Markus Köhler

Sampling Probe Influences on Temperature and Species Concentrations in Molecular Beam Mass Spectroscopic Investigations of Flat Premixed Low-pressure Flames

Abstract New operating regimes for engines and combustors and the advocated use of non-conventional transportation fuels demand investigation of the combustion chemistry of different classes of chemicals, especially under premixed conditions. Detailed species compositions during combustion are needed to estimate hazardous emissions, and models for their prediction must be validated for the intended combustion conditions.Molecular-beam mass spectrometry (MBMS) is a common technique to measure quantitative species concentrations in flames. It is widely employed to characterize the flame chemistry of laminar premixed combustion, and it has been complemented with optical measurements for the detection of a number of molecular species and radicals. Significant progress has been made in recent studies through the introduction of synchrotron-based MBMS instruments. They have improved the identification process by using tunable vacuum-ultraviolet radiation for photoionization of the species to be detected, and isomer-specific measurements are now almost routinely possible. Along with quantitative species measurements, the temperature profile is needed as input parameter for chemical kinetic modeling. It is usually determined either using thermocouples or laser spectroscopic techniques.It is an ongoing discussion how sampling probes affect these measurements, and how MBMS results can be compared to combustion modeling. The present article is intended to contribute to this discussion by providing optical and MBMS results obtained with several sampling configurations.

In situ flame chemistry tracing by imaging photoelectron photoion coincidence spectroscopy

Adaptation of a low-pressure flat flame burner with a flame-sampling interface to the imaging photoelectron photoion coincidence spectrometer (iPEPICO) of the VUV beamline at the Swiss Light Source is presented. The combination of molecular-beam mass spectrometry and iPEPICO provides a new powerful analytical tool for the detailed investigation of reaction networks in flames. First results demonstrate the applicability of the new instrument to comprehensive flame diagnostics and the potentially high impact for reaction mechanism development for conventional and alternative fuels. Isomer specific identification of stable and radical flame species is demonstrated with unrivaled precision. Radical detection and identification is achieved for the initial H-abstraction products of fuel molecules as well as for the reaction controlling H, O, and OH radicals. Furthermore, quantitative evaluation of changing species concentrations during the combustion process and the applicability of respective results for kinetic model validation are demonstrated. Utilization of mass-selected threshold photoelectron spectra is shown to ensure precise signal assignment and highly reliable spatial profiles.

Phase separation in monotectic alloys as a route for liquid state fabrication of composite materials

The mechanism of liquid–liquid phase separation and factors determining the solid-state microstructure of monotectic alloys are discussed. The effect of the cooling rate on the phase-separated morphology is shown in examples of Al–In, Al–Pb, Ni–Nb–Y and Zr–Gd–Co–Al alloys solidified by different techniques. A remarkable improvement of the microstructure for the Al91Pb9 hypermonotectic alloy cast with TiB2 particles, which catalyze the phase separation, is demonstrated.

High Harmonic Generation Via Continuum Wave-Packet Interference

High-order harmonic generation (HHG) is investigated theoretically in the over-the-barrier ionization regime revealing the strong signature of interference between two separately ionized and separately propagating free wave packets of a single electron. The interference leads to the emission of coherent light at a photon energy corresponding to the kinetic-energy difference of the two recolliding electron quantum paths, thus complementary to the well-known classical three-step picture of HHG. As will be shown by time-frequency analysis of the emitted radiation, the process entirely dominates the coherent HHG emission after the atomic ground state has been depleted by a strong field. Moreover, it can be isolated from the continuum-bound harmonics via phase matching.

Quantitative laser diagnostic and modeling study of C2 and CH chemistry in combustion.

Quantitative concentration measurements of CH and C(2) have been performed in laminar, premixed, flat flames of propene and cyclopentene with varying stoichiometry. A combination of cavity ring-down (CRD) spectroscopy and laser-induced fluorescence (LIF) was used to enable sensitive detection of these species with high spatial resolution. Previously, CH and C(2) chemistry had been studied, predominantly in methane flames, to understand potential correlations of their formation and consumption. For flames of larger hydrocarbon fuels, however, quantitative information on these small intermediates is scarce, especially under fuel-rich conditions. Also, the combustion chemistry of C(2) in particular has not been studied in detail, and although it has often been observed, its role in potential build-up reactions of higher hydrocarbon species is not well understood. The quantitative measurements performed here are the first to detect both species with good spatial resolution and high sensitivity in the same experiment in flames of C(3) and C(5) fuels. The experimental profiles were compared with results of combustion modeling to reveal details of the formation and consumption of these important combustion molecules, and the investigation was devoted to assist the further understanding of the role of C(2) and of its potential chemical interdependences with CH and other small radicals.

High-order harmonic generation enhanced by XUV light

The combination of high-order harmonic generation (HHG) with resonant XUV excitation of a core electron into the transient valence vacancy that is created in the course of the HHG process is investigated theoretically. In this setup, the first electron performs a HHG three-step process, whereas the second electron Rabi flops between the core and the valence vacancy. The modified HHG spectrum due to recombination with the valence and the core is determined and analyzed for krypton on the 3d→4p resonance in the ion. We assume an 800 nm laser with an intensity of about 10(14) W/cm2 and XUV radiation from the Free Electron Laser in Hamburg (FLASH) with an intensity in the range 10(13)-10(16)W cm2. Our prediction opens perspectives for nonlinear XUV physics, attosecond x rays, and HHG-based spectroscopy involving core orbitals.

Attochirp-free high-order harmonic generation

A method is proposed for arbitrarily engineering the high-order harmonic generation phase achieved by shaping a laser pulse and employing xuv light or x rays for ionization. This renders the production of bandwidth-limited attosecond pulses possible while avoiding the use of filters for chirp compensation. By adding the first 8 Fourier components to a sinusoidal field of 1016 W/cm2, the bandwidth-limited emission of 8 as is shown to be possible from a Li2+ gas. The scheme is extendable to the zs-scale.

Relativistic nonperturbative above-threshold phenomena in strong laser fields

Relativistic features of various nonperturbative above-threshold phenomena in strong laser fields are discussed and compared. This includes above-threshold ionization of multiply charged ions as well as pair production in an ultrastrong laser wave, superimposed with either a nuclear Coulomb field or another counterpropagating laser wave. For the probability of above-threshold pair production, a new scaling relation is given. Particular attention is paid to similarities among these processes, regarding the energy and angular spectra of the particles as well as the total reaction rates.

An atmospheric pressure high-temperature laminar flow reactor for investigation of combustion and related gas phase reaction systems

A new high-temperature flow reactor experiment utilizing the powerful molecular beam mass spectrometry (MBMS) technique for detailed observation of gas phase kinetics in reacting flows is presented. The reactor design provides a consequent extension of the experimental portfolio of validation experiments for combustion reaction kinetics. Temperatures up to 1800 K are applicable by three individually controlled temperature zones with this atmospheric pressure flow reactor. Detailed speciation data are obtained using the sensitive MBMS technique, providing in situ access to almost all chemical species involved in the combustion process, including highly reactive species such as radicals. Strategies for quantifying the experimental data are presented alongside a careful analysis of the characterization of the experimental boundary conditions to enable precise numeric reproduction of the experimental results. The general capabilities of this new analytical tool for the investigation of reacting flows are demonstrated for a selected range of conditions, fuels, and applications. A detailed dataset for the well-known gaseous fuels, methane and ethylene, is provided and used to verify the experimental approach. Furthermore, application for liquid fuels and fuel components important for technical combustors like gas turbines and engines is demonstrated. Besides the detailed investigation of novel fuels and fuel components, the wide range of operation conditions gives access to extended combustion topics, such as super rich conditions at high temperature important for gasification processes, or the peroxy chemistry governing the low temperature oxidation regime. These demonstrations are accompanied by a first kinetic modeling approach, examining the opportunities for model validation purposes.

A novel vacuum ultra violet lamp for metastable rare gas experiments

We report on a new design of a vacuum ultra violet (VUV) lamp for direct optical excitation of high laying atomic states, e.g., for excitation of metastable rare gas atoms. The lamp can be directly mounted to ultra-high vacuum vessels (p ≤ 10(-10)mbar). It is driven by a 2.45 GHz microwave source. For optimum operation, it requires powers of ~20 W. The VUV light is transmitted through a magnesium fluoride window, which is known to have a decreasing transmittance for VUV photons with time. In our special setup, after a run-time of the VUV lamp of 550 h the detected signal continuously decreased to 25% of its initial value. This corresponds to a lifetime increase of two orders of magnitude compared to previous setups or commercial lamps.