便携式激光诱导击穿光谱最新研究进展
doi: 10.37188/CO.2020-0093
Research progress on portable laser-induced breakdown spectroscopy
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摘要: 作为一种新型快速的物质成分分析技术,激光诱导击穿光谱(Laser-Induced Breakdown Spectroscopy, LIBS)已经在越来越多的工业领域中被证明具有巨大的应用潜力。然而,由于野外作业或工业现场检测环境嘈杂恶劣,对仪器设备的尺寸和抗恶劣环境的能力提出了更高的要求。近年来,新型激光器的发展进一步促进了LIBS仪器化的进程,使得其逐渐从实验室迈向工业应用,同时也使得LIBS系统逐渐趋于仪器化、专业化、便携化。本文综述了便携式LIBS的发展历程,对各种激光光源(小型Nd:YAG固体激光器、二极管泵浦固体激光器、微片激光器、光纤激光器以及光纤传能的方案)应用于便携式LIBS系统的最新研究进展进行了综述和分类讨论,探讨了当前便携式LIBS存在的基本问题,并对其未来发展趋势进行了展望。
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关键词:
- 激光诱导击穿光谱 /
- 便携式 /
- 激光器 /
- 元素检测
Abstract:As a new rapid element analysis technique, Laser-Induced Breakdown Spectroscopy (LIBS) has proven iteself to have great potential for applications in increasingly numerous industrial fields. However, due to harsh outdoor and industrial environments, newer and higher requirements are being demanded of the LIBS system, such as the size of its instruments and the ability to resist a harsh environment. The rapid development of new laser technology promotes instrumentation for LIBS, allowing it to gradually step outside the laboratory and into the industry, and allows the LIBS system to gradually move towards instrumentation, miniaturization and portability.In this paper, the development of a portable LIBS that was developed in recent years was reviewed. The application and latest research progress of different kinds of laser source (small lamp pumped solid-state laser, diode pump solid-state laser and micro laser, fiber laser) applied to the portable LIBS system were summarized and discussed, providing insight into both the fiber optic LIBS (FO-LIBS) and the handheld LIBS. In addition, the basic problems of current portable LIBS and the prospects of its future were proposed and discussed.-
Key words:
- laser-induced breakdown spectroscopy /
- portable /
- laser /
- element detection
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图 1 激光诱导击穿光谱系统原理图
Figure 1. Principle diagram of LIBS system
图 2 世界上第一台便携式LIBS系统(Nd:YAG, 1064 nm, 15~20 mJ/pulse, 4~8 ns)[ 19]
Figure 2. The first portable LIBS system in the world (Nd:YAG, 1064 nm, 15~20 mJ/pulse, 4~8 ns)[ 19]
图 3 Laserna等人研发的两种便携式LIBS设备:(a)箱式(Nd: YAG, 1064 nm, 50 mJ/pulse, 6.5 ns)[ 26], (b)背包式 (Nd: YAG, 1064 nm, 50 mJ/pulse, 10 ns)[ 27]
Figure 3. Two types of portable LIBS equipment developed by Laserna et al. : (a) a box type (Nd: YAG, 1064 nm, 50 mJ/pulse, 6.5 ns)[ 26], (b) a backpack type (Nd: YAG, 1064 nm, 50 mJ/pulse, 10 ns)[ 27]
图 4 SECOPTA公司生产的FiberLIBS(总体积:44.9 cm×52 cm×17.7 cm,探测头:35.5 cm×16.5 cm×10 cm, 1 kg)[ 42]
Figure 4. FiberLIBS produced by SECOPTA (total volume: 44.9 cm×52 cm×17.7 cm, probe head: 35.5 cm×16.5 cm×10 cm, 1 kg)[ 42]
图 5 华中科技大学曾晓雁、李祥友等人研制的便携式LIBS样机[ 48]
Figure 5. The portable LIBS system prototype developed by Xiaoyan Zeng and Xiangyou Li et al. in Huazhong University of Science and Technology[ 48]
图 6 光纤激光器实物图
Figure 6. Picture of fiber laser
图 7 Gravel等人采用光纤激光器和紧凑型光谱仪搭建的LIBS系统[ 52]
Figure 7. The LIBS system developed by Gravel et al. using a fiber laser and a compact spectrometer[ 52]
图 8 德国Noll等人开发的移动式LIBS系统[ 53]
Figure 8. The mobile LIBS system developed by Noll et al. in Germany[ 53]
图 9 华中科技大学曾庆栋、李祥友等人采用光纤激光器搭建的便携式LIBS系统[ 54- 55]
Figure 9. The portable LIBS system using a fiber laser developed by Qingdong Zeng and Xiangyou Li et al. in Huazhong University of Science and Technology[ 54- 55]
图 10 Whitehouse等人设计的FO-LIBS原理图[ 58]
Figure 10. Schematic of FO-LIBS developed by Whitehouse et al.[ 58]
图 11 华中科技大学曾庆栋、李祥友等人研制的光纤传能移动式LIBS[ 18, 61]
Figure 11. The mobile LIBS developed by Qingdong Zeng and Xiangyou Li et al. in Huazhong University of Science and Technology[ 18, 61]
图 12 英国牛津mPulse手持式LIBS合金分析仪[ 63]
Figure 12. The mPulse handheld LIBS alloy analyzer, Oxford, UK[ 63]
图 13 美国Rigaku公司研发的型号为KT-100S的手持式LIBS分析仪[ 64]
Figure 13. KT-100S handheld LIBS analyzer from Rigaku, USA[ 64]
图 14 四川大学段忆翔教授等人研发的手持式LIBS[ 65]
Figure 14. The handheld LIBS developed by Yixiang Duan et al. in Sichuan University[ 65]
图 15 必达泰克公司的手持式μ-LIBS分析仪[ 67]
Figure 15. The handheld μ-LIBS instrument of B&W Tek, Inc.[ 67]
表 1 基于DPSS激光器、光纤激光器和光纤传能的便携式LIBS的比较
Table 1. The comparison of several kinds of LIBS systems based on a DPSS laser, a fiber laser and FO-LIBS
激光器 优点 缺点 分析性能 适用领域 DPSS激光器 工作寿命长、功耗低、
自然冷却、小巧便携能量较低、谱线波动性较大 生铁中Mn、V、Ti和Cr元素的LOD分别为171 μg/g、128 μg/g、99 μg/g和
59 μg/g,R2分别为0.994、0.996、
0.994和0.991[ 2]手持式野外测量、电池
供电、原位测量光纤激光器 抗恶劣环境、体积小、
价格便宜连续背景干扰、烧蚀坑深,
破坏性较大铝基中Mg的LOD为1.1 μg/g,R2=0.994;黄铜中Ni的LOD为21.3 ug/g,R2=0.997[ 52];生铁中的Mn、V,Si的LOD分别为195 μg/g、48 μg/g和110 μg/g, R2分别为0.997、0.991和0.992[ 54] 工厂、矿山等恶劣工作
环境,在线测量光纤传能 避免复杂光路系统和外界
干扰、降低自吸收效应能量低,LOD较差 生铁中Mn和Ti元素LOD分别为1219 μg/g, 257 μg/g, R2分别为0.997, 0.998[ 61] 在线、原位测量,
移动式测量表 2 几种手持式LIBS的参数比较
Table 2. Parameters of several handheld LIBS
型号 研发单位 激光光源 体积、重量 参数及性能 LEA Handheld LIBS[ 62] 芬兰Lasersec Systems公司 DPSS激光器 22.6 cm×9 cm×29 cm,
1.75 kg平均功率0.5 W,光谱范围220~400 nm,续航2 h,LOD可达到μg/g级,可用于爆炸物、金属、食品与药品分类。 MPulse[ 63] 英国牛津公司 准连续固体调Q激光器 9 cm×23 cm×21 cm,
1.8 kg频率4 kHz,峰值功率小于0.5 W,电池支持250次测试,可用于合金鉴别与金属分拣。 高能手持式LIBS[ 65] 四川大学 被动调Q的Nd: YAG
激光器33 cm×11 cm×32 cm,
2.95 kg单脉冲能量达100 mJ,光谱范围220~397 nm,可元素定量测定,岩屑岩性识别等。 KT-100S[ 64] 美国Rigaku公司 波长1064 nm的3B级
激光器24.3 cm×8.4 cm×25.7 cm,
1.5 kg光谱范围200~480 nm,分辨率小于0.2 nm,电池供电10 h,可用于样品分类。 ChemLite[ 66] 美国TSI公司 波长1574 nm的人眼安全激光器 30.5 cm×25.4 cm×10.2 cm,
2.4 kg1574 nm人眼安全波长,光谱范围200~700 nm,一次充电支持1300次检测,探测范围低至0.01%。 μ-LIBS[ 67] 必达泰克公司 DPSS激光器 27.9 cm×8.9 cm×27.9 cm,
1.8 kg最大输出功率200 mW,脉宽小于1 ns,脉冲频率2 kHz,波长范围185~680 nm,分辨率0.4 nm。 z-200c+手持式LIBS
分析仪[ 68]SciAps公司 波长1064 nm的Nd: YAG激光器 21 cm×30 cm×12 cm,
1.82 kg脉宽1~2 ns,单脉冲能量5.5 mJ,重复频率50 Hz,光谱范围190~620 nm,用于原位分析钢中C含量。 PHP网站源码石岩百姓网标王永湖网络广告推广民治外贸网站制作沙井关键词排名包年推广坑梓标王大运网站建设东莞网络广告推广宝安模板推广布吉网站建设南联seo优化观澜关键词排名大芬阿里店铺托管永湖SEO按天计费石岩网站关键词优化罗湖网站优化按天计费石岩网站优化按天计费木棉湾营销网站丹竹头设计公司网站民治SEO按天收费南澳关键词按天收费民治关键词排名塘坑百度竞价包年推广惠州模板网站建设南山百度标王宝安网页设计坪山SEO按天计费福永SEO按天扣费大运网站建设宝安网站seo优化深圳关键词排名歼20紧急升空逼退外机英媒称团队夜以继日筹划王妃复出草木蔓发 春山在望成都发生巨响 当地回应60岁老人炒菠菜未焯水致肾病恶化男子涉嫌走私被判11年却一天牢没坐劳斯莱斯右转逼停直行车网传落水者说“没让你救”系谣言广东通报13岁男孩性侵女童不予立案贵州小伙回应在美国卖三蹦子火了淀粉肠小王子日销售额涨超10倍有个姐真把千机伞做出来了近3万元金手镯仅含足金十克呼北高速交通事故已致14人死亡杨洋拄拐现身医院国产伟哥去年销售近13亿男子给前妻转账 现任妻子起诉要回新基金只募集到26元还是员工自购男孩疑遭霸凌 家长讨说法被踢出群充个话费竟沦为间接洗钱工具新的一天从800个哈欠开始单亲妈妈陷入热恋 14岁儿子报警#春分立蛋大挑战#中国投资客涌入日本东京买房两大学生合买彩票中奖一人不认账新加坡主帅:唯一目标击败中国队月嫂回应掌掴婴儿是在赶虫子19岁小伙救下5人后溺亡 多方发声清明节放假3天调休1天张家界的山上“长”满了韩国人?开封王婆为何火了主播靠辱骂母亲走红被批捕封号代拍被何赛飞拿着魔杖追着打阿根廷将发行1万与2万面值的纸币库克现身上海为江西彩礼“减负”的“试婚人”因自嘲式简历走红的教授更新简介殡仪馆花卉高于市场价3倍还重复用网友称在豆瓣酱里吃出老鼠头315晚会后胖东来又人满为患了网友建议重庆地铁不准乘客携带菜筐特朗普谈“凯特王妃P图照”罗斯否认插足凯特王妃婚姻青海通报栏杆断裂小学生跌落住进ICU恒大被罚41.75亿到底怎么缴湖南一县政协主席疑涉刑案被控制茶百道就改标签日期致歉王树国3次鞠躬告别西交大师生张立群任西安交通大学校长杨倩无缘巴黎奥运
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