CN108344729A - A kind of laser induced breakdown spectroscopy rapid detection method based on the calibration of multiline internal calibration - Google Patents

A kind of laser induced breakdown spectroscopy rapid detection method based on the calibration of multiline internal calibration Download PDF

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Publication number
CN108344729A
CN108344729A CN201810479699.2A CN201810479699A CN108344729A CN 108344729 A CN108344729 A CN 108344729A CN 201810479699 A CN201810479699 A CN 201810479699A CN 108344729 A CN108344729 A CN 108344729A
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China
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calibration
spectral line
intensity
laser induced
induced breakdown
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CN201810479699.2A
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Chinese (zh)
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CN108344729B (en
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朱德华
王满仓
徐玲杰
蔡燕
陈孝敬
袁雷明
刘文文
张健
曹宇
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温州大学
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using infra-red, visible or ultra-violet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/718Laser microanalysis, i.e. with formation of sample plasma

Abstract

The present invention discloses a kind of laser induced breakdown spectroscopy rapid detection method calibrated based on multiline internal calibration, the method is by selecting and calculating the ratio (as ordinate) of the sum of the sum of a plurality of analysis spectral line intensity and a plurality of internal standard the intensity of spectral line, and calibration curve is established (as abscissa) with the concentration value of analytical element, the calibration curve of high related coefficient is obtained, the application of quantitative analysis elemental composition is used for.The analytical error that the method can introduce to avoid the irregular form of sample improves LIBS accuracy in detection.

Description

It is a kind of based on multiline internal calibration calibration laser induced breakdown spectroscopy quickly detect Method

Technical field

The invention belongs to material tests field, in particular to laser induced breakdown spectroscopy rapid detection methods, particularly relate to Laser induced breakdown spectroscopy rapid detection method based on the calibration of multiline internal calibration.

Background technology

Laser induced breakdown spectroscopy method (Laser Induced Breakdown Spectroscopy) is referred to as LIBS, is It was proposed and was realized in 1962 by the David Cremers research groups of Los Alamos National Laboratories of the U.S..Since The group member Brech in 1962 is proposed at first induces the spectrochemistry for generating plasma with ruby maser After method, laser induced breakdown spectroscopy starts to be widely used in the every field such as gas, liquid and solid.

Wavelength of the laser induced breakdown spectroscopy based on atom spectrum and ion spectra is corresponded with specific element Relationship, and spectral signal intensity and the content of corresponding element also have a certain amount relationship, and laser exists through lens focus Sample surfaces will locally generate plasma, referred to as swash when the energy density of laser pulse is more than breakdown threshold energy Photoinduction plasma.Plasma is gradually cooled down with outwardly environment expansion process, concurrent firing table sign sample component letter The spectrum of breath is acquired using photodetector and spectrometer plasma emission spectrum.By parsing plasma light Spectrum, and Quantitative Analysis Model is combined, the classification and content information of analysis sample component can be obtained.

The original position of elemental composition and on-line analysis are one of most important developing direction of modern spectral technique.Especially in geology Real-time analysis field, in-situ study and the on-line analyses such as exploration, environmental monitoring, coal quality on-line analysis, smelting iron and steel quality-monitoring Seem of crucial importance.Compared to transmission spectra analysis method (such as AAS, ICP, ICP-MS etc.), laser induced breakdown spectroscopy skill Art (LIBS) has the ability of in-situ study and on-line analysis, without being pre-processed to sample, can fast implement it is long-range or Online qualitative and quantitative analysis can be used for the detection of solid, liquid or gaseous sample, therefore be applied with boundless market Foreground.

But there is inspection in laser induced breakdown spectroscopy in carrying out the application process of in-situ study and on-line analysis The shortcomings of survey precision is low, poor repeatability, analytic process is easy to be excited optical energy density, focusing parameter, sample surfaces characteristic, matrix The influences such as effect, spectra collection parameter.Especially in quantitative analysis application, laser induced breakdown spectroscopy testing result is accurate Degree can not show a candle to Analytical Laboratory Results, to be caused to the in-situ study of laser induced breakdown spectroscopy and on-line analysis application Certain puzzlement.

Wherein, a key factor for influencing in-situ study and on-line analysis is the irregular form of sample surfaces.In general, In-situ study and on-line analysis require sample to detect in real time, are not necessarily to sample pretreatment, but find in actual application, wait for The sample morphology of detection is different, such as ore or coal etc..Irregular sample surfaces can influence laser induced breakdown spectroscopy skill Laser energy density size in art (LIBS) detection process, and then sample ablation amount and plasma light spectral intensity are influenced, from And larger error is brought to experimental result.Sample must just be pre-processed to improve accuracy of detection, but thus The original idea of in-situ study and on-line analysis is violated.

Therefore, sample can not be carried out in external environment out of office it is unified it is pretreated under the premise of, in face of the to be measured of various forms How sample ensures that the accuracy of detection of LIBS and repeatability are letter a great problems to be solved.

Invention content

The purpose of the invention is to overcome shortcoming and defect of the existing technology, and provide a kind of based in multiline Calibrate calibration laser induced breakdown spectroscopy rapid detection method, by this method under the premise of not doing sample pretreatment significantly LIBS accuracy of detection is improved, to greatly improve the application value of laser induced breakdown spectroscopy.

To achieve the above object, the technical scheme is that

(1) multiline internal calibration calibration curve is established, laser induced breakdown spectroscopy detection is carried out to object sample to be measured, and The sum of the sum of selected in laser induced breakdown spectroscopy figure and calculate a plurality of analysis spectral line intensity with a plurality of internal standard the intensity of spectral line Ratio be specially as the first coordinate:In data processing, a plurality of analytical element spectral line and a plurality of internal standard are selected Element spectral line, and calculate the ratio of its intensity sum:Wherein p is analytical element the intensity of spectral line, and q is internal standard Element spectral line intensity;Using the concentration value of analytical element as the second coordinate, multiline internal calibration calibration curve is established;

(2) the multiline internal calibration calibration curve established according to step (1), carry out quantitative analysis and inspection to object to be measured Survey the analysis of elemental composition.

After establishing calibration curve, under identical experiment condition, experiment detection, record pair are carried out to object to be measured The intensity of spectral lines I answeredx, and it is equal to I by compared with calibration curve, that is, finding ordinate y valuesxPoint, further according to calibration curve Read the concentration of element value C of corresponding X-axisx, the CxValue is the concentration of element of object to be measured.

It is ledrite that further setting, which is the object to be measured, wherein a plurality of analytical element spectral line is different wave length The intensity of spectral line calibration curve of Pb, a plurality of internal standard element spectral line are the intensity of spectral line calibration curve of the Cu of different wave length.

Further setting is that the wavelength selection of the intensity of spectral line calibration curve of the Pb of the different wave length is: Two or more in 261.42nm, 280.20nm, 283.31nm, 368.35nm, 405.78nm, 424.49nm, 504.26nm.

Further setting is that the wavelength selection of the intensity of spectral line calibration curve of the Cu of the different wave length is: Two or more in 324.75nm, 327.40nm, 510.55nm, 515.32nm, 521.82nm.

It is ordinate that further setting, which is the first coordinate, and the second coordinate is abscissa.

Present invention has the advantages that:

(1) present invention proposes a kind of calibration method of multiline internal calibration, and the method is by selecting and calculating a plurality of point Analyse the ratio (as ordinate) of the sum of the intensity of spectral line with the sum of a plurality of internal standard the intensity of spectral line, and with the concentration value of analytical element (as abscissa) establishes calibration curve, obtains the calibration curve of high related coefficient, is used for quantitative analysis and detection elements ingredient Application.The analytical error that the method can introduce to avoid the irregular form of sample improves LIBS accuracy in detection.

(2) method of the invention is other than it can reduce because of the error that sample irregularly generates, moreover it is possible to be applied to other one The empirical factor for being readily incorporated measurement error is cut, including Laser Energy Change, environmental gas Parameters variation, matrix effect influence Deng.

(3) this method need not handle experimental result by complicated computer digital animation algorithm, only need simple Excel operations, you can achieve the effect that computer multivariate data mining algorithm program, it is cost-effective, it is particularly suitable for original position Analysis and on-line analysis environment, fast and easy are highly practical.

Description of the drawings

In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, according to These attached drawings obtain other attached drawings and still fall within scope of the invention.

The brief installation drawings of simple LIBS that Fig. 1 embodiment of the present invention is built;

The single analysis spectral line intensity-concentration calibration curve of Fig. 2 embodiment of the present invention as a comparison, wherein (a) is Pb 405.78nm the intensity of spectral line calibration curves;(b) it is the calibration curve of Pb 405.78nm/Cu 510.55nm the intensity of spectral line ratios;

The multiline internal calibration calibration curve of Fig. 3 embodiment of the present invention, wherein (a) is the sum of 3 Pb the intensity of spectral line and 1 The calibration curve of the ratio and Pb concentration of Cu internal standard spectral lines;(b) it is the sum of 5 Pb the intensity of spectral line and 1 Cu internal standard spectral line The calibration curve of ratio and Pb concentration;

Specific implementation mode

To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing Step ground detailed description.

By verification process in following embodiment, verification technical scheme may be implemented before not doing sample pretreatment It puts and greatly improves LIBS accuracy of detection, it is specific as follows:

(1) as shown in Figure 1, building LIBS test experiences device and platform, including pulse laser, spectrometer, computer, Several, motorized precision translation stage of optical element etc..Certainly, commercially available laser-induced breakdown can also directly be purchased in progress LIBS detections Spectrometer is detected.

(2) it is several to choose surface imperfection sample, a set of copper alloy sample (totally 7 pieces) is selected to state clear the present embodiment As case, sample blocks thickness differs, and the thickness differences of different samples is about ± 2mm (lens distance sample surfaces in testing Range difference variation range is ± 2mm), and sample does not do any surface treatment.Sample is moved horizontally by motorized precision translation stage, is made every Primary laser pulse all acts on different regions, avoids continuous ablation from generating surface crater, to influence experimental precision.

(3) parameters such as suitable pulsed laser energy, repetition rate, delay time and the time of integration are set, and keep phase The LIBS spectrograms of same experiment condition acquisition all samples, it is to be analyzed that data import computer.

(4) generally, for the sample of rule, in the case where keeping experiment condition constant, in plasma spectrometry Analysis spectral line intensity can be changed linearly with the concentration of analytical element, pass through different the intensity of spectral line-concentration experiment value Straight line, i.e. calibration curve (being also calibration curve) can be fitted, by the curve can to the sample of unknown concentration into Row element quantitative analysis.

It is violent for the plasma spectrometry changes in intensity values of different samples but when sample surfaces are irregular, spectral line Intensity-concentration value is no longer presented linear relationship,

As shown in Fig. 2, wherein (a) is that (abscissa is Pb concentration of element to Pb 405.78nm the intensity of spectral line calibration curve, is indulged Coordinate is Pb the intensity of spectral line), the intensity of spectral line and concentration value are substantially not present linear relationship as seen from the figure, and (b) are Pb The calibration curve (internal calibration) of 405.78nm/Cu 510.55nm the intensity of spectral line ratios, it can be found that can by default calibration method To greatly improve the linearly related degree of curve, but related coefficient is still very low, thus can not be determined by the calibration curve Amount analysis.

(5) in order to improve the calibration curve accuracy of irregular sample LIBS spectrum, the present embodiment proposes a kind of multiline Internal calibration calibration method.By taking Pb Element detections in copper alloy as an example, there is a plurality of spectrum in LIBS spectrograms as analytical element Pb Line common are Pb 261.42nm, Pb 280.20nm, Pb 283.31nm, Pb 368.35nm, Pb 405.78nm, Pb 424.49nm, Pb 504.26nm etc., and internal standard spectral line then selects the spectral line of matrix element Cu, such as Cu 324.75nm, Cu 327.40nm, Cu 510.55nm, Cu 515.32nm, Cu 521.82nm etc..In data processing, a plurality of analysis is selected Spectral line and a plurality of internal standard element spectral line, and calculate the ratio of its intensity sum:Wherein p is that analysis spectral line is strong Degree, q are internal standard the intensity of spectral line, and using the concentration of analytical element Pb as abscissa, above-mentioned ratio y establishes calibration song as ordinate Line can greatly improve the linearly related degree of curve, and then improve the accuracy of detection and repeatability of LIBS quantitative analyses.

As shown in figure 3, wherein (a) is the calibration curve for selecting 3 analysis spectral lines and 1 internal standard spectral line to establish, (b) it is choosing The calibration curve that 5 analysis spectral lines and 1 internal standard spectral line are established is selected, it can be found that the calibration curve related coefficient of two kinds of situations is equal Reach 0.95 or more, work well, therefore avoid the irregular of sample surfaces and the detection error of introducing, to improve detection Precision.

To sum up, the present embodiment and use multiline internal standard method (the relative intensity summation for considering a plurality of analysis spectral line) calculate hair Existing, calibration curve Linear Quasi is right to reach 0.97, that is, eliminates sample irregularly caused spectral intensity fluctuating error, significantly Improve measurement accuracy and repeatability.In addition, can also eliminate matrix effect and spectrum to a certain extent by multiline internal standard method The influences such as interference, are data processing methods that is a kind of simple and effective and having universality.The research can be LIBS in situ detections Reference value is provided with on-line checking application.

The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly It encloses, therefore equivalent changes made in accordance with the claims of the present invention, is still within the scope of the present invention.

Claims (5)

1. a kind of laser induced breakdown spectroscopy rapid detection method based on the calibration of multiline internal calibration, it is characterised in that:
(1) multiline internal calibration calibration curve is established, laser induced breakdown spectroscopy detection is carried out to object sample to be measured, and swashing It the sum of is selected in photoinduction breakdown spectral figure and calculates a plurality of analysis spectral line intensity and the ratio of the sum of a plurality of internal standard the intensity of spectral line It is worth, as the first coordinate, is specially:In data processing, a plurality of analytical element spectral line and a plurality of internal standard element are selected Spectral line, and calculate the ratio of its intensity sum:Wherein p is analytical element the intensity of spectral line, and q is internal standard element The intensity of spectral line;Using the concentration value of analytical element as the second coordinate, multiline internal calibration calibration curve is established;
(2) the multiline internal calibration calibration curve established according to step (1), to the analytical element of the unknown concentration of object to be measured into The analysis of row quantitative analysis and detection elements ingredient.
2. a kind of quick side of detection of laser induced breakdown spectroscopy based on the calibration of multiline internal calibration according to claim 1 Method, it is characterised in that:The object to be measured is ledrite, wherein a plurality of analytical element spectral line is the spectrum of the Pb of different wave length Line intensity calibration curve, a plurality of internal standard element spectral line are the intensity of spectral line calibration curve of the Cu of different wave length.
3. a kind of quick side of detection of laser induced breakdown spectroscopy based on the calibration of multiline internal calibration according to claim 2 Method, it is characterised in that:The wavelength selection of the intensity of spectral line calibration curve of the Pb of the different wave length is:261.42nm、 Two or more in 280.20nm, 283.31nm, 368.35nm, 405.78nm, 424.49nm, 504.26nm.
4. a kind of laser induced breakdown spectroscopy based on the calibration of multiline internal calibration according to claim 2 or 3 is quickly examined Survey method, it is characterised in that:The wavelength selection of the intensity of spectral line calibration curve of the Cu of the different wave length is:324.75nm、 Two or more in 327.40nm, 510.55nm, 515.32nm, 521.82nm.
5. a kind of quick side of detection of laser induced breakdown spectroscopy based on the calibration of multiline internal calibration according to claim 1 Method, it is characterised in that the first coordinate is ordinate, and the second coordinate is abscissa.
CN201810479699.2A 2018-05-18 2018-05-18 Laser-induced breakdown spectroscopy rapid detection method based on multi-spectral-line internal calibration CN108344729B (en)

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Citations (4)

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CN104374753A (en) * 2014-11-17 2015-02-25 浙江大学 Double-pulse laser induced breakdown spectroscopy-based method applied to detection of heavy metals and microelements in crops
CN104502329A (en) * 2014-12-28 2015-04-08 冶金自动化研究设计院 Method for establishing optimal element operation line in LIBS component analysis
CN105717094A (en) * 2016-01-29 2016-06-29 清华大学 Metal element analysis method based on large database recognition

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