6 resultados para Liability of Manufacturers for Goods with Safety Defects

em CaltechTHESIS


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With the installation by the Pacific Electric Railway of a bus system in Pasadena to supplant most of its trolley lines, the problem of the comparison of the costs of the two systems naturally presented itself. The study here undertaken was originally started as just a comparison of the motor bus and Birney Safety Car, but as the work progressed it seemed advisable to include the trolley bus as well - a method of transportation that is comparatively new as far as development is concerned, but which seems to be finding increasing favor in the East.

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Whereas stoichiometric activation of C-H bonds by complexes of transition metals is becoming increasingly common, selective functionalization of alkanes remains a formidable challenge in organometallic chemistry. The recent advances in catalytic alkane functionalization by transition-metal complexes are summarized in Chapter I.

The studies of the displacement of pentafluoropyridine in [(tmeda)Pt(CH_3)(NC_5F_5)][BAr^f_4] (1) with γ- tetrafluoropicoline, a very poor nucleophile, are reported in Chapter II. The ligand substitution occurs by a dissociative interchange mechanism. This result implies that dissociative loss of pentafluoropyridine is the rate-limiting step in the C-H activation reactions of 1.

Oxidation of dimethylplatinum(II) complexes (N-N)Pt(CH_3)_2 (N-N = tmeda(1), α-diimines) by dioxygen is described in Chapter III. Mechanistic studies suggest a two-step mechanism. First, a hydroperoxoplatinum(IV) complex is formed in a reaction between (N-N)Pt(CH_3)_2 and dioxygen. Next, the hydroperoxy complex reacts with a second equivalent of (N-N)Pt(CH_3)_2 to afford the final product, (N-N)Pt(OH)(OCH_3)(CH_3)_2. The hydroperoxy intermediate, (tmeda)Pt(OOH)(OCH_3)(CH_3)_2 (2), was isolated and characterized. The reactivity of 2 with several dime thylplatinum(II) complexes is reported.

The studies described in Chapter IV are directed toward the development of a platinum(II)-catalyzed oxidative alkane dehydrogenation. Stoichiometric conversion of alkanes (cyclohexane, ethane) to olefins (cyclohexene, ethylene) is achieved by C-H activation with [(N-N)Pt(CH_3)(CF_3CH_2OH)]BF_4 (1, N-N is N,N'-bis(3,5-di-t- butylphenyl)-1,4-diazabutadiene) which results in the formation of olefin hydride complexes. The first step in the C-H activation reaction is formation of a platinum(II) alkyl which undergoes β-hydrogen elimination to afford the olefin hydride complex. The cationic ethylplatinum(II) intermediate can be generated in situ by treating diethylplatinum(II) compounds with acids. Treatment of (phen)PtEt_2 with [H(OEt_2)_2]Bar^f_4 at low temperatures resulted in the formation of a mixture of [(phen)PtEt(OEt_2)]Bar^f_4 (8) and [(phen)Pt(C_2H_4)H] Bar^f_4 (7). The cationic olefin complexes are unreactive toward dioxygen or hydrogen peroxide. Since the success of the overall catalytic cycle depends on our ability to oxidize the olefin hydride complexes, a series of neutral olefin complexes of platinum(II) with monoanionic ligands (derivatives of pyrrole-2-carboxyaldehyde N-aryl imines) was prepared. Unfortunately, these are also stable to oxidation.

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The Earth is very heterogeneous, especially in the region close to the surface of the Earth, and in regions close to the core-mantle boundary (CMB). The lowermost mantle (bottom 300km of the mantle) is the place for fast anomaly (3% faster S velocity than PREM, modeled from Scd), for slow anomaly (-3% slower S velocity than PREM, modeled from S,ScS), for extreme anomalous structure (ultra-low velocity zone, 30% lower inS velocity, 10% lower in P velocity). Strong anomaly with larger dimension is also observed beneath Africa and Pacific, originally modeled from travel time of S, SKS and ScS. Given the heterogeneous nature of the earth, more accurate approach (than travel time) has to be applied to study the details of various anomalous structures, and matching waveform with synthetic seismograms has proven effective in constraining the velocity structures. However, it is difficult to make synthetic seismograms in more than 1D cases where no exact analytical solution is possible. Numerical methods like finite difference or finite elements are too time consuming in modeling body waveforms. We developed a 2D synthetic algorithm, which is extended from 1D generalized ray theory (GRT), to make synthetic seismograms efficiently (each seismogram per minutes). This 2D algorithm is related to WKB approximation, but is based on different principles, it is thus named to be WKM, i.e., WKB modified. WKM has been applied to study the variation of fast D" structure beneath the Caribbean sea, to study the plume beneath Africa. WKM is also applied to study PKP precursors which is a very important seismic phase in modeling lower mantle heterogeneity. By matching WKM synthetic seismograms with various data, we discovered and confirmed that (a) The D" beneath Caribbean varies laterally, and the variation is best revealed with Scd+Sab beyond 88 degree where Sed overruns Sab. (b) The low velocity structure beneath Africa is about 1500 km in height, at least 1000km in width, and features 3% reduced S velocity. The low velocity structure is a combination of a relatively thin, low velocity layer (200 km thick or less) beneath the Atlantic, then rising very sharply into mid mantle towards Africa. (c) At the edges of this huge Africa low velocity structures, ULVZs are found by modeling the large separation between S and ScS beyond 100 degree. The ULVZ to the eastern boundary was discovered with SKPdS data, and later is confirmed by PKP precursor data. This is the first time that ULVZ is verified with distinct seismic phase.

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In this thesis I present a study of W pair production in e+e- annihilation using fully hadronic W+W- events. Data collected by the L3 detector at LEP in 1996-1998, at collision center-of-mass energies between 161 and 189 GeV, was used in my analysis.

Analysis of the total and differential W+W- cross sections with the resulting sample of 1,932 W+W- → qqqq event candidates allowed me to make precision measurements of a number of properties of the W boson. I combined my measurements with those using other W+W- final states to obtain stringent constraints on the W boson's couplings to fermions, other gauge bosons, and scalar Higgs field by measuring the total e+e- → W+W- cross section and its energy dependence

σ(e+e- → W+W-) =

{2.68+0.98-0.67(stat.)± 0.14(syst.) pb, √s = 161.34 GeV

{12.04+1.38-1.29(stat.)± 0.23(syst.) pb, √s = 172.13 GeV

{16.45 ± 0.67(stat.) ± 0.26(syst.) pb, √s = 182.68 GeV

{16.28 ± 0.38(stat.) ± 0.26(syst.) pb, √s = 188.64 GeV

the fraction of W bosons decaying into hadrons

BR(W →qq') = 68.72 ± 0.69(stat.) ± 0.38(syst.) %,

invisible non-SM width of the W boson

ΓinvisibleW less than MeV at 95% C.L.,

the mass of the W boson

MW = 80.44 ± 0.08(stat.)± 0.06(syst.) GeV,

the total width of the W boson

ΓW = 2.18 ± 0.20(stat.)± 0.11(syst.) GeV,

the anomalous triple gauge boson couplings of the W

ΔgZ1 = 0.16+0.13-0.20(stat.) ± 0.11(syst.)

Δkγ = 0.26+0.24-0.33(stat.) ± 0.16(syst.)

λγ = 0.18+0.13-0.20(stat.) ± 0.11(syst.)

No significant deviations from Standard Model predictions were found in any of the measurements.

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Part I

Regression analyses are performed on in vivo hemodialysis data for the transfer of creatinine, urea, uric acid and inorganic phosphate to determine the effects of variations in certain parameters on the efficiency of dialysis with a Kiil dialyzer. In calculating the mass transfer rates across the membrane, the effects of cell-plasma mass transfer kinetics are considered. The concept of the effective permeability coefficient for the red cell membrane is introduced to account for these effects. A discussion of the consequences of neglecting cell-plasma kinetics, as has been done to date in the literature, is presented.

A physical model for the Kiil dialyzer is presented in order to calculate the available membrane area for mass transfer, the linear blood and dialysate velocities, and other variables. The equations used to determine the independent variables of the regression analyses are presented. The potential dependent variables in the analyses are discussed.

Regression analyses were carried out considering overall mass-transfer coefficients, dialysances, relative dialysances, and relative permeabilities for each substance as the dependent variables. The independent variables were linear blood velocity, linear dialysate velocity, the pressure difference across the membrane, the elapsed time of dialysis, the blood hematocrit, and the arterial plasma concentrations of each substance transferred. The resulting correlations are tabulated, presented graphically, and discussed. The implications of these correlations are discussed from the viewpoint of a research investigator and from the viewpoint of patient treatment.

Recommendations for further experimental work are presented.

Part II

The interfacial structure of concurrent air-water flow in a two-inch diameter horizontal tube in the wavy flow regime has been measured using resistance wave gages. The median water depth, r.m.s. wave height, wave frequency, extrema frequency, and wave velocity have been measured as functions of air and water flow rates. Reynolds numbers, Froude numbers, Weber numbers, and bulk velocities for each phase may be calculated from these measurements. No theory for wave formation and propagation available in the literature was sufficient to describe these results.

The water surface level distribution generally is not adequately represented as a stationary Gaussian process. Five types of deviation from the Gaussian process function were noted in this work. The presence of the tube walls and the relatively large interfacial shear stresses precludes the use of simple statistical analyses to describe the interfacial structure. A detailed study of the behavior of individual fluid elements near the interface may be necessary to describe adequately wavy two-phase flow in systems similar to the one used in this work.

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It has been well-established that interfaces in crystalline materials are key players in the mechanics of a variety of mesoscopic processes such as solidification, recrystallization, grain boundary migration, and severe plastic deformation. In particular, interfaces with complex morphologies have been observed to play a crucial role in many micromechanical phenomena such as grain boundary migration, stability, and twinning. Interfaces are a unique type of material defect in that they demonstrate a breadth of behavior and characteristics eluding simplified descriptions. Indeed, modeling the complex and diverse behavior of interfaces is still an active area of research, and to the author's knowledge there are as yet no predictive models for the energy and morphology of interfaces with arbitrary character. The aim of this thesis is to develop a novel model for interface energy and morphology that i) provides accurate results (especially regarding "energy cusp" locations) for interfaces with arbitrary character, ii) depends on a small set of material parameters, and iii) is fast enough to incorporate into large scale simulations.

In the first half of the work, a model for planar, immiscible grain boundary is formulated. By building on the assumption that anisotropic grain boundary energetics are dominated by geometry and crystallography, a construction on lattice density functions (referred to as "covariance") is introduced that provides a geometric measure of the order of an interface. Covariance forms the basis for a fully general model of the energy of a planar interface, and it is demonstrated by comparison with a wide selection of molecular dynamics energy data for FCC and BCC tilt and twist boundaries that the model accurately reproduces the energy landscape using only three material parameters. It is observed that the planar constraint on the model is, in some cases, over-restrictive; this motivates an extension of the model.

In the second half of the work, the theory of faceting in interfaces is developed and applied to the planar interface model for grain boundaries. Building on previous work in mathematics and materials science, an algorithm is formulated that returns the minimal possible energy attainable by relaxation and the corresponding relaxed morphology for a given planar energy model. It is shown that the relaxation significantly improves the energy results of the planar covariance model for FCC and BCC tilt and twist boundaries. The ability of the model to accurately predict faceting patterns is demonstrated by comparison to molecular dynamics energy data and experimental morphological observation for asymmetric tilt grain boundaries. It is also demonstrated that by varying the temperature in the planar covariance model, it is possible to reproduce a priori the experimentally observed effects of temperature on facet formation.

Finally, the range and scope of the covariance and relaxation models, having been demonstrated by means of extensive MD and experimental comparison, future applications and implementations of the model are explored.