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双波长近红外拉曼光谱仪及在腐蚀产物分析中的应用

Double-Wavelength NIR Raman Spectroscopy and the Application on Corrosion Products

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在拉曼光谱测试中某些物质存在荧光发射背景,由于荧光强度一般比拉曼散射强度高几个数量级,在荧光干扰时几乎无法获得有效的拉曼光谱信号.为抑制荧光背景,可选用近红外波段激光作为激发光源,而硅基探测器在1 000 nm以上波段时光量子效率严重下降,导致近红外拉曼光谱仪器难以探测3 000 cm-1以上的波段,存在荧光抑制效果与检测范围无法兼顾的问题.由于高波数的拉曼特征峰是识别材料种类和解析材料结构的重要依据,如氨基的N—H伸缩振动峰在3 300 cm-1附近、OH-伸缩振动峰在3 650 cm-1,这些基团是分析材料腐蚀产物、水合物、有机物等的重要依据.因此,迫切需要开发一种解决拉曼光谱仪器无法兼顾荧光抑制效果和检测光谱范围问题的方法.该工作提出一种采用光谱仪固定检测波段、730和830 nm双波长激光"接力"激发的方案(即830 nm激发低波数拉曼、730 nm激发高波数拉曼).通过双激光波长"接力"激发、固定检测波段的新设计,可有效拓宽检测范围至200~3 700 cm-1,并且不会降低光谱分辨率(达到6 cm-1),与此同时整机光路无机械可动部件,可靠性高便于实现便携式设计.通过样机进行测试,证明该技术方案具备高灵敏度、较好荧光抑制效果、宽检测范围和较高光谱分辨率等优势.通过研制的双波长近红外拉曼光谱仪获得了铀腐蚀产物、有机涂层下的LiH潮解产物的清晰拉曼信号,解决了特种材料无损检测的技术难题.该技术也适用于其他研究及检测领域,特别是拉曼散射截面小、荧光背景高的物质检测.由于双波长近红外拉曼光谱仪可覆盖200~3 700 cm-1检测范围,为多数水合物、含羟基及氨基官能团物质的拉曼检测提供了一种可行的技术途径.
In Raman spectroscopy tests,some substances have a fluorescence emission background.Since the fluorescence intensity is generally orders of magnitude higher than the Raman scattering intensity,it is almost impossible to obtain an effective Raman spectroscopy signal during fluorescence interference.In order to suppress the fluorescence background,a near-infrared band laser can be used as the excitation light source,but the quantum efficiency of silicon-based detectors in the band above 1 000 nm is seriously reduced,resulting in the difficulty of near-infrared Raman spectroscopy instruments to detect the band above 3 000 cm-1,that is,there is a problem that the fluorescence suppression effect and detection range cannot be balanced.Since the Raman characteristic peaksat high wavenumber are important for identifying material types and analyzing material structures,such as the N—H telescopic vibration peak of the amino group around 3 300 cm-1 and OH-telescopic vibration peak at 3 650 cm-1.These groups are important for analyzing material corrosion products,hydrates,organic matter,etc.Therefore,a method is urgently needed to solve the problem that the fluorescence suppression effect and detection range cannot be balanced for Raman spectroscopy instruments.In this work,this project proposes a scheme using a spectrometer with fixed detection wavelength,730 and 830 nm dual wavelength laser"relay"excitation(i.e.830 nm excitation of the Raman peaks with low wavenumber,730 nm excitation the Raman peaks with high wavenumber),which can extend the detection range to 200~3 700 cm-1 without reducing the spectral resolution(up to 6 cm-1).At the same time,the whole machine optical path has no mechanical moving parts,and the high reliability is convenient to realize the portable design.The prototype test proved that the technical scheme has the advantages of high sensitivity,good fluorescence suppression effect,wide detection range and high spectral resolution.Through the dual-wavelength near-infrared Raman spectrometer,the clear Raman signal of uranium corrosion products and LiH deliquescence products under organic coating was obtained,which solved the technical problems of non-destructive testing of special materials.This technique is also suitable for other research and testing areas,especially substances with small Raman scattering cross-sections and high fluorescence backgrounds.Since the dual-wavelength NIR Raman spectrometer can cover the detection range of 200~3 700 cm-1,it provides a feasible technical approach for the Raman detection of most hydrate,hydroxyl and amino functional substances.

Fluorescence suppressionHigh wave-numberNon-destroyable detectionPortable RamanDual wavelength excitation in-field detection

王茂成、李赣、程浩、姜维、陈广、李海波

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中国工程物理研究院材料研究所表面物理化学重点实验室,四川绵阳 621908

中国工程物理研究院材料研究所,四川绵阳 621907

荧光抑制 高波数 无损检测 便携式拉曼光谱仪 双波长激发

国家自然科学基金面上项目中国工程物理研究院院长基金自强项目

22073084YZJJZQ2022012

2024

光谱学与光谱分析
中国光学学会

光谱学与光谱分析

CSTPCD北大核心
影响因子:0.897
ISSN:1000-0593
年,卷(期):2024.44(3)
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