Elemental Analysis of Cement by Calibration-Free Laser Induced Breakdown Spectroscopy (CF-LIBS) and Comparison with Laser Ablation – Time-of-Flight – Mass Spectrometry (LA-TOF-MS), Energy Dispersive X-Ray Spectrometry (EDX), X-Ray Fluorescence Spectroscopy (XRF), and Proton Induced X-Ray Emission Spectrometry (PIXE)

The purpose of the present study is to determine the elemental composition of Pakistani cement brands using calibration-free laser induced breakdown spectroscopy (CF-LIBS) and to compare the obtained results with the other analytical techniques such as, laser ablation – time-of-flight – mass spectrometry (LA-TOF-MS), energy dispersive X-ray spectrometry (EDX), X-ray fluorescence spectroscopy (XRF) and proton induced X-ray emission spectrometry (PIXE). Compositional results reveal that all the cement brands are mainly composed of calcium, silicon, iron, aluminum, magnesium, potassium, sodium, titanium, lithium and strontium with varying concentrations. The compositions obtained by LIBS and LA-TOF-MS are in good agreement with results obtained by the other standard techniques and demonstrate the potential use of LIBS for the online monitoring of industrial cement production.     

Calibration-Free Laser Spectral Analysis of Glasses and Copper Alloys

The calibration-free variant of the laser spectral analysis of the material of solid metal and dielectric samples has been evaluated with the example of determining the component composition of certified copper alloys, an optical filter, a crystal sample with known compositions, and fragments of glass jewelry of archeological origin. It has been shown that there is a good agreement between the measurement and reference data for macrocomponent concentrations (10% and more). Discrepancies have been found between the concentrations of components with a small content (1–5%) in the analyzed sample. All the stages and characteristic features of the methods of calibration-free analysis have been analyzed with specific examples.     

激光诱导空气等离子体的实验研究

本文利用激光诱导等离子体光谱技术(LIPS)测定一个标准大气压强下的空气所含有的元素成分。假设空气全部由氮和氧元素组成,利用自由定标模型获得空气中氮元素和氧元素的含量。由此验证激光诱导等离子体光谱技术进行定量分析的可行性,为其在等离子体定量分析中的应用奠定基础。     

A calibration-free model for laser-induced breakdown spectroscopy using non-gated detectors

Calibration-free (CF) laser-induced breakdown spectroscopy (LIBS) is normally only applicable for gated detectors due to its dependence on the assumption of a steady-state plasma. However, most currently available LIBS systems are equipped with non-gated detectors such as charge-coupled device (CCD), which degrades the accuracy of CF method. In this paper, the reason for the less satisfactory quantification performance of CF for LIBS with non-gated detectors was clarified and a time-integration calibration-free (TICF) model was proposed for applications with non-gated detectors. It was based on an assumed temporal profile of plasma properties, including temperature and electron density, obtained from another pre-experiment. The line intensity at different time during the signal collection time window was estimated with self-absorption correction according to the temporal profile of the plasma properties. The proposed model was validated on titanium alloys and compared with traditional CF. The accuracy of elemental concentration measurement was improved significantly: the average relative error of aluminum and vanadium decreased from 6.07% and 22.34% to 2.01% and 1.92%, respectively. The quantification results showed that TICF method was able to extend the applicability of CF to LIBS with non-gated detectors.     

Analysis of Soil by Magnetic Field Assisted Calibration-Free Laser Induced Breakdown Spectroscopy (CF-LIBS) and Laser Ablation – Time-of-Flight Mass Spectrometry (LA-TOF-MS)

The qualitative and quantitative analysis of soil samples collected from Sialkot, Pakistan (which contains leather industrial plants), has been performed using laser-induced breakdown spectroscopy (LIBS) and laser ablation time of flight mass spectrometry (LA-TOF-MS). The focused beam of a Q-switched Nd: YAG laser (532?nm) was used to ablate the soil samples in air at atmospheric pressure. The optical emission spectra demonstrate the presence of the spectral lines of Si, Fe, Al, Ca, Ti, K, Cr, Mg, Na, Ba, and Li in all of the samples. The emission lines intensities, electron number densities, and excitation temperatures were significantly enhanced in the presence of an external 0.3 T magnetic field applied perpendicular to the plasma plume. A maximum enhancement factor of approximately 8 was observed in the emission intensity. The emergence of several additional lines has also been detected using the magnetic field-assisted LIBS approach. The elemental composition determined using calibration-free laser-induced breakdown spectroscopy (CF-LIBS), with and without magnetic field, reveals that the external magnetic field only adjusts the laser-generated plasma dynamics without affecting the quantitative analysis of the samples. Importantly, the toxic and heavy elements such as chromium and barium were detected and quantified in all of the soil samples by both of these techniques. The variations in the compositional analysis using CF-LIBS with and without the applied magnetic field and LA-TOF-MS were less than 10%.     

用激光感生击穿光谱对大气进行定量分析

研究将激光感生击穿光谱技术用于元素定量分析的可行性。利用Nd∶YAG激光器发出的激光与一个大气压下的空气相互作用产生激光等离子体，等离子体的光经单色仪分光后转化为电信号进入计算机，存储了600～800nm的等离子体光谱数据。利用自由定标模型对等离子体进行了分析。在延迟时间8μs、采样门宽0.4μs时，利用二维波尔兹曼平面得到了大气等离子体处于局部热平衡时的温度（1.62×10K）。在假设空气全部由N和O组成的条件下由自由定标模型得到了空气中氧的含量（20.75%）和氮的含量（79.25%）。试验结果与实际吻合得很好。实验证实了用激光感生击穿光谱对大气进行定量分析是可行的，为大气污染监测研究和试验工作奠定了基础。