CN102788772A - Method for measuring content of powdery substantial elements based on dual pluses - Google Patents
Method for measuring content of powdery substantial elements based on dual pluses Download PDFInfo
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- CN102788772A CN102788772A CN2012102448615A CN201210244861A CN102788772A CN 102788772 A CN102788772 A CN 102788772A CN 2012102448615 A CN2012102448615 A CN 2012102448615A CN 201210244861 A CN201210244861 A CN 201210244861A CN 102788772 A CN102788772 A CN 102788772A
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Abstract
The invention discloses a method for measuring the content of powdery substantial elements based on dual pluses, characterized in that: a powdery sample is put on a transparent glass pallet, the two pulses are focused onto the bottom of the powder through the glass pallet, the first pulse generates plasmas at the bottom of the powder, the second pulse carries out subsequent heating on the generated plasmas, radiant light signals emitted by the plasmas pass through the glass pallet and are collected by a collecting lens arranged below the glass pallet, and the collected radiant light signals are transmitted to a spectrometer through optical fibers for analyzing. According to the invention, there in no need of further treatment of the powdery sample, thus the speed of on-line detection is raised; the measuring signal fluctuation caused by the unevenness of the powder layer surface is overcome, and the repeatability of the measurement is raised; in addition, the application of the dual pluses allows the plasmas to be more close to a local thermal equilibrium state, thus the raising of the measurement precision is benefited.
Description
Technical field
The present invention relates to a kind of measuring method of material element content, specifically, this method is to adopt LIBS technology (being called for short LIBS) that constituent content is measured, and belongs to the atomic emission spectrum field of measuring technique.
Background technology
LIBS is a kind of brand-new material element analytical technology that grows up in the twentieth century later stage.The principle of work of LIBS is: under the intense laser pulse effect; The material of sample surfaces is provoked into and is plasma and decay rapidly; In attenuation process, give off the photon of CF, produce characteristic spectral line, its frequency and strength information have comprised the element kind and the concentration information of analytic target.LIBS technical operation cost is low, and measuring speed is fast, and have high sensitivity, need not or need sample pretreatment seldom and realize advantage such as multielement measurement, and radiationless harm, in commercial production, have great development potentiality.
But, because the laser action point of LIBS is very little, the ablation amount of substance seldom, for inhomogeneous, anisotropic material matrix effect is very obvious; Simultaneously, the fluctuation of laser energy, the repeatable accuracy that the difference of physical parameters such as plasma temperature, electron density causes LIBS to measure is lower; In addition, the electronic noise of the influence of environmental parameter and instrument internal components and parts itself etc. all is prone to LIBS produced and disturbs; Therefore utilize the measuring accuracy of the direct measuring samples of LIBS not to be guaranteed, limited the application of LIBS in production reality.Through discovering that single laser pulse impacts in sample surfaces, the plasma zone on the laser pulse incident direction; Electron density is bigger, thereby laser energy has been played the effect that shields, and makes follow-up laser energy can't arrive sample surfaces; Stoped the continuation of sample to be ablated; And the double-pulse laser technology can weaken this shielding action, reaches the purpose that increases the ablation quality, when having increased signal intensity; Make plasma more near local thermodynamic equilibrium's state, help improving the measuring accuracy of LIBS.
Directly powdered sample being carried out LIBS measures aspect repeated relatively poor; This is because on the one hand powdered sample can splash after receiving the effect of laser pulse; Sample surfaces is no longer smooth; Be difficult to guarantee the constant distance of condenser lens, can cause bigger uncertainty to laser ablation like this to sample surfaces; On the other hand, the powdered sample gasoloid that produces that splashes can absorb follow-up laser pulse, influence the ratio that laser energy arrives sample surfaces, can the repeatability of measurement be impacted equally.
At the disclosed (application number: 201110040537.7 of patent documentation based on the LIBS measuring technique; 201110210361.5) in, effectively improved the precision that LIBS measures with powdered sample compression moulding.But powder is pressed makes system comparatively complicated, has reduced the travelling speed of measuring system, is difficult to realize on-line measurement, becomes the bottleneck that restriction LIBS technology further develops.Therefore directly carrying out the LIBS measurement for powdered sample is a very potential application direction.
Summary of the invention
Technical scheme of the present invention is:
Based on the flour constituent content measuring method of double-pulse laser, it is characterized in that this method has comprised following steps:
1) element of desire in the sample being measured is decided to be object element; With the known one group of powdered sample of object element mass concentration as calibration sample; The object element concentration of each calibration sample is designated as C respectively
1, C
2, C
3
2) choose any one kind of them in one group of calibration sample from step 1) and be tiled on the transparent glass pallet;
3) utilize the LIBS system to detect: to adopt two pulsed lasers; First pulsed laser and second pulsed laser are placed the below of glass pallet; The position of two pulsed lasers and calibration sample conllinear or conllinear not; With the pulsed laser is excitation source;, first pulsed laser emitting laser passes the glass pallet after focusing on through condenser lens, the position of adjustment condenser lens, and the laser after feasible the focusing is at the inner plasma that produces of the calibration sample at the surface of contact place of calibration sample and glass pallet; After the time interval through 5～10 μ s, focus on the plasma from second pulsed laser emitting laser, the article on plasma body heats;
4) the radiant light signal of plasma generation is collected through the collection lens that the glass pallet is set at glass pallet bottom; Through optical fiber lead-in light spectrometer; Change into electric signal by computer acquisition through behind the spectrometer; Obtain step 2) in the characteristic light spectrogram of selected calibration sample, from this characteristic light spectrogram, obtain the characteristic spectral line intensity I of object element;
5) to each calibration sample repeating step 2) to step 4), obtain the corresponding object element characteristic spectral line intensity I of each calibration sample successively
1, I
2, I
3
6) with the object element concentration C
1, C
2, C
3Be independent variable, the characteristic spectral line intensity I
1, I
2, I
3For dependent variable is set up calibration curve through approximating method, the equation of calibration curve is y=f (x), and wherein, x is an independent variable, and y is a dependent variable;
When 7) the unknown testing sample of object element mass concentration being detected, at first testing sample is handled, obtained line strength I of object element in the testing sample according to step 1) to step 4)
c, on calibration curve, find I then
cPairing concentration value is the concentration of object element in the testing sample.
The present invention has the following advantages and the high-lighting effect:
The present invention utilizes the laser after the focusing to see through the glass pallet from glass pallet below and impacts powdered sample; At the inner plasma that produces of the powdered sample at the surface of contact place of powdered sample and glass pallet; Prevent to splash after powder from receiving the laser pulse effect, not only cause the distance of condenser lens and sample surfaces to change, and the powdered sample that splashes can absorb laser pulse next time; The energy that causes arriving sample surfaces reduces, and finally reduces Measurement Uncertainty.Compare with disclosed other measuring methods based on LIBS, the operation that the present invention need not be pressed to powdered sample makes this method to be applied on the fast on-line measurement better.And because at the inner plasma that produces of powdered sample; Receive the influence of the gravity of powdered sample own; Powder bed can produce the space constraint effect by the article on plasma body; Can strengthen line strength of plasma emission spectroscopy so to a certain extent, increase the signal to noise ratio (S/N ratio) of characteristic spectral line, reduce the detectability of object element.In addition, the application of double-pulse laser is bigger than monopulse laser-produced plasma volume; More near the state of local thermodynamic equilibrium; The light signal of collecting is stronger, can further reduce the detectability of object element effectively, and is significant to the detection of trace element in the sample.
Description of drawings
Fig. 1 is a LIBS system architecture diagram of the present invention.
Among the figure: 1-the first pulsed laser; 2-the second pulsed laser; 3-condenser lens; 4-glass pallet; 5-sample; 6-plasma; 7-collection lens; 8-optical fiber; 9-spectrometer; 10-computing machine.
Embodiment
Below in conjunction with accompanying drawing the present invention is further described.
Based on the flour constituent content measuring method of double-pulse laser, it is characterized in that this method has comprised following steps:
1) element of desire in the sample being measured is decided to be object element; With the known one group of powdered sample of object element mass concentration as calibration sample; The object element concentration of each calibration sample is designated as C respectively
1, C
2, C
3
2) choose any one kind of them in one group of calibration sample from step 1) and be tiled on the transparent glass pallet 4;
3) utilize the LIBS system to detect: to adopt two pulsed lasers; First pulsed laser 1 and second pulsed laser 2 are placed the below of glass pallet; The position of two pulsed lasers and calibration sample conllinear or conllinear not; With the pulsed laser is excitation source;, first pulsed laser emitting laser passes glass pallet (the shared condenser lens of following two pulsed lasers of conllinear situation) after focusing on through condenser lens 3, the position of adjustment condenser lens, and the laser after feasible the focusing is at the inner plasma 6 that produces of the calibration sample 5 and the calibration sample at the surface of contact place of glass pallet; After the time interval through 5～10 μ s, focus on the plasma 6 from second pulsed laser emitting laser, the article on plasma body heats;
4) the radiant light signal of plasma generation is collected through the collection lens 7 that the glass pallet is set at glass pallet bottom; Through optical fiber 8 lead-in light spectrometers 9; Gathered by computing machine 10 through changing into electric signal behind the spectrometer, obtain step 2) in the characteristic light spectrogram of selected calibration sample, from this characteristic light spectrogram, select the object element characteristic spectral line; Obtain the peak area of spectral line through the method for integration, peak area is the characteristic spectral line intensity I of object element;
5) to each calibration sample repeating step 2) to step 4), obtain the corresponding object element characteristic spectral line intensity I of each calibration sample successively
1, I
2, I
3
6) with the object element concentration C
1, C
2, C
3Be independent variable, the characteristic spectral line intensity I
1, I
2, I
3For dependent variable is set up calibration curve through approximating method, the equation of calibration curve is y=f (x), and wherein, x is an independent variable, and y is a dependent variable;
When 7) the unknown testing sample of object element mass concentration being detected, at first testing sample is handled, obtained line strength I of object element in the testing sample according to step 1) to step 4)
c, on calibration curve, find I then
cPairing concentration value is the concentration of object element in the testing sample.
Embodiment:
To utilize LIBS to measure the carbon content in coal element is example, and the flour constituent content measuring method based on double-pulse laser is set forth.
1) carbon of desire in the coal sample being measured is decided to be object element, at first uses ten kinds of known coal samples of each element mass concentration as calibration sample, and the mass concentration of the essential element of each coal sample is as shown in table 1; The carbon concentration of each calibration sample is designated as C successively
1, C
2, C
3
Table 1. mark coal sample composition
2) selecting first kind in one group of calibration sample from step 1) is tiled on the transparent glass pallet 4;
3) utilize the LIBS system to detect: to adopt two pulsed lasers; First pulsed laser 1 and second pulsed laser 2 are placed the below of glass pallet; The position of two pulsed lasers and calibration sample conllinear or conllinear not; With the pulsed laser is excitation source;, first pulsed laser emitting laser passes the glass pallet after focusing on through condenser lens 3, the position of adjustment condenser lens, and the laser after feasible the focusing is at the inner plasma 6 that produces of the calibration sample 5 and the calibration sample at the surface of contact place of glass pallet; After the time interval through 5 μ s, focus on the plasma 6 from second pulsed laser emitting laser, the article on plasma body heats;
4) the radiant light signal of plasma generation is collected through the collection lens 7 that the glass pallet is set at glass pallet bottom; Through optical fiber 8 lead-in light spectrometers 9; Gathered by computing machine 10 through changing into electric signal behind the spectrometer; Obtain step 2) in the characteristic light spectrogram of selected calibration sample, from this characteristic light spectrogram, select the characteristic spectral line of carbon 193.09nm as carbon, integration obtains the characteristic spectral line intensity I of carbon;
5) to each calibration sample repeating step 2) to step 4), obtain the corresponding carbon characteristic spectral line intensity I of each calibration sample successively
1, I
2, I
3
6) with the carbon concentration C
1, C
2, C
3Be independent variable, the characteristic spectral line intensity I
1, I
2, I
3For dependent variable is set up calibration curve through fit method, adopting the simplest single argument linear fit method to obtain the calibration curve equation in this example is y=0.0081x-0.0076, and wherein x is an independent variable, and y is a dependent variable;
When 7) the unknown testing sample of carbon mass concentration being detected, at first testing sample is handled, obtained line strength I of object element in the testing sample according to step 1) to step 4)
c, on calibration curve, find I then
cPairing concentration value is the concentration of object element in the testing sample.
Accuracy for verification method; When using each element mass concentration to be respectively carbon: 60.26%, hydrogen: 2.75%, nitrogen: 1.06% coal sample is as testing sample; The mass concentration that obtains its carbon after tested is 61.46%; Measuring relative errors is 2.0%, and visible this method precision is higher, can accords with production need.
Principle of work of the present invention is:
The LIBS technology is meant that sample can be gasificated into high temperature, highdensity plasma in moment when intense pulse laser shines on the sample through focusing on, and the plasma cognition that is in excited state externally discharges different rays.Wavelength that the plasma emission spectroscopy spectral line is corresponding and intensity reflect the component and its concentration in the object of surveying respectively.This technology has high detection sensitivity, and cost is lower, can be simultaneously multiple element such as be analyzed at advantage.
The present invention utilizes the laser after the focusing to see through the glass pallet from glass pallet below and impacts powdered sample; At the inner plasma that produces of the powdered sample at the surface of contact place of powdered sample and glass pallet; Prevent to splash after powder from receiving the laser pulse effect, not only cause the distance of condenser lens and sample surfaces to change, and the powdered sample that splashes can absorb laser pulse next time; The energy that causes arriving sample surfaces reduces, and finally reduces Measurement Uncertainty.Compare with disclosed other measuring methods based on LIBS, the operation that the present invention need not be pressed to powdered sample makes this method to be applied on the fast on-line measurement better.
In addition; At the inner plasma that produces of powdered sample; Because the influence of the gravity of powdered sample own, powder bed can produce the space constraint effect by the article on plasma body, can strengthen line strength of plasma emission spectroscopy so to a certain extent; Increase the signal to noise ratio (S/N ratio) of characteristic spectral line, reduce the detectability of object element.The good effect that the space constraint effect is measured LIBS is at patent documentation (application number: illustrate 201110040537.7); Space constraint effect through cavity; Plasma shape changes and reduces; The ablation quality is also more stable, can reduce the uncertainty of experiment like this, thereby makes calibration curve that the better goodness of fit arranged.
Utilize double-pulse laser to produce plasma, have the following advantages than monopulse laser.At first; Gas around the plasma that first pulse produces makes thins out; Shielding action to follow-up laser energy weakens to some extent; Second pulse has more laser energy to be used to the sample of ablating, so total population increases to some extent in the plasma, helps reducing the LIBS Measurement Uncertainty; The second, owing to absorb increasing of laser energy, the radiant light signal of plasma is strengthened greatly, helps detecting of the lower element of mass concentration.The 3rd, through the heat effect of second pulse, electron density is higher in the plasma, and distribution of particles is more even, more near local thermodynamic equilibrium's state, helps improving the goodness of fit and the precision of prediction of calibration model.
Claims (1)
1. based on the flour constituent content measuring method of double-pulse laser, it is characterized in that this method has comprised following steps:
1) element of desire in the sample being measured is decided to be object element; With the known one group of powdered sample of object element mass concentration as calibration sample; The object element concentration of each calibration sample is designated as C respectively
1, C
2, C
3
2) choose any one kind of them in one group of calibration sample from step 1) and be tiled on the transparent glass pallet (4);
3) utilize the LIBS system to detect: to adopt two pulsed lasers; First pulsed laser (1) and second pulsed laser (2) are placed the below of glass pallet; The position of two pulsed lasers and calibration sample conllinear or conllinear not; With the pulsed laser is excitation source;, first pulsed laser emitting laser passes the glass pallet after focusing on through condenser lens (3), the position of adjustment condenser lens, and the laser after feasible the focusing is at the inner plasma (6) that produces of the calibration sample (5) and the calibration sample at the surface of contact place of glass pallet; After the time interval through 5～10 μ s, focus on the plasma (6) from second pulsed laser emitting laser, the article on plasma body heats;
4) the radiant light signal of plasma generation is collected through the collection lens (7) that the glass pallet is set at glass pallet bottom; Through optical fiber (8) lead-in light spectrometer (9); Gathered by computing machine (10) through changing into electric signal behind the spectrometer; Obtain step 2) in the characteristic light spectrogram of selected calibration sample, from this characteristic light spectrogram, obtain the characteristic spectral line intensity I of object element;
5) to each calibration sample repeating step 2) to step 4), obtain the corresponding object element characteristic spectral line intensity I of each calibration sample successively
1, I
2, I
3
6) with the object element concentration C
1, C
2, C
3Be independent variable, the characteristic spectral line intensity I
1, I
2, I
3For dependent variable is set up calibration curve through approximating method, the equation of calibration curve is y=f (x), and wherein, x is an independent variable, and y is a dependent variable;
When 7) the unknown testing sample of object element mass concentration being detected, at first testing sample is handled, obtained line strength I of object element in the testing sample according to step 1) to step 4)
c, on calibration curve, find I then
cPairing concentration value is the concentration of object element in the testing sample.
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103063623A (en) * | 2012-12-26 | 2013-04-24 | 清华大学 | Method for increasing measurement accuracy of laser induced breakdown spectroscopy |
| CN104374778A (en) * | 2014-11-27 | 2015-02-25 | 南京大学 | Optical system of low-temperature scanning laser microscope |
| CN114486772A (en) * | 2021-12-29 | 2022-05-13 | 中国烟草总公司郑州烟草研究院 | Heavy metal detection equipment and detection method for cigarette products |
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Patent Citations (4)
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| JPH05104266A (en) * | 1991-05-16 | 1993-04-27 | Nikon Corp | Laser beam machine |
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|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103063623A (en) * | 2012-12-26 | 2013-04-24 | 清华大学 | Method for increasing measurement accuracy of laser induced breakdown spectroscopy |
| CN104374778A (en) * | 2014-11-27 | 2015-02-25 | 南京大学 | Optical system of low-temperature scanning laser microscope |
| CN114486772A (en) * | 2021-12-29 | 2022-05-13 | 中国烟草总公司郑州烟草研究院 | Heavy metal detection equipment and detection method for cigarette products |
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