2-巯基苯并噻唑的太赫兹时域光谱定量研究
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摘要
为了减少由于橡胶促进剂2-巯基苯并噻唑(MBT)掺假而导致橡胶制品质量不过关的问题,提出利用太赫兹时域光谱技术对MBT的有效含量进行定量研究。利用太赫兹透射测量得到MBT和聚乙烯混合物在0.3THz～1.4THz的吸收特征谱,提出了一种基于最小二乘支持向量回归(LS-SVR)的MBT定量检测模型,将LS-SVR模型分别与偏最小二乘模型和支持向量机回归模型进行比较,得到模型预测集均方根误差分别为1.1330%,2.5583%和2.3869%。结果表明,LS-SVR的定量模型可取得更好的效果,其精度更高,稳定性更好。本研究为MBT定量检测提供了新的快速且有效的方法。
The serious adulteration of the rubber accelerator 2-mercaptobenzothiazole(MBT) will lead to the failure quality of rubber products.Aiming at this problem,a method which uses terahertz time-domain spectroscopy(THz-TDS) was proposed for quantifying the effective content of MBT.The absorption characteristic spectrum of the mixture of MBT and polyethylene in 0.3THz～1.4THz was obtained by terahertz transmission measurement.A MBT quantitative detection model based on least squares-support vector regression(LS-SVR) was proposed.LS-SVR model was compared with partial least squares model and support vector regression model respectively.The results show that,the root mean square errors of the model prediction sets are 1.1330%,2.5583% and 2.3869% respectively.The quantitative model of LS-SVR can achieve better results with higher accuracy and better stability.This study provides a new fast and effective method for quantitative detection of MBT.
The serious adulteration of the rubber accelerator 2-mercaptobenzothiazole(MBT) will lead to the failure quality of rubber products.Aiming at this problem,a method which uses terahertz time-domain spectroscopy(THz-TDS) was proposed for quantifying the effective content of MBT.The absorption characteristic spectrum of the mixture of MBT and polyethylene in 0.3THz～1.4THz was obtained by terahertz transmission measurement.A MBT quantitative detection model based on least squares-support vector regression(LS-SVR) was proposed.LS-SVR model was compared with partial least squares model and support vector regression model respectively.The results show that,the root mean square errors of the model prediction sets are 1.1330%,2.5583% and 2.3869% respectively.The quantitative model of LS-SVR can achieve better results with higher accuracy and better stability.This study provides a new fast and effective method for quantitative detection of MBT.
引文
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[14]XU F.Research on terahertz spectrum used to detect different rubber materials[J].Modern Electronics Technique,2016,39(8):135-137(in Chinese).
[15]YANG L,GAO M T.Experimental study about measurement of optical parameters of biological tissue based on least square support vector machine[J].Laser Technology,2015,39(3):300-303(in Chinese).
[16]LI Y J,TANG X J,LIU J H.Application of least square support vector machine based on particle swarm optimization in quantitative analysis of gas mixture[J].Spectroscopy and Spectral Analysis,2010,30(3):774-778(in Chinese).
[17]ZHANG Y Q,DONG W,ZHANG B,et al.Research on detection method of adulterated olive oil by raman spectroscopy and least squares support vector machine[J].Spectroscopy and Spectral Analysis,2012,32(6):1554-1558(in Chinese).
[18]CHEN T.Qualitative and quantitative detection of materials based on terahertz time-domain spectroscopy[D].Xi’an:Xidian University,2013:24-27(in Chinese).
[19]HUA Y F.Qualitative and quantitative detection of pesticides by terahertz time-domain spectroscopy[D].Hangzhou:Zhejiang University,2010:69-75(in Chinese).
[20]LI B,LONG Y,LIU H Sh,et al.The determination of glucose based on terahertz spectroscopy[J].Spectroscopy and Spectral Analysis,2017,37(7):2165-2170(in Chinese).
[2]LI H B.Application of pyrolysis gas chromatography in rubber fertilizer quality management[J].China Rubber/Plastics Technology and E-quipment,2016,42(6):60-61(in Chinese).
[3]LI Y,SUN X Y,LI Ch F,et al.Determination of 2-mercaptoimidazoline in rubber products containing chlorine by gas chromatography[J].Chinese Journal of Analysis Laboratory,2011,30(10):27-30(in Chinese).
[4]YIN M.Research on the authentication and adulteration detection of the edible oil by broadband terahertz spectroscopy and chemometrics[D].Xuzhou:China University of Mining and Technology,2017:5-6(in Chinese).
[5]ZHAO B Q,WEI X L,YANG Zh G,et al.Terahertz nondestructive inspection of heat shield[J].Laser Technology,2015,39(2):185-189(in Chinese).
[6]ZHOU Y,WANG T Y,LI W J,et al.Design of visualization systems for terahertz non destructive testing[J].Laser Technology,2017,41(3):351-355(in Chinese).
[7]QIN B Y,LI Zh,LUO Zh H,et al.Terahertz time-domain spectroscopy combined with PCA-CFSFDP applied for pesticide detection[J].Optical and Quantum Electronics,2017,49(7):244-256.
[8]ZHAO G Zh,SHEN Y Ch,LIU Y.Application of terahertz technology in military and security field[J].Journal of Electronic Measurement and Instrumentation,2015,29(8):1097-1101(in Chinese).
[9]ZHANG W T,WANG S Y,ZHAN P P,et al.Method of identifying red wood based on terahertz time-domain spectroscopy[J].Acta Optica Sinica,2017,37(2):0230006(in Chinese).
[10]HUA Y F,ZHANG H J,ZHOU H L.Quantitative determination of cyfluthrin in n-hexane by terahertz time-domain spectroscopy with chemometrics methods[J].IEEE Transactions on Instrumentation and Measurement,2010,59(5):1414-1423.
[11]CHEN T,LI Zh,MO W,et al.Simultaneous quantitative determination of multicomponents in tablets based on terahertz time-domain spectroscopy[J].Spectroscopy and Spectral Analysis,2013,33(5):1220-1225(in Chinese).
[12]HIRAKWA Y,OHNO Y,GONDOH T,et al.Nondestructive evaluation of rubber compounds by terahertz time-domain spectroscopy[J].Journal of Infrared,Millimeter and Terahertz Waves,2011,32(12):1457-1463.
[13]IZUTSU T,KOMATSU M,OHKI Y,et al.Estimation of talc contents in ethylene-propylene-diene copolymer by terahertz absorption spectroscopy[J].IEEJ Transactions on Fundamentals and Materials,2016,136(2):81-85.
[14]XU F.Research on terahertz spectrum used to detect different rubber materials[J].Modern Electronics Technique,2016,39(8):135-137(in Chinese).
[15]YANG L,GAO M T.Experimental study about measurement of optical parameters of biological tissue based on least square support vector machine[J].Laser Technology,2015,39(3):300-303(in Chinese).
[16]LI Y J,TANG X J,LIU J H.Application of least square support vector machine based on particle swarm optimization in quantitative analysis of gas mixture[J].Spectroscopy and Spectral Analysis,2010,30(3):774-778(in Chinese).
[17]ZHANG Y Q,DONG W,ZHANG B,et al.Research on detection method of adulterated olive oil by raman spectroscopy and least squares support vector machine[J].Spectroscopy and Spectral Analysis,2012,32(6):1554-1558(in Chinese).
[18]CHEN T.Qualitative and quantitative detection of materials based on terahertz time-domain spectroscopy[D].Xi’an:Xidian University,2013:24-27(in Chinese).
[19]HUA Y F.Qualitative and quantitative detection of pesticides by terahertz time-domain spectroscopy[D].Hangzhou:Zhejiang University,2010:69-75(in Chinese).
[20]LI B,LONG Y,LIU H Sh,et al.The determination of glucose based on terahertz spectroscopy[J].Spectroscopy and Spectral Analysis,2017,37(7):2165-2170(in Chinese).