Spark-induced breakdown spectroscopy of methane/air and hydrogen-enriched methane/air mixtures at engine relevant conditions

Highlights: • Spatial dependence of OH, NH, N₂ and CN radicals identified across electrode gap • Metal emission lines of nickel, iron and copper confirmed by X-ray spectroscopy • Temporally resolved SIBS measurements during the glow phase • Measured spectral intensity varies with supplied secondary power. An experimental study of temporally and spatially resolved spark-induced breakdown spectroscopy (SIBS) of methane and hydrogen-enriched methane mixtures is reported for premixed combustion in internal combustion engines. Experiments were conducted at quiescent conditions in a small constant volume chamber, varying pressure, stoichiometry and hydrogen admixture rates. Spectral emissions of hydroxyl (OH) at 306 nm, NH at 336 nm, the cyanogen (CN) band at 388 nm and the nitrogen second positive system (N₂) were spatially resolved on a time-integrated setup. OH emissions were found to be strongest between the electrodes, whereas CN emissions were more pronounced at the center and ground electrode. Metal emission lines were observed, partially interfering with the radicals of interest. Energy dispersive X-ray spectroscopy showed nickel, copper and iron shares in the noble metal electrodes, confirming the origin of these metal emissions. Simultaneously to time-integrated spectra, temporally-resolved spectra at a frame rate of 100 kHz were recorded during the glow phase of the electrical discharge. Comparison of both spectra revealed a good agreement in terms of spectral characteristics and resolved species. Temporally-resolved spectra highlighted the strong dependence on the electric discharge characteristics of the inductive coil ignition system in the early phase of ignition. Ratios of CN/OH and CN/NH were found to correlate with the fuel-air equivalence ratio, but shot to shot repeatability was up to a factor 3 larger than the dependence on the mixture composition. Moreover, these ratios changed with increasing pressure at ignition timing, and with the higher pressure metal emission lines became more pronounced. Additionally, at pressures higher than 2 bar, the equilibrium position shifted to the disadvantage of the second positive system of nitrogen, suppressing this emission. Hydrogen admixture to methane of up to 50 vol% were found to not significantly alter the spectral signature between 300 and 400 nm, only marginally affecting the signal ratios of CN/OH and CN/NH.