Institute of Bismuth Science, University of Shanghai for Science and Technology, Shanghai 200093, China.
Technical Center for Industrial Product and Raw Material Inspection and Testing of Shanghai Customs, Shanghai 200135, China.
Anal Methods. 2022 Jan 27;14(4):427-437. doi: 10.1039/d1ay01881g.
The rapid and accurate quantitative analysis of the total iron (TFe) content in iron ores is extremely important in global iron ore trade. Due to the matrix effect among iron ores from different origins, it is a major challenge to accurately determine the TFe content of iron ores by laser-induced breakdown spectroscopy (LIBS). The double back propagation artificial neural network (DBP-ANN) proposed in this paper provides a solution to improve the accuracy of LIBS in determining the TFe content of branded iron ores, which is a combination of pattern recognition and regression analysis based on BP-ANN. In this study, LIBS spectra of 80 batches of representative iron ore samples from 4 brands were collected. The univariate regression methods based on brand-independent and brand-hybrid were analyzed and compared for determining the TFe content of branded iron ores, and the multivariate model based on DBP-ANN was constructed for the first time. BP-ANN was employed to establish different quantitative models of the TFe content of each type of brand after brand classification of iron ores based on the BP-ANN algorithm. Compared with the brand-hybrid BP-ANN, the coefficient of determination () of the test samples using DBP-ANN increased from 0.972 to 0.996, and the root mean square error of prediction () and the average relative error of prediction () were reduced from 0.456 wt% and 0.584% to 0.177 wt% and 0.228% respectively. Moreover, the prediction error based on the DBP-ANN model was within the error range (<0.275 wt%) accepted by the traditional chemical analysis method GB/T 6730.5-2009. Meanwhile, the established DBP-ANN method was also compared with the common multivariate method, and it showed better analytical performance. The results showed that LIBS combined with DBP-ANN has the potential to achieve rapid and accurate analysis of the TFe content of branded iron ores.
快速准确地定量分析铁矿石中的全铁(TFe)含量对于全球铁矿石贸易至关重要。由于来自不同产地的铁矿石之间存在基质效应,因此通过激光诱导击穿光谱(LIBS)准确测定铁矿石的 TFe 含量是一个重大挑战。本文提出的双反向传播人工神经网络(DBP-ANN)提供了一种解决方案,可以提高 LIBS 测定品牌铁矿石 TFe 含量的准确性,它是基于 BP-ANN 的模式识别和回归分析的结合。在这项研究中,采集了来自 4 个品牌的 80 批代表性铁矿石样品的 LIBS 光谱。分析并比较了基于品牌独立和品牌混合的单变量回归方法,以确定品牌铁矿石的 TFe 含量,并首次构建了基于 DBP-ANN 的多元模型。在基于 BP-ANN 算法对铁矿石进行品牌分类后,BP-ANN 用于为每种品牌的 TFe 含量建立不同的定量模型。与品牌混合 BP-ANN 相比,使用 DBP-ANN 的测试样品的决定系数()从 0.972 增加到 0.996,预测值的均方根误差()和预测值的平均相对误差()分别从 0.456wt%和 0.584%降低到 0.177wt%和 0.228%。此外,基于 DBP-ANN 模型的预测误差在传统化学分析方法 GB/T 6730.5-2009 接受的误差范围内(<0.275wt%)。同时,还将建立的 DBP-ANN 方法与常用的多元方法进行了比较,结果表明其具有更好的分析性能。结果表明,LIBS 结合 DBP-ANN 有可能实现品牌铁矿石 TFe 含量的快速准确分析。