An experimental and modeling study of the autoignition of 3-methylheptane

An experimental and kinetic modeling study of the autoignition of 3-methylheptane, a compound representative of the high molecular weight lightly branched alkanes found in large quantities in conventional and synthetic aviation kerosene and diesel fuels, is reported. Shock tube and rapid compression machine ignition delay time measurements are reported over a wide range of conditions of relevance to combustion engine applications: temperatures from 678 to 1356 K; pressures of 6.5, 10, 20, and 50 atm; and equivalence ratios of 0.5, 1.0, and 2.0. The wide range of temperatures examined provides observation of autoignition in three reactivity regimes, including the negative temperature coefficient (NTC) regime characteristic of paraffinic fuels. Comparisons made between the current ignition delay measurements for 3-methylheptane and previous results for n-octane and 2-methylheptane quantifies the influence of a single methyl substitution and its location on the reactivity of alkanes. It is found that the three C₈ alkane isomers have indistinguishable high-temperature ignition delay but their ignition delay times deviate in the NTC and low-temperature regimes in correlation with their research octane numbers. The experimental results are compared with the predictions of a proposed kinetic model that includes both high- and low-temperature oxidation chemistry. The model mechanistically explains the differences in reactivity for n-octane, 2-methylheptane, and 3-methylheptane in the NTC through the influence of the methyl substitution on the rates of isomerization reactions in the low-temperature chain branching pathway, that ultimately leads to ketohydroperoxide species, and the competition between low-temperature chain branching and the formation of cyclic ethers, in a chain propagating pathway.     

Finding thermoacoustic limit cycles for a ducted Burke-Schumann flame

This paper examines nonlinear thermoacoustic oscillations of a ducted Burke-Schumann diffusion flame. The nonlinear dynamics of the thermoacoustic system are studied using two distinct approaches. In the first approach, a continuation analysis is performed to find limit cycle amplitudes over a range of operating conditions. The strength of this approach is that one can characterize the coupled system’s nonlinear behaviour over a large parameter space with relative ease. It is not able to give physical insight into that behaviour, however. The second approach uses a Flame Describing Function (FDF) to characterize the flame’s response to harmonic velocity fluctuations over a range of forcing frequencies and forcing amplitudes, from which limit cycle amplitudes can be found. A strength of the FDF approach is that it reveals the physical mechanisms responsible for the behaviour observed. However, the calculation of the FDF is time consuming, and it must be recalculated if the flame’s operating conditions change. With the strengths and shortcomings of the two approaches in mind, this paper advocates combining the two to provide the dynamics over a large parameter space and, furthermore, physical insight into that behaviour at judiciously-chosen points in the parameter space. Further physical insight concerning the flame’s near-linear response at all forcing amplitudes is given by studying the forced flame in the time domain. It is shown that, for this flame model, the limit cycles arise because of the flame’s nonlinear behaviour when it is close to the inlet.     

Molecular vacancies in herringbone crystals

We have found evidence of molecular vacancies in the herringbone molecular crystals pentacene and hexabenzo[bc,?ef,?hi,?kl,?no,?qr]coronene using electron diffraction. Experimental electron diffraction patterns taken parallel to the long molecular axis from these crystals exhibited streaking in two characteristic directions, and the streaking approximately followed the molecular herringbone directions. Molecular dynamics simulations of vacancies in pentacene showed that the streaks can be explained by anisotropic lattice relaxations near the defects. Simulated electron diffraction patterns from the crystal–vacancy models at finite temperatures showed streaking similar to the experimental data. The energy of formation of vacancies in pentacene was calculated to be 1.7?eV. The vacancy entropy in pentacene was simulated to be approximately 40 times the Boltzmann constant. We expect these molecular vacancies to influence charge transport and mechanical properties.     

Unification and hierarchy from 5D anti-de Sitter space

We show that perturbative high scale unification and a solution to the hierarchy problem are possible with extra dimensions in the context of the warped geometry of 5D anti-de Sitter space ( AdS(5)). This is possible because the couplings for bulk gauge bosons run logarithmically below the AdS(5) curvature scale. The calculation is done in five dimensions, rather than in the effective theory, which is strongly coupled above the TeV scale.     

Chiral mirror and optical resonator designs for circularly polarized light: suppression of cross-polarized reflectances and transmittances

A left-handed chiral sculptured thin film (STF) that reflects strongly at the wavelength of the circular Bragg resonance tends to partially convert the handedness of incident LCP (left-circularly-polarized) light to RCP (right-circularly-polarized). We show that the cross-polarized component of the reflected RCP beam can be eliminated by interference with an additional RCP beam that is reflected at the interface of an isotropic cover and an AR (antireflecting) layer. For best results the refractive index and thickness of the AR layer need to accommodate a phase change on reflection that occurs at the chiral film. Effective suppression of the reflectances R_RR, R_RL, R_LR and the transmittances T_RL, T_LR can be achieved by sandwiching the chiral reflector between such amplitude and phase-matched AR coatings. Co-polarized chiral reflectors of this type may form efficient handed optical resonators. For LCP light the optical properties of such a handed resonator are formally the same as the properties of the isotropic passive or active Fabry–Perot resonators, but the handed resonator is transparent to RCP light.     

Quantum hair and quantum gravity

A black hole may carry quantum numbers that arenot associated with massless gauge fields, contrary to the spirit of the no-hair theorems. The quantum hair is invisible in the classical limit, but measurable via quantum interference experiments. Quantum hair alters the temperature of the radiation emitted by a black hole. It also induces non-zero expectation values for fields outside the event horizon; these expectation values are non-perturbative in , and decay exponentially far from the hole. The existence of quantum hair demonstrates that a black hole can have an intricate quantum-mechanical structure that is completely missed by standard semiclassical theory.Based on an essay which received second award from the Gravity Research Foundation, 1991     

A Lie theoretic galois theory for the spectral curves of an integrable system: I

In the study of integrable systems of ODE's arising from a Lax pair with a parameter, the constants of the motion occur as spectral curves. The specific curves depend upon the representation of the Lie algebra. In this paper a Galois theory of spectral curves is given that classifies the spectral curves from an integrable system. The spectral curves correspond to conjugacy classes of certain subgroups of the Weyl group for the Lie algebra. The theory is illustrated with the periodic Toda lattice.Partially supported by a Louisiana Education Quality Support Fund grant LEQSF (87-89)-RD-A-8     

Synthesis of Fluorinated Graphene Oxide and its Amphiphobic Properties

The richly functionalized basal plane bonded to polar organic moieties makes graphene oxide (GO) innately hydrophilic. Here, a methodology to synthesize fluorinated graphene oxide by oxidizing the basal plane of fluorinated graphite, allowing for tunable hydrophobicity of GO, is reported. Fluorine exists as tertiary alkyl fluorides covalently bonded to graphitic carbons, and using magic‐angle spinning (MAS) ¹³C NMR as a primary tool chemical structures for the two types of synthesized fluorinated graphene oxides (FGOs) with significantly different fluorine contents are proposed. The low surface energy of the C–F bond drastically affects GO's wetting behavior, leading to amphiphobicity in its highly fluorinated form. Ease of solution processing enables the fabrication of inks that are spray‐painted on various porous/non‐porous substrates. These coatings maintain amphiphobicity for solvents with surface tensions down to 59 dyn/cm, thus bypassing existing lithographic means to create similar surfaces. The approach towards fluorinating GO and fabricating graphene‐based surfaces with tunable wettability opens the path towards unique, accessible, carbon‐based amphiphobic coatings.     

Impaired pulmonary blood flow distribution in congestive heart failure assessed using synchrotron radiation microangiography

Synchrotron radiation microangiography is a powerful tool for assessing adverse changes in pulmonary vessel density associated with primary pulmonary hypertension (PH). Congestive heart failure (CHF) leads to a `secondary' onset of PH, yet it is unknown whether secondary PH is also associated with reduced vessel density. This study utilized synchrotron radiation to assess both pulmonary vessel density and endothelial function in a Dahl rat model of CHF with secondary PH. High salt‐fed Dahl salt‐sensitive (Dahl‐S) and salt‐resistant (Dahl‐R) rats were anesthetized and microangiography was performed to assess the pulmonary vessel density and vascular responses to (i) sodium nitroprusside (5.0 µg kg^?1 min^?1), (ii) acetylcholine (3.0 µg kg^?1 min^?1) and (iii) ET‐1_A receptor blockade, BQ‐123 (1 mg kg^?1). Dahl‐S rats developed CHF and secondary PH as evident by endothelial dysfunction, impaired vasodilatory responses to acetylcholine, enhanced vasodilatory responses to BQ‐123 and extensive pulmonary vascular remodeling. Consequently, the pulmonary vessel density was adversely reduced. Interestingly, the etiology of secondary PH manifests with structural and functional changes that are comparable with that previously reported for primary PH. One important discrepancy, however, is that ET‐1 modulation of pulmonary vessels is most striking in vessels with a diameter range of 100–200 µm in secondary PH, in contrast to a range of 200–300 µm in primary PH. Such discrepancies should be considered in future studies investigating primary and secondary forms of PH.