Ultraviolet laser filaments for remote laser-induced breakdown spectroscopy (LIBS) analysis: applications in cultural heritage monitoring

We report experiments with subpicosecond UV laser filaments for the remote analysis of samples related to objects of cultural heritage. The classic laser-induced breakdown spectroscopy (LIBS) technique finds new avenues through femtosecond filamentation, and dynamic remote LIBS becomes possible. Advantages such as self-regulated laser intensity deposition on the target suggest that there is significant potential for using UV femtosecond filaments for the remote analysis of sculpture and large monuments.     

Large variation in Young's modulus of carbon nanotube yarns with different diameters

Twist-spun carbon nanotube (CNT) yarns are composed of numerous CNTs and their bundles with entangled and twisted structures. In this paper, we studied the mechanical properties of CNT yarns. The individual CNT, a component of yarn, is well known to have an extremely high mechanical strength. However, CNT yarns are very flexible and relatively free to transform their shapes, showing the potential for application in the design of wearable devices. Since CNT yarns have two opposing characteristics at the same time, a wide range of Young's modulus can be achieved by simply changing the geometrical structure while using the same fabrication process. We also suggest that CNT yarns can be utilized as the base material for several applications that require different stresses in a structure, such as bioimplants or foldable devices.     

A novel continuous process for synthesis of carbon nanotubes using iron floating catalyst and MgO particles for CVD of methane in a fluidized bed reactor

A novel continuous process is used for production of carbon nanotubes (CNTs) by catalytic chemical vapor deposition (CVD) of methane on iron floating catalyst in situ deposited on MgO in a fluidized bed reactor. In the hot zone of the reactor, sublimed ferrocene vapors were contacted with MgO powder fluidized by methane feed to produce Fe/MgO catalyst in situ. An annular tube was used to enhance the ferrocene and MgO contacting efficiency. Multi-wall as well as single-wall CNTs was grown on the Fe/MgO catalyst while falling down the reactor. The CNTs were continuously collected at the bottom of the reactor, only when MgO powder was used. The annular tube enhanced the contacting efficiency and improved both the quality and quantity of CNTs.The SEM and TEM micrographs of the products reveal that the CNTs are mostly entangled bundles with diameters of about 10-20 nm. Raman spectra show that the CNTs have low amount of amorphous/defected carbon with I_G/I_D ratios as high as 10.2 for synthesis at 900 °C. The RBM Raman peaks indicate formation of single-walled carbon nanotubes (SWNTs) of 1.0-1.2 nm diameter.     

基于激光诱导击穿光谱技术的土壤泥浆中Pb元素检测

激光诱导击穿光谱(LIBS)作为一种新兴的元素分析技术,具有实时在线、非接触、多元素同时探测等渚多优点.将LIBS技术引入土壤泥浆重金属污染的检测分析,力图发展一种针对泥浆重金属污染监测的原位传感技术.实验选择Pb作为探测元素,Mn为内标元素;采用重复频率10 Hz的Nd:YAG调Q激光器的二倍频(532 nm)输出作为激发光源,OCD收集信号,对实验室配制的不同浓度Pb泥浆样品的LIBS信号进行了探测分析.获得了各种浓度下Pb泥浆样品在Pb 405.78 nm和Mn 403.07 nm处的原子线强度比IPb/IMn及其随浓度变化的规律.结果显示IPb/IMn与样品的含铅浓度有着很好的线性关系,线性拟合相关系数R2达到0.994 9.初步证实了采用内标法对土壤泥浆中重金属Pb进行LIBS检测分析的可行性.文章还对泥浆重金属LIBS检测的影响因素进行了讨论.     

Particle emissions from laboratory activities involving carbon nanotubes

This site study was conducted in a chemical laboratory to evaluate nanomaterial emissions from 20–30-nm-diameter bundles of single-walled carbon nanotubes (CNTs) during product development activities. Direct-reading instruments were used to monitor the tasks in real time, and airborne particles were collected using various methods to characterize released nanomaterials using electron microscopy and elemental carbon (EC) analyses. CNT clusters and a few high-aspect-ratio particles were identified as being released from some activities. The EC concentration (0.87 μg/m³) at the source of probe sonication was found to be higher than other activities including weighing, mixing, centrifugation, coating, and cutting. Various sampling methods all indicated different levels of CNTs from the activities; however, the sonication process was found to release the highest amounts of CNTs. It can be cautiously concluded that the task of probe sonication possibly released nanomaterials into the laboratory and posed a risk of surface contamination. Based on these results, the sonication of CNT suspension should be covered or conducted inside a ventilated enclosure with proper filtration or a glovebox to minimize the potential of exposure.     

真空环境熔融金属成分检测的激光诱导击穿光谱系统

激光诱导击穿光谱(LIBS)技术是应用于冶金在线分析最具前景的技术之一。为了研究真空和高温条件下LIBS光谱特性和物质成分定量分析方法,设计并搭建了可实现真空环境高温熔融金属LIBS光谱测量的实验系统。系统以调Q Nd: YAG脉冲激光器为光源,采用不同焦距透镜实现激光聚焦和信号光采集,并利用光谱仪进行光谱检测,真空获取和高温加热通过真空泵和中频感应电炉实现,感应加热线圈通过陶瓷封接引线法兰与真空系统进行整合。经过安装测试,搭建系统在未加热情况下真空度可达1×10-4Pa,加热温度可达到1 600 ℃,可实现真空环境下铁、铝等金属加热或熔融,并获得相应环境下的LIBS测量光谱。利用该系统进行真空和熔融条件下标准钢样品的LIBS实验,得到了固态钢样品LIBS光谱在不同真空度下的光谱对比,以及真空环境熔融态和固态钢样品光谱对比。通过对测得的LIBS光谱进行数据处理和理论分析,所得初步实验结果与现有研究结论相符合,表明该系统工作状况良好,可满足真空环境下的熔融金属成分分析研究的基本需求。     

火星车载激光诱导击穿光谱仪(MarsCoDe)在轨定标样品选取研究

我国首次火星全球遥感与区域巡视探测任务已获批立项,首个火星探测器也即将前往火星。为满足火星物质成分分析的需求,我国研制了不同类型的火星物质成分分析仪器,其中包括火星表面成分探测仪（MarsCoDe）,应用了激光诱导击穿光谱技术（laser-induced breakdown spectroscopy,LIBS）。火星表面覆盖尘埃,探测仪器想要准确获取火星尘埃之下的物质成分,必须剥去尘埃或者进行破坏从而深入岩层取样。LIBS可以用激光烧蚀待测物体表面,获得深部物质光谱信息,在火星表面探测中具有其他仪器无法取代的优势。LIBS在火星探测中几乎适用于探测每一个元素,包括轻元素H,Li,Be,B,C,N,O等,帮助寻找有机物和含水地质过程的证据。由于LIBS在火星环境工作,等离子体的物理性质与地球上完全不同。为了确保火星车载LIBS返回数据的光谱质量,需要对LIBS在着陆后开展在轨定标。借助火星车的携带在轨定标样品,对探测数据进行在轨定标,确保返回数据的可靠性。定标样品的选择是一项十分重要的工作,存在仪器工程条件限制、定标样品类型的代表性、元素成分分布范围、样品稳定性等多种考虑因素,需满足科学任务的同时达到加工工艺要求。总结了国外已有的火星车载LIBS在轨定标的研究进展,重点分析了LIBS在轨定标样品选择依据、国外选择样品的优缺点,并总结经验提出了几点建议,为我国在轨定标工作提供参考。对火星探测数据的正确解译,对未来研究火星的起源、火星的长期地质演变过程等具有重要的科学意义。     

Application of laser-induced breakdown spectroscopy in carbon sequestration research and development

The success of carbon capture and storage (CCS) programme relies on the long-term isolation of CO₂ from the atmosphere. Therefore, technologies concomitant to physical storage of CO₂ such as reliable measurement, monitoring, and verification (MMV) techniques are needed to ensure that the integrity of the storage site is maintained. We propose the use of laser-induced breakdown spectroscopy (LIBS) analytical technique to detect carbon dioxide leaks to aid in the successful application of CCS. LIBS has a real-time monitoring capability and can be reliably used for the elemental and isotopic analysis of solid, liquid, and gas samples. The flexibility of probe design and use of fibre optics make it a suitable technique for real time measurements in harsh conditions and at hard-to-reach places. Proposed monitoring with LIBS includes terrestrial soil samples, water samples from monitoring wells or from different formations, air samples from monitoring wells or suspected leakage areas. This work details the laboratory scale experiments to measure carbon contents in rock, soil, aqueous, and air samples. The potential of the technology for measurements in high pressure high-temperature conditions will also be discussed.     

Mixing Si and carbon nanotubes by a method of ball-milling and its application to pyrotechnic delay composition

The original delay composition cannot ensure the reliability and safety of the ammunition under complicated environment, for example low precision of burning rate at high density charge. Carbon nanotubes are added into the delay composition for the first time. Si and CNTs were mixed by the ball-milling method. Particle size analysis showed that particle size exponential declined with increase in milling time. TEM showed that individual nanotubes were dispersed in silicon powder after 48 h of milling, and then they did not appear damaged. Optimum conditions of preparing Si/CNTs were found to be: milling time 48 h, milling intensity 300 rpm, CNTs-to-Si weight ratio=1:10 and ball-to-powder weight ratio=150:1. Then Si/CNTs were applied to fuel agent of delay composition. We studied the burning rate of Pb₃O₄/Si and Pb₃O₄/CNTs/Si delay composition with flaming velocity measurement. Results show that burning rate and delay precision of Pb₃O₄/CNTs/Si delay composition (5.85 mm/s and 1.03%) were higher than the ones of Pb₃O₄/Si delay composition (3.80 mm/s and 3.00%). Especially reliability of ignition is improved when charge density exceeds 6000 Kg/m³. It is proved that certain amount of CNTs added to delay composition can increase delay precision and further doing so achieved less temperature dependence.     

合金钢的激光诱导击穿光谱实验条件优化

利用1 064 nm波长Nd∶YAG脉冲激光诱导击穿合金钢产生激光等离子体光谱,采用高分辨率及门宽控制的ICCD探测LIBS信号光谱。选用铁元素原子谱线404.581,414.387,427.176和438.355 nm进行分析,研究了不同实验参数对LIBS光谱信号强度的影响结果。实验结果表明,激光脉冲能量、激光聚焦位置以及ICCD探测器的延时等实验参数对合金钢LIBS信号有较大影响。通过优化这些实验参数,获得高光谱强度和信背比的LIBS信号,确定了LIBS技术用于合金钢微量元素成分分析的最佳实验条件,从而开展合金钢样品成分分析。     

Aligned carbon nanotube from catalytic chemical vapor deposition technique for energy storage device: a review

Carbon nanomaterial especially carbon nanotube (CNT) possesses remarkably significant achievements towards the development of sustainable energy storage applications. This article reviews aligned CNTs grown from chemical vapor deposition (CVD) technique as electrode material in batteries and electrochemical capacitors. As compared to the entangled CNTs, aligned or well-organized CNTs have advantages in specific surface area and ion accessibility in which more electrolyte ions can access to CNT surfaces for better charge storage performance. CVD known as the most popular technique to produce CNTs enables the use of various substrates and CNT can grow in a variety of forms, such as powder, films, aligned or entangled. Also, CVD is a simple and economic technique, and has good controllability of direction and CNT dimension. High purity of as-grown CNTs is also another beauty of the CVD technique. The current trend and performance of devices utilizing CNTs as electrode material is also extensively discussed.     

激光波长对煤激光诱导击穿光谱特性影响的试验研究

我国电站入炉煤种复杂多变,实时快速获取煤质成分对保障锅炉的安全、高效、低污染运行具有重大意义。将激光诱导击穿光谱(LIBS)技术应用于燃煤煤质测量,观测了不同波长激光(355,532和1 064 nm)诱导产生的等离子体时间演变特性和不同电离特性元素的谱线时间特性,对比了出现屏蔽效应时的能量阈值随激光波长的变化特征,并研究了激光波长对煤LIBS光谱特性的影响规律。结果发现：使用532 nm激光作为激发光源时,煤LIBS光谱具有最强的谱线信号强度,且出现等离子体屏蔽效应的能量阈值也较高,是一种较理想的激发光源,为LIBS技术在煤质测量领域的工业应用提供了实验依据。     

Determination of Chloride Content in Different Types of Cement Using Laser-Induced Breakdown Spectroscopy

The characterization and accurate determination of the chloride content in cement/concrete is very important for the assessment of the durability and safety of a concrete structure. The available analytical techniques are relatively expensive and time consuming. In this study, a laser-induced breakdown spectroscopy (LIBS) system was used for determination of elemental composition in three different types of cement samples. The plasma was generated by focusing a pulsed Nd: YAG laser at 1064 nm on the cement samples. The concentrations of different elements of significance for structural stability in cement samples were determined. The evaluation of the potential and the capabilities of LIBS as a rapid tool for characterization of cement samples is discussed. The optimum LIBS setup and experimental conditions to detect and measure chloride in building materials are reported. The LIBS results were compared with the results obtained using a standard analytical technique such as inductively coupled plasma emission spectroscopy (ICP–ES). The limits of detection were determined, and calibration curves were measured. The results of this investigation indicate the reliability of LIBS to characterize different cement samples and to assess the chloride content in these cements.     

利用激光诱导击穿光谱分析土壤成份

 搭建了一套激光诱导击穿光谱实验装置,并通过配置特定样品,开展了一系列激光诱导击穿光谱探测实验。根据含有不同质量分数的同种元素样品的激光诱导击穿光谱实验结果,获得元素质量分数与谱线强度的关系曲线(定标曲线)。对中南民族大学附近的土壤进行激光诱导击穿光谱实验,发现土壤中含有Mg,Ca,Na等18种元素,对河南云台山茱萸峰岩石的激光诱导击穿光谱实验结果仅获得Fe,Mg,Ca 3种金属元素。比较这2种实际样品的激光诱导击穿光谱结果表明,检测样品的物理结构影响激光诱导光谱的实验结果。     

利用激光诱导击穿光谱分析土壤成份

搭建了一套激光诱导击穿光谱实验装置,并通过配置特定样品,开展了一系列激光诱导击穿光谱探测实验。根据含有不同质量分数的同种元素样品的激光诱导击穿光谱实验结果,获得元素质量分数与谱线强度的关系曲线(定标曲线)。对中南民族大学附近的土壤进行激光诱导击穿光谱实验,发现土壤中含有Mg,Ca,Na等18种元素,对河南云台山茱萸峰岩石的激光诱导击穿光谱实验结果仅获得Fe,Mg,Ca 3种金属元素。比较这2种实际样品的激光诱导击穿光谱结果表明,检测样品的物理结构影响激光诱导光谱的实验结果。     

Recent progress on the application of LIBS for metallurgical online analysis in China

Recent progress on the application of laser-induced breakdown spectroscopy (LIBS) for metallurgical analysis particularly achieved by Chinese research community is briefly reviewed in this article. The content is mainly focused on the progress in experimental research and calibration methods toward LIBS applications for metallurgical online analysis over the past few years. Different experiment setups such as single-pulse and double-pulses LIBS schematics are introduced. Various calibration methods for different metallic samples are presented. Quantitative results reported in the literature and obtained in the analysis of various samples with different calibration methods are summarized. At the last section of this article, the difficulties of LIBS application for molten metal analysis in a furnace are discussed.     

Aerosol formation of Sea-Urchin-like nanostructures of carbon nanotubes on bimetallic nanocomposite particles

With the advantage of continuous production of pure carbon nanotubes (CNTs), a new simple aerosol process for the formation of CNTs was developed. A combination of conventional spray pyrolysis and thermal chemical vapor deposition enabled the formation unusual sea-urchin-like carbon nanostructures composed of multi-walled CNTs and metal composite nanoparticles. The CNTs formed were relatively untangled and uniform with a diameter of less than ~10 nm. The key to the formation of CNTs in this way was to create a substrate particle containing both a catalytic and non-catalytic component, which prevented coking. The density of the CNTs grown on the spherical metal nanoparticles could be controlled by perturbing the density of the metal catalysts (Fe) in the host non-catalytic metal particle matrix (Al). Mobility size measurement was identified as a useful technique to real-time characterization of either the catalytic formation of thin carbon layer or CNTs on the surface of the metal aerosol. These materials have shown unique properties in enhancing the thermal conductivity of fluids. Other potential advantages are that the as-produced material can be manipulated easily without the concern of high mobility of conventional nanowires, and then subsequently released at the desired time in an unagglomerated state.     

Quantitative analysis of ITO film by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is an effective method for nondestructive rapid element analysis in a wide range of media in situ. We use the LIBS technique for quantitative analysis of indium tin oxide (ITO) films, which are transparent conducting materials widely used in industry. The plasma is generated by focusing a Nd:YAG laser pulse with a duration of 10 ns and a wavelength of 1064 nm onto the ITO-sample surface. We perform test experiments to define optimum values of the laser-pulse energy and the time delay between the laser pulse and the beginning of the LIBS spectra acquisition. Next, by the calibration-free Boltzmann plot method, we assess the plasma temperature and finally calculate the content of In and Sn in the test ITO specimen, and this agrees well with real concentration values.     

激光诱导击穿光谱技术在土壤元素检测中的应用

激光诱导击穿光谱(laser-induced breakdown spectroscopy,LIBS)是一种原子发射光谱,具有对样本简单(或不需要)预处理,多元素同步、远距离测量,适用性广等独特优势。因此,LIBS分析技术被看作是未来化学分析和快速绿色分析技术领域的新兴技术。目前,土壤污染(重金属、有机污染等)检测与防治已成为现代农业和农业可持续发展关注和研究的热点问题。介绍了常见LIBS系统的结构组成以及工作原理,综述了LIBS技术对土壤中大量营养元素,重金属元素和土壤相关其他物质的研究现状和主要进展,提出了LIBS检测技术在土壤元素等方面的研究方向和发展趋势。     

激光诱导击穿光谱与拉曼光谱技术在危险物检测中的研究进展

炸药、生物及化学危险物检测在反恐和公共安全领域具有重要应用价值,也是目前亟需解决的问题。激光诱导击穿光谱技术利用高能激光脉冲诱导材料产生等离子体,通过探测等离子体辐射光谱从而分析其组成成分。拉曼光谱技术是基于非弹性光散射的一种光谱检测方法,可以反映分子的振动信息。由于它们都具有快速和非接触遥测的优点,成为最有发展潜力和应用前景的危险物检测技术。介绍了激光诱导击穿光谱、拉曼光谱以及二者联合探测技术在危险物检测中的国内外发展现状,并对各自的优缺点进行了分析。激光诱导击穿光谱信号强、实时性好,但重复性差、基底效应影响显著,在判别组成元素相同而分子结构不同的危险物和干扰物时面临巨大挑战。拉曼光谱能够提供被测物的分子信息,适合于鉴别有机危险物,但信号弱、受荧光干扰大、检测低浓度样品及分析混合物的能力弱,外场使用时受周围杂散光以及环境变化的影响大。将这两种光谱探测技术相融合,发挥各自的优点,可以有效地提高探测危险物的准确度。但两种光谱联合探测系统结构和数据处理复杂,成本高,还有许多技术难点亟需解决。文章最后,对危险物激光诱导击穿光谱和拉曼光谱研究的前景进行了展望。