Calculation of the electronic structure of carbon films using electron energy loss spectroscopy.

The detailed understanding of the electronic properties of carbon-based materials requires the determination of their electronic structure and more precisely the calculation of their joint density of states (JDOS) and dielectric constant. Low electron energy loss spectroscopy (EELS) provides a continuous spectrum which represents all the excitations of the electrons within the material with energies ranging between zero and about 100 eV. Therefore, EELS is potentially more powerful than conventional optical spectroscopy which has an intrinsic upper information limit of about 6 eV due to absorption of light from the optical components of the system or the ambient. However, when analysing EELS data, the extraction of the single scattered data needed for Kramers Kronig calculations is subject to the deconvolution of the zero loss peak from the raw data. This procedure is particularly critical when attempting to study the near-bandgap region of materials with a bandgap below 1.5 eV. In this paper, we have calculated the electronic properties of three widely studied carbon materials; namely amorphous carbon (a-C), tetrahedral amorphous carbon (ta-C) and C60 fullerite crystal. The JDOS curve starts from zero for energy values below the bandgap and then starts to rise with a rate depending on whether the material has a direct or an indirect bandgap. Extrapolating a fit to the data immediately above the bandgap in the stronger energy loss region was used to get an accurate value for the bandgap energy and to determine whether the bandgap is direct or indirect in character. Particular problems relating to the extraction of the single scattered data for these materials are also addressed. The ta-C and C60 fullerite materials are found to be direct bandgap-like semiconductors having a bandgaps of 2.63 and 1.59eV, respectively. On the other hand, the electronic structure of a-C was unobtainable because it had such a small bandgap that most of the information is contained in the first 1.2 eV of the spectrum, which is a region removed during the zero loss deconvolution.

The structure of turbulent stratified and premixed methane/air flames I: Non-swirling flows

A series of flames in a turbulent methane/air stratified swirl burner is presented. The degree of stratification and swirl are systematically varied to generate a matrix of experimental conditions, allowing their separate and combined effects to be investigated. Non-swirling flows are considered in the present paper, and the effects of swirl are considered in a companion paper (Part II). A mean equivalence ratio of φ=0.75 is used, with φ for the highest level of stratification spanning 0.375-1.125. The burner features a central bluff-body to aid flame stabilization, and the influence of the induced recirculation zone is also considered. The current work focuses on non-swirling flows where two-component particle image velocimetry (PIV) measurements are sufficient to characterize the main features of the flow field. Scalar data obtained from Rayleigh/Raman/CO laser induced fluorescence (CO-LIF) line measurements at 103μm resolution allow the behavior of key combustion species-CH 4, CO 2, CO, H 2, H 2O and O 2-to be probed within the instantaneous flame front. Simultaneous cross-planar OH-PLIF is used to determine the orientation of the instantaneous flame normal in the scalar measurement window, allowing gradients in temperature and progress variable to be angle corrected to their three dimensional values. The relationship between curvature and flame thickness is investigated using the OH-PLIF images, as well as the effect of stratification on curvature.The main findings are that the behavior of the key combustion species in temperature space is well captured on the mean by laminar flame calculations regardless of the level of stratification. H 2 and CO are significant exceptions, both appearing at elevated levels in the stratified flames. Values for surface density function and by extension thermal scalar dissipation rate are found to be substantially lower than laminar values, as the thickening of the flame due to turbulence dominates the effect of increased strain. These findings hold for both premixed and stratified flames. The current series of flames is proposed as an interesting if challenging set of test cases for existing and emerging turbulent flame models, and data are available on request. © 2012 The Combustion Institute.

The structure of turbulent stratified and premixed methane/air flames II: Swirling flows

Experimental results are presented from a series of turbulent methane/air stratified flames stabilized on a swirl burner. Nine operating conditions are considered, systematically varying the level of stratification and swirl while maintaining a lean global mean equivalence ratio of φ̄=0.75. Scalar data are obtained from Rayleigh/Raman/CO laser induced fluorescence (CO-LIF) line measurements at 103μm resolution, allowing the behavior of the major combustion species-CH 4, CO 2, CO, H 2, H 2O and O 2-to be probed within the instantaneous flame front. The corresponding three-dimensional surface density function and thermal scalar dissipation rate are investigated, along with geometric characteristics of the flame such as curvature and flame thickness. Hydrogen and carbon monoxide levels within the flame brush are raised by stratification, indicating models with laminar premixed flame chemistry may not be suitable for stratified flames. However, flame surface density, scalar dissipation and curvature all appear insensitive to the degree of stratification in the flames surveyed. © 2012 The Combustion Institute.

Probing the electronic structure of multi-walled carbon nanotubes by transient optical transmittivity

High-resolution time resolved transmittivity measurements on horizontally aligned free-standing multi-walled carbon nanotubes reveal a different electronic transient behavior from that of graphite. This difference is ascribed to the presence of discrete energy states in the multishell carbon nanotube electronic structure. Probe polarization dependence suggests that the optical transitions involve definite selection rules. The origin of these states is discussed and a rate equation model is proposed to rationalize our findings. © 2013 Elsevier Ltd. All rights reserved.

Structure of cryogenic flames at elevated pressures

This paper presents new experimental results on cryogenic jet flames formed by a coaxial injector at a pressure of 70 bar, which approaches the pressures found in rocket engines. This element, fed with liquid oxygen and gaseous hydrogen, is placed in a square combustion chamber equipped with quartz windows. The flame is examined via spectroscopy, OH* emission, and backlighting, the aim being to provide basic information on the flame structure. It is found that some of the OH* emission is absorbed by the OH radicals present in the flame. A detailed examination of this effect is presented, in which it is shown that, for this turbulent flame, the Abel transform gives the position of the intense reaction region, whether or not absorption is signficant. The flame is attached to the oxygen injector, as at low pressure. At high pressure, flame expansion is reduced compared with low pressure and is also less dependent on the momentum flux ratio between the hydrogen and the oxygen streams. An analysis of the relevant Damköhler numbers suggests that this is because the rate of combustion is mainly controlled by large-scale turbulent mixing at high pressure, and it is dominated by jet break-up, atomization, and vaporization at low pressures. Jet break-up is particularly dependent on the momentum flux ratio. Finally, the mean volumetric heat release rates and flame surface density in the experimental facility are estimated.