State Key Lab of Power System, Department of Energy and Power Engineering, Tsinghua-BP Clean Energy Centre, Tsinghua University, Beijing, 100084, China.
State Key Lab of Power System, Department of Energy and Power Engineering, Tsinghua-BP Clean Energy Centre, Tsinghua University, Beijing, 100084, China.
Anal Chim Acta. 2019 Jun 13;1058:39-47. doi: 10.1016/j.aca.2019.01.016. Epub 2019 Jan 18.
The self-absorption effect due to optically thick property greatly influences the measured line intensities as well as the performance of quantification for laser-induced breakdown spectroscopy (LIBS) especially for calibration-free LIBS which requires proper correction. In this paper, a new self-absorption correction method for Calibration-Free LIBS (CF-LIBS), called blackbody radiation referenced self-absorption correction (BRR-SAC) is proposed. An iterative algorithm was designed to calculate the plasma temperature and normally hard-to-obtain collection efficiency of the optical collection system by directly comparing the measured spectrum with the corresponding theoretical blackbody radiation for self-absorption correction. Compared with generally applied self-absorption correction methods based on the principle of curve of growth, the proposed method has obvious advantages of simpler programming, higher computation efficiency, and its independency of the availability or accuracy of line broadening coefficients. Experiments were conducted on titanium alloy samples. The experimental results showed that the self-absorption was corrected with increased linearity of the Boltzmann plots and the measurement accuracy of the elemental concentration was significantly improved through BRR-SAC. Compared with the traditional CF-LIBS with self-absorption correction, the proposed method also showed better performance. In addition, BRR-SAC provides a simple way to obtain the collection efficiency of the experimental setup, which benefits the plasma diagnostics and quantitative analysis.
由于光学厚的特性,自吸收效应对激光诱导击穿光谱(LIBS)的测量谱线强度以及定量性能有很大影响,特别是对于不需要校准的 LIBS,这需要适当的校正。本文提出了一种新的用于无校准激光诱导击穿光谱(CF-LIBS)的自吸收校正方法,称为黑体辐射参考自吸收校正(BRR-SAC)。通过直接比较测量光谱与相应的理论黑体辐射,设计了一种迭代算法来计算等离子体温度和通常难以获得的光学收集系统的收集效率,以进行自吸收校正。与基于生长曲线原理的常用自吸收校正方法相比,该方法具有编程更简单、计算效率更高、以及不依赖于谱线展宽系数的可用性或准确性的明显优势。在钛合金样品上进行了实验。实验结果表明,通过 BRR-SAC 对自吸收进行校正,可提高玻尔兹曼图的线性度,显著提高元素浓度的测量精度。与具有自吸收校正的传统 CF-LIBS 相比,该方法还表现出更好的性能。此外,BRR-SAC 提供了一种获取实验装置收集效率的简单方法,这有利于等离子体诊断和定量分析。