激光诱导离解光谱技术及其宝石学应用
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摘要
激光诱导离解光谱(LIBS)为一新兴的化学成分测试技术,它因无需提前制备样品、快速简便、灵敏度高且破坏性小等优势在许多领域引起重视并得到了迅速的发展。LIBS应用于宝石学研究起源于对于Be扩散处理红、蓝宝石的鉴定。这种扩散处理宝石具较少的常规鉴别特征,只能通过化学成分分析对Be的检测予以确认。LIBS对Be具较好的灵敏度且可保证近似无损,而与其它同样具备这两种条件的LA-ICP-MS、SIMS等测试技术相比,LIBS测试简单、体积小而且价格低,具有独特的优势。当然,作为一种成分分析技术,其在宝石学的应用应不单单限于检测Be扩散处理红、蓝宝石,但是目前对于LIBS在宝石学其他方面的应用研究较少。因此本文在珠宝学院自行搭建的LIBS系统的基础上从设备、软件及定量等几个方面进行了研究,试图建立一个适合于宝石学应用的较完整的LIBS测试分析系统。并对其在宝石学应用的几个方面进行了实践和探讨。
本文首先对前人的研究工作进行了总结,简要介绍了目前在仪器设备、分析软件、定量方法及应用等几个方面LIBS的研究情况,以及现有的LIBS应用于宝石学的一些研究。
其次介绍了激光诱导离解光谱的基本原理及本文的LIBS装置,并对在实践经验的基础上对其进行了改进,主要有:采用了在光纤前增加透镜方式增强了采集谱线的强度;装备了Ar气以降低其检测限;改善了准焦系统。随后研究了现有LIBS系统的稳定性,主要是激光能量的波动的影响。用无色透明的CZ作为标样,以保证避免样品成分不均匀性的影响。实验得出激光能量波动对仪器精度的影响较大,而采取多次测试取平均的方法可以大大降低其影响。但同时也提出此种方法可能会增大对于宝石样品的损耗。大概分析了本文中LIBS系统的检测限。
针对现有测试分析软件的缺陷进行了LIBS软件的开发。使用VC++6.0开发环境及Access数据库,基本实现了与适用于本文中LIBS设备的测试分析软件系统。其功能主要分为光谱测试、光谱处理及数据库三大部分。光谱测试功能使用动态链接库重现了光谱仪自带测试软件的功能,光谱处理及数据库功能则为笔者自己设计和开发。光谱处理主要包括寻峰、基线校正、自动谱线分析、谱线扩展、光谱存储等功能。其中自动谱线分析功能提供了一种较为智能化的分析过程,实现了测试光谱中所有种类元素的快速标注。数据库功能则为快速鉴别样品种类提供了方便,它支持用户建立和管理自己的标准光谱库,并可对未知的光谱进行查询匹配。同时笔者也建立了存储有70余个光谱的宝石、矿物光谱数据库。需指出的是,虽然软件是针对本文中LIBS设备开发而成,但是其光谱处理及数据库这两大类功能适用于所有的激光诱导离解光谱,并可为激光诱导离解光谱技术的软件研究提供一些借鉴。
使用本文初步实现的LIBS系统,进行了初步的宝石学方面的定量分析研究。总结了目前LIBS定量分析的三种主要模型:外标法、内标法及自由定标法。并介绍了一种优化的外标法。对翡翠、黑耀岩等宝石矿物和不同纯度的黄金样品进行了不同方法的定量分析实验,结果认为对于黄金等容易制备标样的贵金属样品,最好采用准确度较好的传统定标方法,而对于成分复杂的矿物样品,由于其具明显的基体效应,不适合使用传统方法进行分析。而自由定标法对于矿物的定量分析结果准确度也不理想。在对几个方法进行实践比较后认为,将等离子体模型与传统定标方法结合的优化的外标法在宝石矿物分析中展现了比以上几种方法都要好的效果。
对于LIBS在宝石学的应用进行了实践和探讨。主要涉及的方面有:检测Be扩散红、蓝宝石;检测充胶处理翡翠;区分淡水珍珠及海水珍珠;检测过渡族金属元素;快速鉴别宝石种;产地鉴别及贵金属纯度分析。从这几个方面的初步研究展示了LIBS应用于宝石学研究的潜力。在实践基础上总结了LIBS应用于宝石学的注意事项及测试时应注意的问题。
最后对本文的研究内容进行了探讨和总结,并指出了需进一步研究的问题,明确了以后的研究方向。
Laser-Induced Breakdown Spectroscopy - which we call it LIBS,is a new developed technology for chemical elements analyses.It has several important advantages such as no need to prepare samples,easy operation,and high sensitivity.So there have many researches on it and make a rapid development.The first used for LIBS to Gemmology is to identify the Be-diffused corundum,which is a kind of new diffuse method and is hard to identify by usual test.There are three method be found to identify the Be-diffused corundum,which are LA-ICP-MS,SIMS,and LIBS.Compare whit the former two technologies,LIBS has a simpler setup and lower price. Also,to identify Be-diffused corundum is not the only use of LIBS for Gemmology,but because of the late appearance there is no many research about this now.This article is mainly about the research of our LIBS system and its application to Gemmology.
The first part of this article is summarizing the current research about LIBS,from the aspects of setup,analyses software,quantitative methods and the application.Also have some introductions about the application research for gemology.
The second part is about our LIBS system.After explaining the fundamental theory of laser-induced breakdown spectroscopy,we mainly introduced our LIBS setup:the equipments and the abilities.There are some improvements for this system,such as the environment gas,the spectrum collection mode and so on.Also the stability research is done,and from the result we can found that laser is the main influence to the apparatus precision.The method to avoid this influence is putted up,which is taking the average of many tests at the same place.But this method would increase the damage and seemed not good for gemstone test.Detect limit of this LIBS system is also computed in this part.
The third part of this thesis is the development of LIBS software.The development environment is visual C++ 6.0,and uses the Microsoft Access database.The software have three parts of functions,there are spectrum measure,spectrum analysis and the spectrum database.The first function is based on the DLL file,recurs all the measure fictions which the spectrometer's own software have.The second and the third functions are wrote and designed by ourselves. Spectrum analysis contains many functions,which are peak-seeking,baseline correction, auto-elements analyses,spectrum extending,and so on.Spectrum database allow user set up their sample spectrum database,and by the spectrum match function,user can identify the type of the sample quickly.We also set up ourselves gemstone database,which contains more than seventy spectrums of gemstones,minerals and noble metals.Also the spectrum analysis and the spectrum database function can be used to all the laser-induced breakdown spectroscopy.
The fourth party uses the above LIBS system to quantitative analyze some gemstones and the gold alloy.There are three quantitative models be used,the traditional quantitative method, calibration free LIBS method and external standard normalization method.Compared the three method,we can find that the quantitative analysis for gold alloy can use the traditional quantitative method and for the rocks the external standard normalization method seemed can achieve a better accuracy than other two methods.
The fifth part takes many practices to the LIBS use for Gemmology and concludes seven aspects of the potential use for Gemmology research.LIBS can be used to identify the Be-diffused corundum,identify the glue-filled jadeite,distinguish the sea water pearl and the fresh water pearl,measure the transition metal elements,identify the type of stones quickly, identify the origin of the gemstones and analysis the purity of the noble metal.Form above practices,we summarize some notice for the LIBS use to Gemmology.
At the end of this article,we discuss and sum up the all researches above,and make a clearly and definitely goal for the further study.
本文首先对前人的研究工作进行了总结,简要介绍了目前在仪器设备、分析软件、定量方法及应用等几个方面LIBS的研究情况,以及现有的LIBS应用于宝石学的一些研究。
其次介绍了激光诱导离解光谱的基本原理及本文的LIBS装置,并对在实践经验的基础上对其进行了改进,主要有:采用了在光纤前增加透镜方式增强了采集谱线的强度;装备了Ar气以降低其检测限;改善了准焦系统。随后研究了现有LIBS系统的稳定性,主要是激光能量的波动的影响。用无色透明的CZ作为标样,以保证避免样品成分不均匀性的影响。实验得出激光能量波动对仪器精度的影响较大,而采取多次测试取平均的方法可以大大降低其影响。但同时也提出此种方法可能会增大对于宝石样品的损耗。大概分析了本文中LIBS系统的检测限。
针对现有测试分析软件的缺陷进行了LIBS软件的开发。使用VC++6.0开发环境及Access数据库,基本实现了与适用于本文中LIBS设备的测试分析软件系统。其功能主要分为光谱测试、光谱处理及数据库三大部分。光谱测试功能使用动态链接库重现了光谱仪自带测试软件的功能,光谱处理及数据库功能则为笔者自己设计和开发。光谱处理主要包括寻峰、基线校正、自动谱线分析、谱线扩展、光谱存储等功能。其中自动谱线分析功能提供了一种较为智能化的分析过程,实现了测试光谱中所有种类元素的快速标注。数据库功能则为快速鉴别样品种类提供了方便,它支持用户建立和管理自己的标准光谱库,并可对未知的光谱进行查询匹配。同时笔者也建立了存储有70余个光谱的宝石、矿物光谱数据库。需指出的是,虽然软件是针对本文中LIBS设备开发而成,但是其光谱处理及数据库这两大类功能适用于所有的激光诱导离解光谱,并可为激光诱导离解光谱技术的软件研究提供一些借鉴。
使用本文初步实现的LIBS系统,进行了初步的宝石学方面的定量分析研究。总结了目前LIBS定量分析的三种主要模型:外标法、内标法及自由定标法。并介绍了一种优化的外标法。对翡翠、黑耀岩等宝石矿物和不同纯度的黄金样品进行了不同方法的定量分析实验,结果认为对于黄金等容易制备标样的贵金属样品,最好采用准确度较好的传统定标方法,而对于成分复杂的矿物样品,由于其具明显的基体效应,不适合使用传统方法进行分析。而自由定标法对于矿物的定量分析结果准确度也不理想。在对几个方法进行实践比较后认为,将等离子体模型与传统定标方法结合的优化的外标法在宝石矿物分析中展现了比以上几种方法都要好的效果。
对于LIBS在宝石学的应用进行了实践和探讨。主要涉及的方面有:检测Be扩散红、蓝宝石;检测充胶处理翡翠;区分淡水珍珠及海水珍珠;检测过渡族金属元素;快速鉴别宝石种;产地鉴别及贵金属纯度分析。从这几个方面的初步研究展示了LIBS应用于宝石学研究的潜力。在实践基础上总结了LIBS应用于宝石学的注意事项及测试时应注意的问题。
最后对本文的研究内容进行了探讨和总结,并指出了需进一步研究的问题,明确了以后的研究方向。
Laser-Induced Breakdown Spectroscopy - which we call it LIBS,is a new developed technology for chemical elements analyses.It has several important advantages such as no need to prepare samples,easy operation,and high sensitivity.So there have many researches on it and make a rapid development.The first used for LIBS to Gemmology is to identify the Be-diffused corundum,which is a kind of new diffuse method and is hard to identify by usual test.There are three method be found to identify the Be-diffused corundum,which are LA-ICP-MS,SIMS,and LIBS.Compare whit the former two technologies,LIBS has a simpler setup and lower price. Also,to identify Be-diffused corundum is not the only use of LIBS for Gemmology,but because of the late appearance there is no many research about this now.This article is mainly about the research of our LIBS system and its application to Gemmology.
The first part of this article is summarizing the current research about LIBS,from the aspects of setup,analyses software,quantitative methods and the application.Also have some introductions about the application research for gemology.
The second part is about our LIBS system.After explaining the fundamental theory of laser-induced breakdown spectroscopy,we mainly introduced our LIBS setup:the equipments and the abilities.There are some improvements for this system,such as the environment gas,the spectrum collection mode and so on.Also the stability research is done,and from the result we can found that laser is the main influence to the apparatus precision.The method to avoid this influence is putted up,which is taking the average of many tests at the same place.But this method would increase the damage and seemed not good for gemstone test.Detect limit of this LIBS system is also computed in this part.
The third part of this thesis is the development of LIBS software.The development environment is visual C++ 6.0,and uses the Microsoft Access database.The software have three parts of functions,there are spectrum measure,spectrum analysis and the spectrum database.The first function is based on the DLL file,recurs all the measure fictions which the spectrometer's own software have.The second and the third functions are wrote and designed by ourselves. Spectrum analysis contains many functions,which are peak-seeking,baseline correction, auto-elements analyses,spectrum extending,and so on.Spectrum database allow user set up their sample spectrum database,and by the spectrum match function,user can identify the type of the sample quickly.We also set up ourselves gemstone database,which contains more than seventy spectrums of gemstones,minerals and noble metals.Also the spectrum analysis and the spectrum database function can be used to all the laser-induced breakdown spectroscopy.
The fourth party uses the above LIBS system to quantitative analyze some gemstones and the gold alloy.There are three quantitative models be used,the traditional quantitative method, calibration free LIBS method and external standard normalization method.Compared the three method,we can find that the quantitative analysis for gold alloy can use the traditional quantitative method and for the rocks the external standard normalization method seemed can achieve a better accuracy than other two methods.
The fifth part takes many practices to the LIBS use for Gemmology and concludes seven aspects of the potential use for Gemmology research.LIBS can be used to identify the Be-diffused corundum,identify the glue-filled jadeite,distinguish the sea water pearl and the fresh water pearl,measure the transition metal elements,identify the type of stones quickly, identify the origin of the gemstones and analysis the purity of the noble metal.Form above practices,we summarize some notice for the LIBS use to Gemmology.
At the end of this article,we discuss and sum up the all researches above,and make a clearly and definitely goal for the further study.
引文
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