The validity of commercial LIBS for quantitative analysis of brass alloy — comparison of WDXRF and AAS

Commercial low-cost laser induced breakdown spectroscopy (LIBS) has been successfully employed for the quantitative analysis of a Cu-based alloy using a Nd:YAG laser at 1064 nm. The main aim of the present investigation is to explore the benefits of a commercial low-cost LIBS setup. It was recognized that some trace elements such as Al and S could not be detected by LIBS even with a high-resolution spectrometer. The main difficulties in quantifying Cu as a basic component of a brass alloy are related to the self-absorption of Cu spectral lines, with the effect complicated at Cu concentrations higher than 65%. However, few Cu lines such as that at 330.795 nm would be helpful to use due to their lower susceptibility to self-absorption. LIBS, flame atomic absorption spectrometry (FAAS), and wavelength dispersive X-ray fluorescence (WDXRF) were compared for the detection of major and trace metals in the Cu-based alloy. In the case of WDXRF, the brass samples were identified by using a standardless quantitative analysis program depending on a fundamental parameter approach. The quantitative analysis results were acceptable for most of the major and minor elements of the brass sample. Therefore, commercial low cost LIBS would be useful for quantitative analysis of most elements in different types of alloys.     

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.     

Detection of sulfur in the reinforced concrete structures using a dual pulsed LIBS system

In concrete structures, an excessive amount of sulfate ions can cause severe damage to the strength and the stability of the building structures and hence a sensitive and reliable technique for sulfate ion detection in concrete is highly desirable. Laser-induced breakdown spectroscopy (LIBS) is one of the most reliable and sensitive techniques to identify the presence of potentially dangerous sulfur in the concrete structure. The atomic emission lines of sulfur lying in the 200–900 nm region are mostly singly ionized states and hence inherently very weak. In order to enhance the sensitivity of the conventional LIBS system, we employed a dual pulsed LIBS system for detection of weak spectral line of sulfur in concrete using the S II peak at 545.38 nm as a marker for quantifying sulfur content in the concrete. The 1064 nm fundamental and 266 nm fourth harmonic of the Nd:YAG laser in conjunction with Spectrograph/gated ICCD camera are the core factors in improvement of sensitivity. Furthermore, the dual pulsed LIBS system and the fine maneuvering of the gate parameters and interpulse delay yielded improvement in the sensitivity, and resulted in a systematic correlation of the LIBS signal with the concentration of sulfur in the concrete sample. In order to quantify the sulfur content in concrete, a calibration curve was also drawn by recording the LIBS spectra of sample having sulfur in various concentrations. The limit of detection achieved with our dual pulsed LIBS system is approximately 38 μg/g.     

Laser Induced Breakdown Spectroscopy for Comparative Quantitative Analysis of Betel Leaves from Pakistan

Laser induced breakdown Spectroscopy (LIBS) was applied for the elemental analysis and exposure of the heavy metals in betel leaves in air. Pulsed Nd∶YAG (1064 nm) in conjunction with a suitable detector (LIBS 2000+, Ocean Optics, Inc) having the optical resolution of 0.06 nm was used to record the emission spectra from 220 to 720 nm. Elements like Al, Ba, Ca, Cr, Cu, P, Fe, K, Mg, Mn, Na, P, S, Sr, and Zn were found to present in the samples. The relative abundances of the observed elements were calculated through standard calibration curve method, integrated intensity ratio method, and weight percentage LIBS approach. LIBS findings were validated by comparing its results with the results obtained using a typical analytical technique of Inductively Coupled plasma-optical emission spectroscopy (ICP-OES). Limit of detection (LOD) of the LIBS system was also estimated for heavy metals. The experience gain through this work implies that LIBS could be highly applicable for testing the quality and purity of food products.     

Contaminant concentration in environmental samples using LIBS and CF-LIBS

The present paper deals with the detection and quantification of toxic heavy metals like Cd, Co, Pb, Zn, Cr, etc. in environmental samples by using the technique of laser-induced breakdown spectroscopy (LIBS) and calibration-free LIBS (CF-LIBS). A MATLAB^TM program has been developed based on the CF-LIBS algorithm given by earlier workers and concentrations of pollutants present in industrial area soil have been determined. LIBS spectra of a number of certified reference soil samples with varying concentrations of toxic elements (Cd, Zn) have been recorded to obtain calibration curves. The concentrations of Cd and Zn in soil samples from the Jajmau area, Kanpur (India) have been determined by using these calibration curves and also by the CF-LIBS approach. Our results clearly demonstrate that the combination of LIBS and CF-LIBS is very useful for the study of pollutants in the environment. Some of the results have also been found to be in good agreement with those of ICP-OES.     

Detection of mercury in water by laser-induced breakdown spectroscopy with sample pre-concentration

A method based on pre-concentration, using electrolysis, has been proposed and used for the improvement of detection sensitivity of mercury ions at ultra-trace level of concentration in an aqueous matrix by laser-induced breakdown spectroscopy (LIBS). The experimental evaluation of this method was carried out on mercury chloride (HgCl₂) in triple-distilled water for a concentration range of the element of 0.01–10 mg l⁻¹. A pre-concentration factor of ∼180 was obtained for LIBS detection of mercury emission line at 253.65 nm. The limit of detection (LoD) of ∼0.011 mg l⁻¹ (or ∼11 ppb) for mercury in the water sample was achieved.     

Laser-induced breakdown spectroscopy: A tool for analysis of different types of liquids

Laser-induced breakdown spectroscopy (LIBS) was applied to detect elements in different liquids (water and oil). Spectra of plasmas generated by focusing the second harmonic 5=532 nm of a pulsed Nd:YAG laser on the liquids' surfaces at atmospheric pressure were recorded. Calibration curves for chromium in water and in oil were obtained, and detection limits were deduced.     

In-Situ Monitoring of Chromium Uptake in Different Parts of the Wheat Seedling (Triticum aestivum) using Laser-Induced Breakdown Spectroscopy

The present work is a methodological study to investigate the effect of chromium (VI) stress on wheat seedlings. Point detection capability of laser-induced breakdown spectroscopy (LIBS) was utilized for the monitoring of in-situ chromium uptake in wheat (Triticum aestivum) seedlings. Chromium accumulation and its effects on other elements in wheat seedling were investigated by comparing the intensities of spectral lines of chromium and other minerals present in the LIBS spectra. In-situ LIBS spectra of the different parts of the wheat seedlings were recorded by directly focusing the laser beam on the surface of root, stem, and leaf of the seedlings grown with and without chromium-containing solutions. The spectra obtained from the different parts (root, stem, and leaf) of the wheat plant were analyzed to determine the distribution pattern/accumulation of chromium. Effect of the chromium uptake on the distribution pattern of other elements like calcium (Ca), magnesium (Mg), sodium (Na), and potassium (K) was also investigated. It was observed that chromium concentrations in plant organs decreased in the following order: roots > leaves > stems.     

Determination of Ca content of coral skeleton by analyte additive method using the LIBS technique

Laser-induced breakdown spectroscopic (LIBS) technique was used to study the elemental pro?le of coral skeletons. Apart from calcium and carbon, which are the main elemental constituents of coral skeleton, elements like Sr, Na, Mg, Li, Si, Cu, Ti, K, Mn, Zn, Ba, Mo, Br and Fe were detected in the coral skeletons from the Inani Beach and the Saint Martin’s island of Bangladesh and the coral from the Philippines. In addition to the qualitative analysis, the quantitative analysis of the main elemental constituent, calcium (Ca), was done. The result shows the presence of (36.15±1.43)% by weight of Ca in the coral skeleton collected from the Inani Beach, Cox’s Bazar, Bangladesh. It was determined by using six calibration curves, drawn for six emission lines of Ca I (428.301 nm, 428.936 nm, 431.865 nm, 443.544 nm, 443.569 nm, and 445.589 nm), by standard analyte additive method. Also from AAS measurement the percentage content of Ca in the same sample of coral skeleton obtained was 39.87% by weight which compares fairly well with the result obtained by the analyte additive method.     

Calibration-free laser-induced breakdown spectroscopy for quantitative elemental analysis of materials

The application of calibration-free laser-induced breakdown spectroscopy (CF-LIBS) for quantitative analysis of materials, illustrated by CF-LIBS applied to a brass sample of known composition, is presented in this paper. The LIBS plasma is produced by a 355?nm pulsed Nd:YAG laser with a pulse duration of 6?ns focussed onto a brass sample in air at atmospheric pressure. The time-resolved atomic and ionic emission lines of Cu and Zn from the LIBS spectra recorded by an Echelle spectrograph coupled with a gated intensified charge coupled detector are used for the plasma characterization and the quantitative analysis of the sample. The time delay where the plasma is optically thin and is also in local thermodynamic equilibrium (LTE), necessary for the elemental analysis of samples from the LIBS spectra, is deduced. An algorithm relating the experimentally measured spectral intensity values with the basic physics of the plasma is developed. Using the algorithm, the Zn and Cu concentrations in the brass sample are determined. The analytical results obtained from the CF-LIBS technique agree well with the certified values of the elements in the sample, with an accuracy error <1%.     

532和1 064 nm激光的水下LIBS探测对比研究

海洋是国家可持续发展的战略要地,迫切需要海洋探测技术的快速发展,光谱类的化学传感器由于具有原位、非接触和长期探测的优势日益成为研究热点。为了将激光诱导击穿光谱（LIBS）技术应用于海洋原位探测,采用532和1 064 nm波长激光在能量分别为3和40 mj附近进行烧蚀,对比实验研究了532和1 064 nm激光作用下的LIBS击穿特性,并重点探讨了水下激光传输距离对LIBS信号的影响。结果显示,采用1 064 nm的激光能够获得更高的谱线强度和信背比,以及更长的等离子体寿命,但LIBS信号稳定性较差;受水体对不同波长激光能量衰减不同的影响,在水下传输距离2～5 cm范围内,随着1 064 nm激光能量的衰减LIBS信号衰减也很明显,而位于海水“透射窗口”的532 nm的激光LIBS信号基本保持不变。为今后LIBS海洋原位探测系统的开发提供了有价值的设计依据。     

多次放电的激光诱导击穿光谱信号增强

激光诱导击穿光谱技术(LIBS)是一种广泛应用于科学和工程方面的元素分析技术。LIBS测量一些微量元素时存在探测极限高的不足,因此增强LIBS信号强度,降低元素探测极限,对扩展其应用范围有着重要的意义。为了实现LIBS光谱信号的增强,提出多次放电增强激光诱导击穿光谱方法,并以固体铝合金材料为例进行了光谱信号强度增强的研究。实验发现,激光作用在铝合金材料上烧蚀样品产生等离子体并溅射到样品上方高压放电电极所在区域,该区域在等离子体产生之后50 μs之内均可以诱导高压电极放电。因此采用高频脉冲电源可以实现一次LIBS产生的等离子体诱导电极多次放电。多次放电会对等离子体进行多次激发,同时多次放电对等离子的加热作用会延缓等离子体冷却速率从而延长等离子体的持续时间,两者共同作用可以增强LIBS光谱信号强度,进而降低LIBS对微量元素的探测极限。使用频率为100 kHz的高频直流脉冲电源,利用数字延迟脉冲发生器同步激光与高压电源,在激光过后3.6 μs触发高压放电,一次LIBS产生的等离子体可以诱导电极5次放电,即对等离子体进行5次激发和加热。利用光谱仪对5次放电等离子体光谱进行积分测量。实验结果表明：使用多次放电增强之后,等离子体持续时间得到大幅延长,光谱信号强度得到大幅增强,其中,Mg Ⅱ (~279 nm)的信号强度可以增强约48倍,Al Ⅱ (~358 nm)的信号强度可以增强约72倍,微量元素Mn Ⅰ (~403 nm)的信号强度增强约6.3倍,微量元素Cu Ⅰ (~403 nm) 的信号强度增强约8.3倍。Mn Ⅰ (~403 nm)和Cu Ⅰ (~403 nm) 的探测极限分别降低为LIBS单次放电的1/6和1/8。多次放电增强激光诱导击穿光谱方法很好地增强了LIBS的光谱信号强度,降低了对微量元素的探测极限,扩展了LIBS技术的应用范围。该方法有潜力应用到贵重物品、稀有材料及文物的鉴定之中。     

LIBS-Raman光谱联合水下探测系统及初步试验

水下激光诱导击穿光谱技术(LIBS)和水下激光拉曼光谱技术(Raman)已在深海成功获得应用,这两种技术探测对象互补、器件类似,两者联合探测可更好的进行深海研究。针对此需求研发了一套LIBS-Raman光谱联合水下原位探测原理样机,整个系统集成于L790 mm×Φ270 mm的舱体内,在舱体前端有光学窗口和水密插头,舱体内部主要包括脉冲激光器、光谱仪、嵌入式计算机和供电转换装置,甲板控制终端通过水密电缆实现对系统的供电、控制和数据采集。该联合系统采用一台双波长脉冲激光器同时作为LIBS和拉曼光谱的激发光源,LIBS采用1 064 nm波长,拉曼光谱采用532 nm波长。双波长激光器发出的光束经分光镜分为两路,经过后向散射光路收集的两路信号分别进入两个小型光纤光谱仪进行分光探测,LIBS采用AvaSpec-ULS2048光谱仪,拉曼光谱采用QE 65000光谱仪。利用搭建的原理样机在青岛近海进行水下原位探测,在实验室开展了水中固体靶的探测,实验结果证明了LIBS-Raman联合光谱探测装置的可行性。下一步将优化系统并开展深海探测应用。     

Improved LIBS limit of detection of Be, Mg, Si, Mn, Fe and Cu in aluminum alloy samples using a portable Echelle spectrometer with ICCD camera

Laser-induced breakdown spectroscopy (LIBS) is a laser-based technique that can provide non-intrusive, qualitative and quantitative measurement of metals in various environments. LIBS uses the plasma generated by a high-energy laser beam to prepare and excite the sample in one step. In the present work, LIBS has been applied to perform elemental analysis of six trace elements simultaneously in aluminum alloy targets. The plasma is generated by focusing a pulsed Nd:YAG laser on the target in air at atmospheric pressure. LIBS limit of detection (LOD) is affected by many experimental parameters such as interferences, self-absorption, spectral overlap and matrix effect. We aimed to improve the LIBS LOD by optimizing these experimental parameters as possible. In doing so, a portable Echelle spectrometer with intensified CCD camera was used to detect the LIBS plasma emission. This advanced Echelle spectrometer provides a constant spectral resolution (CSR) of 7500 corresponding to 4 pixels FWHM over a wavelength range 200–1000 nm displayable in a single spectrum. Then, the calibration curves for iron, beryllium, magnesium, silicon, manganese and copper as minor elements were achieved with linear regression coefficients between 98–99% on average in aluminum standard sample alloys. New LOD values were achieved in the ppm range with high precision (RSD 3–8%). From the application view point, improving LIBS LOD is very important in the on-line industrial process control to follow-up multi-elements for the correct alloying in metals.     

激光诱导击穿光谱定量分析玉石中的Mg,Fe和Ca

基于对样品进行的激光诱导击穿光谱和X射线荧光光谱分析测试建立了天然玉石中主要元素Mg,Ca和微量元素Fe的定标曲线。实验采用纳秒级的Nd∶YAG激光器(波长:1 064nm)为光源,在延迟时间为3μs,激光脉冲累积数量为110,单个脉冲能量为100mJ,脉冲重复频率为10Hz的实验条件下,采用激光诱导击穿光谱技术装置对天然南阳独山玉石样品中的元素进行等离子体激发测试,得到波长在300~1 000nm的等离子光谱图。通过将得到的光谱图中特征峰与美国国家标准与技术研究院数据库进行对比,发现测试样品中含有Mg,Fe和Ca等元素,以X射线荧光光谱分析技术对四种南阳独山玉标准样品中测量出的Mg,Fe和Ca元素氧化物含量作为标准数据,选取含量比较高的Al元素作为内标元素,采用内标法对玉石光谱图中Mg,Fe和Ca元素特征峰值进行线性拟合,从而得出Mg,Fe和Ca三种元素的定标曲线,求出待测样品中这3种元素氧化物的含量,结果表明这三种元素氧化物的含量与中国珠宝宝石收藏鉴赏全集资料中所给出的元素氧化物含量的百分比范围MgO(0.28%~1.73%),Fe2O3(0~0.8%),CaO(18%~20%)相符合,相比于常用的方法,激光诱导击穿光谱技术可以快速地对待测样品进行检测,样品预处理简单且对样品损害较小。进一步验证了激光诱导击穿光谱技术对于玉石应用的可行性。     

Dynamics of laser-induced cavitation in liquid

This paper presents an analysis of the rate of bubble expansion and an estimate of maximum bubble diameter and bubble lifetime prior to collapse. Such data are needed for the optimization of system parameters for elemental analysis in water by laser-induced breakdown spectroscopy (LIBS). Two techniques were used for this study: pump-probe beam deflection and high-speed photography. Plasma in the water bulk was generated by a focussed laser pulse with energy of 140 mJ and pulse duration of 10 ns, operating at the fundamental Nd:YAG laser wavelength (1064 nm). Reasonable agreement on the value of maximum bubble diameter was obtained between the photographic and probe beam deflection results. Reasonable agreement for the total duration of the oscillating cavitation bubble was also obtained for the two techniques, with a mean value of ∼800 μs. A comparison between empirical results and predictions based on the Rayleigh equation is also presented.     

激光诱导击穿光谱结合神经网络测定土壤中的Cr和Ba

提出了一种基于人工神经网络的激光诱导击穿光谱技术实现元素成分高准确度定量分析的方法.采用基于动量和自适应学习速率梯度下降算法的反向传播神经网络,结合激光诱导击穿光谱技术的方法测定土壤中Cr和Ba元素的含量,得到了Cr和Ba的含量以及多次重复预测的相对标准偏差,并与采用传统的内标法得到的检测结果相比较.研究结果表明:基于动量和自适应学习速率梯度下降算法的反向传播神经网络分析方法,与激光诱导击穿光谱技术相结合能更好地实现对土壤样品中Cr和Ba元素的定量检测.相对内标法,神经网络分析方法与激光诱导击穿光谱技术相结合可以很明显地提高检测准确度和精密度,对采用激光诱导击穿光谱技术定量检测土壤重金属污染具有很好的应用价值.     

金纳米与磁场作用下LIBS检测灵敏度改善研究

针对激光诱导击穿光谱技术（LIBS）中等离子体的发射光谱增强问题,提出一种磁场增强LIBS与纳米颗粒增强LIBS（NELIBS）相结合的方法。采用热蒸发法在样品表面沉积一层直径20 nm的金纳米颗粒。利用波长为1 064 nm,最大能量为200 mJ的Nd∶YAG脉冲激光器在室温,一个标准大气压下对纯铜和黄铜进行诱导击穿。调整激光能量为30~110 mJ,分别使用传统LIBS、磁场增强LIBS、NELIBS以及两种方法结合对纯铜进行激光诱导击穿,得到特征谱线(Cu Ⅰ 521.8 nm)的强度增强因子和信噪比,并对其增强机理进行分析。在相同环境下使用四种方式对黄铜和纯铜进行诱导击穿以探测样品中的微量元素。当在样品表面沉淀金纳米颗粒或者将沉淀有金纳米颗粒的样品放在磁场中进行诱导击穿时,发现纯铜样品的光谱中存在Mg元素的特征谱线Mg Ⅱ 279.569 nm,黄铜样品的光谱中存在Si元素的特征谱线 Si Ⅰ 251.611 nm。实验结果表明：单独施加磁场约束或增加纳米金颗粒均可以有效增强等离子体光谱强度,但增强效果弱于两种方法结合,磁场约束对光谱的增强效果弱于NELIBS的增强效果。当结合NELIBS与磁场约束LIBS时,谱线增强因子最高可达14.3(Cu Ⅰ 521.8 nm),相比于磁场增强LIBS和NELIBS,最大增强因子分别提高了28%和59%。四种情况中当激光脉冲能量逐渐增大时,等离子体向外膨胀的强度增大,磁场产生的洛伦兹力束缚等离子的能力相对减弱,同时纳米金颗粒对等离子体发射光谱的增强作用被削弱,谱线强度降低,等离子体的增强因子逐渐减小后趋于稳定。通过NELIBS与磁场约束LIBS结合方式,不仅可以有效提高等离子体的发射谱线强度,改善光谱信号信噪比,而且传统LIBS方法中由于谱线强度低、背景噪声大而无法探测的微量元素可以被探测到,LIBS技术对微量元素的探测能力得到显著提高,微量元素的探测下限变得更低。NELIBS与磁场约束LIBS结合的方法具有更高的灵敏度和准确度,为激光诱导击穿光谱技术的谱线增强方法提供了新的思路,在该领域具有广阔的应用前景。     

Design and construction of Q-switched Nd:YAG laser system for LIBS measurements

A passive, Q-switched pulsed, Nd:YAG laser system was designed and built, which can provide a potential compact robust laser source for portable laser induced breakdown spectroscopy systems.The developed laser system operates at 1064 nm. Each laser shot contains a train of pulses having maximum total output energy of 170 mJ. The number of pulses varies from 1–6 pulses in each laser shot depending on the pump energy. The pulse width of each pulse ranges from 20 to 30 ns. The total duration of the output pulse train is within 300 μs. The multi-pulse nature of the laser shots was employed to enhance the LIBS signal. To validate the system, LIBS measurements and analysis were performed on ancient ceramic samples collected from Al-Fustat excavation in Old Cairo. The samples belong to different Islamic periods in Egypt history. The results obtained are highly indicative that useful information can be provided to archeologists for use in restoring and repairing of precious archeological objects.     

Stoichiometry analysis of titanium oxide coating by LIBS

In this work, laser induced breakdown spectroscopy (LIBS) is used to determine the composition of titanium oxide film produced by anodized of Ti6Al4V alloy. We have used Ti lines in the spectral region between 470–520 nm to determine temperature of the plasma generated on anodized surface of Ti6Al4V alloy for temperature determination by Boltzmann plot method. In order to measure the content of oxygen and titanium ratio on the surface the alloy, we have used the oxygen lines 777.194, 777.417 and 777.539 nm, and titanium lines 780.597 and 782.491 nm observed in an ambient of argon. Finally, we report the possibilities for the determination of the coating chemical composition using LIBS.