Standard Reference Line Combined with One-Point Calibration-Free Laser-Induced Breakdown Spectroscopy (CF-LIBS) to Quantitatively Analyze Stainless and Heat Resistant Steel.

Due to the influence of self-absorption of major elements, scarce observable spectral lines of trace elements, and relative efficiency correction of experimental system, accurate quantitative analysis with calibration-free laser-induced breakdown spectroscopy (CF-LIBS) is in fact not easy. In order to overcome these difficulties, standard reference line (SRL) combined with one-point calibration (OPC) is used to analyze six elements in three stainless-steel and five heat-resistant steel samples. The Stark broadening and Saha-Boltzmann plot of Fe are used to calculate the electron density and the plasma temperature, respectively. In the present work, we tested the original SRL method, the SRL with the OPC method, and intercept with the OPC method. The final calculation results show that the latter two methods can effectively improve the overall accuracy of quantitative analysis and the detection limits of trace elements.

Calibration-Free Laser-Induced Breakdown Spectroscopy (CF-LIBS) with Standard Reference Line for the Analysis of Stainless Steel.

In this work, calibration-free laser-induced breakdown spectroscopy (CF-LIBS) is used to analyze a certified stainless steel sample. Due to self-absorption of the spectral lines from the major element Fe and the sparse lines of trace elements, it is usually not easy to construct the Boltzmann plots of all species. A standard reference line method is proposed here to solve this difficulty under the assumption of local thermodynamic equilibrium so that the same temperature value for all elements present into the plasma can be considered. Based on the concentration and rich spectral lines of Fe, the Stark broadening of Fe(I) 381.584 nm and Saha-Boltzmann plots of this element are used to calculate the electron density and the plasma temperature, respectively. In order to determine the plasma temperature accurately, which is seriously affected by self-absorption, a pre-selection procedure for eliminating those spectral lines with strong self-absorption is employed. Then, one spectral line of each element is selected to calculate its corresponding concentration. The results from the standard reference lines with and without self-absorption of Fe are compared. This method allows us to measure trace element content and effectively avoid the adverse effects due to self-absorption.

Development of a tunable diode laser absorption sensor for online monitoring of industrial gas total emissions based on optical scintillation cross-correlation technique.

We report the first application of gas total emission using a DFB diode laser for gas concentration measurements combined with two LEDs for gas velocity measurements. In situ gas total emissions and particle density measurements in an industrial pipeline using simultaneous tunable diode laser absorption spectroscopy (TDLAS) and optical scintillation cross-correlation technique (OSCC) are presented. Velocity mean values obtained are 7.59 m/s (OSCC, standard deviation is 1.37 m/s) and 8.20 m/s (Pitot tube, standard deviation is 1.47 m/s) in a steel plant pipeline for comparison. Our experiments demonstrate that the combined system of TDLAS and OSCC provides a new versatile tool for accurate measurements of total gas emissions.

[Research on Temporal and Spatial Evolution of Reheating Double-Pulse Laser-Induced Plasma].

In order to investigate the emission enhancement mechanisms of reheating Double Pulse Laser-Induced Breakdown Spectroscopy (DP-LIBS), single pulse LIBS (SP-LIBS) and reheating DP-LIBS were carried out on an alloy steel sample respectively. The plasma emission was collected by an Echelle spectrometer with high resolution, while the plasma structure was monitored via fast-photography. The temporal and spatial evolutio ns of the plasma generated by SP-LIBS and reheating DP-LIBS were being studied. It is found that the plasma temperature in reheating DP-LIBS was higher than that of SP-LIBS, and there was a turning point for the decay rate of plasma temperature in reheating DP-LIBS when the delay time was equal to the interpulse time of DP-LIBS. Moreover, the inte nsity of the plasma image was increased by reheating DP-LIBS, and the height and width of the central region of the plasma were increased about 23.5% and 15.1% respectively. The results of spatial distribution showed that the intensity of Fe II and N I lines in the plasma were obviously enhanced by reheating DP-LIBS when the distance from the sample surface was larger than 0.6 mm. While the intensity enhancement for Fe I lines were little, even in some positio ns the intensity of Fe I lines decreased. The plasma temperature of double-pulse configuration was about 2 000 K higher than that of SP-LIBS, and a larger hot region in the plasma was generated. It is evidenced that the emission enhancement mechanisms in reheating DP-LIBS is that the second laser pulse re-excited the plasma induced by the first laser pulse, and the higher plasma temperature resulted from the re-exciting process.

Fire Source Localization Based on Distributed Temperature Sensing by a Dual-Line Optical Fiber System.

We propose a method for localizing a fire source using an optical fiber distributed temperature sensor system. A section of two parallel optical fibers employed as the sensing element is installed near the ceiling of a closed room in which the fire source is located. By measuring the temperature of hot air flows, the problem of three-dimensional fire source localization is transformed to two dimensions. The method of the source location is verified with experiments using burning alcohol as fire source, and it is demonstrated that the method represents a robust and reliable technique for localizing a fire source also for long sensing ranges.

The Influence of Acquisition Delay for Calibration-Free Laser-Induced Breakdown Spectroscopy.

Time-resolved spectra of neutral and ionized atomic emissions from slag sample are measured by laser-induced breakdown spectroscopy (LIBS). Various factors affecting the calibration-free CF-LIBS method are carefully analyzed, and subsequently these factors are either avoided or corrected. Plasma temperature and electron density are calculated by Saha-Boltzmann plot and Stark broadening of Ca, respectively. At the same time, self-absorption and local thermodynamic equilibrium have been carefully studied. An automatic spectral lines elimination algorithm is applied to calculate plasma temperature and element concentration. The calculated element concentrations show marked changes with acquisition time increasing. Due to the influence of continuous spectrum at early times and self-absorption at late times, the large absolute errors sum is obtained in these two periods. The smallest absolute errors sum corresponds to the gate delay time 1.5 µs < td < 2 µs for our experimental setup.

[Research on algorithm for self-absorption correction based on multi-particles LIBS spectra].

In order to overcome the influence of self-absorption on quantitative analysis, the optimizing process of very fast simulated annealing algorithm was studied. According to basic theory of plasma emission spectrum, a new algorithm for self-absorpton correction based on multi-particles spectra was proposed, and the algorithm flowchart was given. With the self-absorption correction algorithm mentioned above, the spectra of refining slag and blast furnace slag were corrected. The effect of self-ab sorption correction on the quantitative analysis results was analyzed based on calibration free method. Comparison of Boltzmann plots before and after self-absorption correction indicated that the plasma temperatures calculated with spectra after self-absorption correction tended to be uniform, and remained stable around 11,600 K. The Boltzmann plots constructed with plasma spectra of the same particle after self-absorption correction indicated that the intercepts were almost the same except for one group data. With calibration free method and spectra after self-absorption correction, the contents of components in slag were analyzed. For refining slag, quantitative analysis precision of MgO was low. If ignoring the existence of MgO, the relative errors of quantitative analysis results of CaO, Al2 O3 and SiOs were much smaller. For blast furnace slag in which the content of MgO was 8.49%, the relative error of quantitative analysis result of Al2 O3 was 2.38%, which was the smallest. And the relative error of quantitative analysis result of MgO was 28.27%, which was still the biggest.

[Quantitative analysis of Mn, Cr in steel based on laser-induced breakdown spectroscopy].

Quantitative analysis of trace elements such as manganese and chromium in steel was performed employing laser-induced breakdown spectroscopy (LIBS) technique in the present paper. The experimental measurements indicate that the optimal delay, focal plane and detecting position from the sample surface are 2 micros, -3.5 mm and 1.5 mm,respectively. Mn I: 403.07 nm and Cr I : 427.48 nm were selected as the analytical lines and their contents in the target steel sample were analyzed with traditional quantitative analysis and internal standard methods. Comparison of the results with two kinds of quantitatively analytical methods show that the coefficients of determination gained by internal standard method are 0.998 and 0.979 which are much better than the results obtained by traditional quantitative analysis method. According to the established calibration curve by internal standard method the detection limits of manganese and chromium calculated are 0.005% and 0.040 6%, respectively.

[Quantitative analysis of slag by calibration-free laser-induced breakdown spectroscopy].

Calibration-free laser induced breakdown spectroscopy (CF-LIBS) was employed for the quantitative analysis of slag. Nd:YAG laser ablation was performed in air. The laser-induced plasma emission was measured by an Echelle spectrometer equipped with an ICCD. The plasma temperature and electron number density were determined from Boltzmann plots and a Ca I line width, respectively. The assumption of local thermal equilibrium was validated by the Ne criterion. The concentration of oxides was obtained from the concentration of elements by using stoichiometric relation. The calculated oxide concentrations were compared with those obtained by XRF. The relative errors of major elements were less than 15%. The results indicate that this method can be employed for the analysis of major elements in multi-component complex materials without certified reference.

[Monitoring of oxygen concentration based on tunable diode laser absorption spectroscopy].

Oxygen is a widely used important gas in the industrial process. It is very meaningful to on-line monitor the oxygen concentration for the enhancement of combustion efficiency and reduction in environmental pollution. Tunable diode laser absorption spectroscopy (TDLAS) is a highly sensitive, highly selective and fast time response trace gas detection technique. With the features of tunability and narrow linewidth of distributed feedback (DFB) diode laser and by precisely tuning the laser output wavelength to a single isolated absorption line of the gas, TDLAS technique can be utilized to accurately implement gas concentration measurement with very high sensitivity. In the present paper, the authors used a DFB laser was used as the light source, and by employing wavelength modulation method and measuring the second harmonic signal of one absorption line near 760 nm of oxygen molecule, the authors built a system for online monitoring of oxygen concentration. The characteristics of the system are as follows: the scope of detection is 0.01%-20%; detection accuracy is 0.1%, long term stability is 1%.

[Second-harmonic detection with tunable diode laser absorption spectroscopy of CO and CO2 at 1.58 microm].

Tunable diode laser absorption spectroscopy has been applied in the fields of atmospheric chemistry and monitoring pollutant gases as a new method of measuring trace gases. The technique of remote sensing of CO and CO2 at 760 mm Hg pressure with tunable diode laser absorption spectroscopy in the near-infrared region is introduced. And the relationship between the second-harmonic spectrum of CO2 in Lorentzian line shape and the modulation amplitude is also presented.

Room-temperature multiwavelength erbium-doped fiber ring laser employing sinusoidal phase-modulation feedback.

An effective method for achieving a room-temperature multiwavelength erbium-doped fiber ring laser is presented. Simultaneous multiwavelength lasing with 0.5-nm intervals is achieved both experimentally and theoretically by addition of sinusoidal phase modulation in the ring cavity to prevent single-wavelength oscillation.