¹⁸O depletion (up to 10 per mil) due to interaction with heated meteoric waters. The inner diorite apparently formed from a low-¹⁸O magma with δ¹⁸O ≃ +2.5, but most of the isotopic effects are a result of exchange between H₂O and solidified igneous rocks. The low-¹⁸O inner diorite magma was probably produced by massive assimilation and/or melting of hydrothermally altered country rocks. The δ¹⁸O values of the rocks generally increase with increasing grain size, except that quartz typically has δ¹⁸O = +6 to +8, and is more resistant to hydrothermal exchange than any other mineral studied. Based on atom % oxygen, the outer diorites, gabbros, and volcanic rocks exhibit integrated water/rock ratios of 0.3 ± 0.2, 0.15 ± 0.1, and 0.2 ± 0.1, respectively. Locally, water/rock ratios attain values greater than 1.0. Hydrogen isotopic analyses of sericites, chlorites, biotites, and amphiboles range from -117 to -150. δD in biotites varies inversely with Fe/Fe+Mg, as predicted by Suzuoki and Epstein (1974), and positively with elevation, over a range of 600 m. The calculated δD of the mid-to-late-Tertiary meteoric waters is about -100. Carbonate δ¹³C values average -5.5 (PDB), within the generally accepted range for deep-seated carbon.

Almost all the rocks within 4 km of the central Tertiary intrusive complex of Skye are depleted in ¹⁸O. Whole-rock δ¹⁸O values of basalts (-7. 1 to +8.4), Mesozoic shales (-0.6 to + 12.4), and Precambrian sandstones (-6.2 to + 10.8) systematically decrease inward towards the center of the complex. The Cuillin gabbro may have formed from a ¹⁸O-depleted magma (depleted by about 2 per mil); δ¹⁸O of plagioclase (-7.1 to + 2.5) and pyroxene (-0.5 to + 3.2) decrease outward toward the margins of the pluton. The Red Hills epigranite plutons have δ¹⁸O quartz (-2.7 to + 7.6) and feldspar (-6.7 to + 6.0) that suggest about 3/4 of the exchange took place at subsolidus temperatures; profound disequilibrium quartz-feldspar fractionations (up to 12) are characteristic. The early epigranites were intruded as low-¹⁸O melts (depletions of up to 3 per mil) with δ¹⁸O of the primary, igneous quartz decreasing progressively with time. The Southern Porphyritic Epigranite was apparently intruded as a low-¹⁸O magma with δ¹⁸O ≃ -2.6. A good correlation exists between grain size and δ¹⁸O for the unique, high-¹⁸O Beinn an Dubhaich granite which intrudes limestone having a δ¹⁸O range of +0.5 to +20.8, and δ¹³C of -4.9 to -1.0. The δD values of sericites (-104 to -107), and amphiboles, chlorites, and biotites (-105 to -128) from the igneous rocks , indicate that Eocene surface waters at Skye had δD ≃ -90. The average water/rock ratio for the Skye hydrothermal system is approximately one; at least 2000 km³ of heated meteoric waters were cycled through these rocks.

Thus these detailed isotopic studies of two widely separated areas indicate that (1) ¹⁸O-depleted magmas are commonly produced in volcanic terranes invaded by epizonal intrusions; (2) most of the ¹⁸O-depletion in such areas are a result of subsolidus exchange (particularly of feldspars); however correlation of δ¹⁸O with grain size is generally preserved only for systems that have undergone relatively minor meteoric hydrothermal exchange; (3) feldspar and calcite are the minerals mos t susceptible to oxygen isotopic exchange, whereas quartz is very resistant to oxygen isotope exchange; biotite, magnetite, and pyroxene have intermediate susceptibilities; and (4) basaltic country rocks are much more permeable to the hydrothermal convective system than shale, sandstone, or the crystalline basement complex.

Earthquake response of steel braces and braced steel frames

This thesis consists of three parts. Chapter 2 deals with the dynamic buckling behavior of steel braces under cyclic axial end displacement. Braces under such a loading condition belong to a class of "acceleration magnifying" structural components, in which a small motion at the loading points can cause large internal acceleration and inertia. This member-level inertia is frequently ignored in current studies of braces and braced structures. This chapter shows that, under certain conditions, the inclusion of the member-level inertia can lead to brace behavior fundamentally different from that predicted by the quasi-static method. This result is to have significance in the correct use of the quasi-static, pseudo-dynamic and static condensation methods in the simulation of braces or braced structures under dynamic loading. The strain magnitude and distribution in the braces are also studied in this chapter.

Chapter 3 examines the effect of column uplift on the earthquake response of braced steel frames and explores the feasibility of flexible column-base anchoring. It is found that fully anchored braced-bay columns can induce extremely large internal forces in the braced-bay members and their connections, thus increasing the risk of failures observed in recent earthquakes. Flexible braced-bay column anchoring can significantly reduce the braced bay member force, but at the same time also introduces large story drift and column uplift. The pounding of an uplifting column with its support can result in very high compressive axial force.

Chapter 4 conducts a comparative study on the effectiveness of a proposed non-buckling bracing system and several conventional bracing systems. The non-buckling bracing system eliminates buckling and thus can be composed of small individual braces distributed widely in a structure to reduce bracing force concentration and increase redundancy. The elimination of buckling results in a significantly more effective bracing system compared with the conventional bracing systems. Among the conventional bracing systems, bracing configurations and end conditions for the bracing members affect the effectiveness.

The studies in Chapter 3 and Chapter 4 also indicate that code-designed conventionally braced steel frames can experience unacceptably severe response under the strong ground motions recorded during the recent Northridge and Kobe earthquakes.

I. Foehn winds of southern California. II. Foehn wind cyclo-genesis. III. Weather conditions associated with the Akron disaster. IV. The Los Angeles storm of December 30, 1933 to January 1, 1934

I. Foehn winds of southern California.
An investigation of the hot, dry and dust laden winds occurring in the late fall and early winter in the Los Angeles Basin and attributed in the past to the influences of the desert regions to the north revealed that these currents were of a foehn nature. Their properties were found to be entirely due to dynamical heating produced in the descent from the high level areas in the interior to the lower Los Angeles Basin. Any dust associated with the phenomenon was found to be acquired from the Los Angeles area rather than transported from the desert. It was found that the frequency of occurrence of a mild type foehn of this nature during this season was sufficient to warrant its classification as a winter monsoon. This results from the topography of the Los Angeles region which allows an easy entrance to the air from the interior by virtue of the low level mountain passes north of the area. This monsoon provides the mild winter climate of southern California since temperatures associated with the foehn currents are far higher than those experienced when maritime air from the adjacent Pacific Ocean occupies the region.

II. Foehn wind cyclo-genesis.
Intense anticyclones frequently build up over the high level regions of the Great Basin and Columbia Plateau which lie between the Sierra Nevada and Cascade Mountains to the west and the Rocky Mountains to the east. The outflow from these anticyclones produce extensive foehns east of the Rockies in the comparatively low level areas of the middle west and the Canadian provinces of Alberta and Saskatchewan. Normally at this season of the year very cold polar continental air masses are present over this territory and with the occurrence of these foehns marked discontinuity surfaces arise between the warm foehn current, which is obliged to slide over a colder mass, and the Pc air to the east. Cyclones are easily produced from this phenomenon and take the form of unstable waves which propagate along the discontinuity surface between the two dissimilar masses. A continual series of such cyclones was found to occur as long as the Great Basin anticyclone is maintained with undiminished intensity.

III. Weather conditions associated with the Akron disaster.
This situation illustrates the speedy development and propagation of young disturbances in the eastern United States during the spring of the year under the influence of the conditionally unstable tropical maritime air masses which characterise the region. It also furnishes an excellent example of the superiority of air mass and frontal methods of weather prediction for aircraft operation over the older methods based upon pressure distribution.

IV. The Los Angeles storm of December 30, 1933 to January 1, 1934.
This discussion points out some of the fundamental interactions occurring between air masses of the North Pacific Ocean in connection with Pacific Coast storms and the value of topographic and aerological considerations in predicting them. Estimates of rainfall intensity and duration from analyses of this type may be made and would prove very valuable in the Los Angeles area in connection with flood control problems.