Visualization of the evaporation of a diesel spray using combined Mie and Rayleigh scattering techniques

Evaporating Diesel sprays are studied by laser Rayleigh scattering measurements in an optically accessible high-pressure/high-temperature cell that reproduces the thermodynamic conditions which exist in the combustion chamber of a Diesel engine during injection. n-Decane is injected into the vessel using a state-of-the-art near-production three-hole nozzle. Global images of the distributions of the liquid and vapor phases of the injected fuel are obtained using a combined Schlieren and Mie scattering setup. More details about the evaporation are revealed when the spray is illuminated by a laser light sheet: laser light can be scattered by molecules in the gas phase (Rayleigh scattering) or comparably large fuel droplets (Mie scattering). The former is seen in regions where the fuel has completely evaporated, and the latter is dominant in regions with high droplet concentrations. Studying the polarization of the signal light allows the distinction of three different regions in the spray that are characterized by a moderate, low or negligible concentration of liquid fuel droplets. The characteristics of fuel evaporation are investigated for different observation times after the start of injection, chamber conditions and injection pressures. For the quantification of the fuel concentration measurements based on Rayleigh scattering, a calibration method that uses propane as a reference gas is presented and tested. At high ambient temperatures, the accuracy of the concentration measurements is limited by pyrolysis of the fuel molecules. This paper was originally presented at the 14th International Symposium on Applications of Laser Techniques to Fluid Mechanics, Lisbon, 2008.     

Temperature and species measurement in a quenching boundary layer on a flat-flame burner

A detailed understanding of transport phenomena and reactions in near-wall boundary layers of combustion chambers is essential for further reducing pollutant emissions and improving thermal efficiencies of internal combustion engines. In a model experiment, the potential of laser-induced fluorescence (LIF) was investigated for measurements inside the boundary layer connected to flame-wall interaction at atmospheric pressure. Temperature and species distributions were measured in the quenching boundary layer formed close to a cooled metal surface located parallel to the flow of a premixed methane/air flat flame. Multi-line NO-LIF thermometry provided gas-phase temperature distributions. In addition, flame species OH, CH₂O and CO were monitored by single-photon (OH, CH₂O) and two-photon (CO) excitation LIF, respectively. The temperature dependence of the OH-LIF signal intensities was corrected for using the measured gas-phase temperature distributions. The spatial line-pair resolution of the imaging system was 22 μm determined by imaging microscopic line pairs printed on a resolution target. The experimental results show the expected flame quenching behavior in the boundary layer and they reveal the potential and limitations of the applied diagnostics techniques. Limitations in spatial resolution are attributed to refraction of fluorescence radiation propagating through steep temperature gradients in the boundary layer. For the present experimental arrangements, the applied diagnostics techniques are applicable as close to the wall as 200 μm with measurement precision then exceeding the 15–25% limit for species detection, with estimates of double this value for the case of H₂CO due to the unknown effect of the Boltzmann fraction corrections not included in the data evaluation process. Temperature measurements are believed to be accurate within 50 K in the near-wall zone, which amounts to roughly 10% at the lower temperatures encountered in this region of the flames.     

Molecular Engineering of Conjugated Acetylenic Polymers for Efficient Cocatalyst‐free Photoelectrochemical Water Reduction

Conjugated polymers featuring tunable band gaps/positions and tailored active centers, are attractive photoelectrode materials for water splitting. However, their exploration falls far behind their inorganic counterparts. Herein, we demonstrate a molecular engineering strategy for the tailoring aromatic units of conjugated acetylenic polymers from benzene‐ to thiophene‐based. The polarized thiophene‐based monomers of conjugated acetylenic polymers can largely extend the light absorption and promote charge separation/transport. The C≡C bonds are activated for catalyzing water reduction. Using on‐surface Glaser polycondensation, as‐fabricated poly(2,5‐diethynylthieno[3,2‐b]thiophene) on commercial Cu foam exhibits a record H₂‐evolution photocurrent density of 370 μA cm^?2 at 0.3 V vs. reversible hydrogen electrode among current cocatalyst‐free organic photocathodes (1–100 μA cm^?2). This approach to modulate the optical, charge transfer, and catalytic properties of conjugated polymers paves a critical way toward high‐activity organic photoelectrodes.     

Stress in self-assembled monolayers: omega-biphenyl alkane thiols on Au(111)

Self-assembled monolayers of omega-(4'-methylbiphenyl-4-yl) alkane thiols CH3(C6H4)2(CH2)(n)SH (BPn, n = 2, 3, and 5) on Au(111) substrates, prepared at room and elevated temperatures, were studied using scanning tunneling microscopy. In contrast to the biphenyl thiol analogues with n = 0 or 1, ordered domains of large size are formed which exhibit small, periodic height variations on a length scale of several nanometers. These are attributed to solitons (or domain walls), resulting from structural mismatch between the molecular adlayer and the gold substrate. The implications of these results for the design of aromatic thiols to cope with stress and yield low-defect density self-assembled monolayers are discussed.     

Use of Global Symmetries in Automated Signal Class Recognition by a Bayesian Method

Automated or semiautomated pattern recognition in multidimensional NMR spectroscopy is strongly hampered by the large number of noise and artifact peaks occurring under practical conditions. A general Bayesian method which is able to assign probabilities that observed peaks are members of given signal classes (e.g., the class of true resonance peaks or the class of noise and artifact peaks) was proposed previously. The discriminative power of this approach is dependent on the choice of the properties characterizing the peaks. The automated class recognition is improved by the addition of a nonlocal feature, the similarities of peak shapes in symmetry-related positions. It turns out that this additional property strongly decreases the overlap of the multivariate probability distributions for true signals and noise and hence largely increases the discrimination of true resonance peaks from noise and artifacts.     

Universal bounds on the selfaveraging of random diffraction measures

 We consider diffraction at random point scatterers on general discrete point sets in ℝ^ν, restricted to a finite volume. We allow for random amplitudes and random dislocations of the scatterers. We investigate the speed of convergence of the random scattering measures applied to an observable towards its mean, when the finite volume tends to infinity. We give an explicit universal large deviation upper bound that is exponential in the number of scatterers. The rate is given in terms of a universal function that depends on the point set only through the minimal distance between points, and on the observable only through a suitable Sobolev-norm. Our proof uses a cluster expansion and also provides a central limit theorem. Received: 10 October 2001 / Revised version: 26 January 2003 / Published online: 15 April 2003 Work supported by the DFG Mathematics Subject Classification (2000): 78A45, 82B44, 60F10, 82B20 Key words or phrases: Diffraction theory – Random scatterers – Random point sets – Quasicrystals – Large deviations – Cluster expansions