CN106442431A - Correction method for improving repeatability of LIBS (Laser-Induced Breakdown Spectroscopy) technique measured sample - Google Patents
Correction method for improving repeatability of LIBS (Laser-Induced Breakdown Spectroscopy) technique measured sample Download PDFInfo
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- CN106442431A CN106442431A CN201610798296.5A CN201610798296A CN106442431A CN 106442431 A CN106442431 A CN 106442431A CN 201610798296 A CN201610798296 A CN 201610798296A CN 106442431 A CN106442431 A CN 106442431A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
Abstract
The invention discloses a correction method for improving the repeatability of an LIBS (Laser-Induced Breakdown Spectroscopy) technique measured sample. The principle is that data of the plasma spectrum of a sample is corrected by utilizing a regression correlation expression obtained by the relevance regression of the data of air plasma spectrum. As an experimental environment is stable, the air plasma spectrum is stored in a database as a standard spectrum. When the repeatability of the LIBS technique measured sample is abnormal, the air plasma spectrum at the moment is measured anew; the spectrum is subjected to the relevance regression with the standard air plasma spectrum stored in the database to obtain the regression correlation expression; the plasma spectrum of the sample is corrected by applying the correlation expression; the final plasma spectrum of the sample is obtained. By using the correction method for improving the repeatability of the LIBS technique measured sample, the repeatability of the LIBS technique measured sample is effectively improved; the method is simple and reliable.
Description
Technical field
The present invention relates to improving the modification method of LIBS commercial measurement sample repeatability, utilize airlight particularly to one kind
Spectrum correlation returns the method revising sample spectra.
Background technology
LIBS (Laser-Induced Breakdown Spectroscopy, LIBS) technology adopts arteries and veins
Impulse light as the induction instrument of emission spectrographic analysis, by need not or simple sample pretreatment, micro- to sample damage and polynary
Element such as simultaneously and rapidly detects at the advantage, has progressively developed into a kind of potential industrial process online measuring technique, has been attempted application
Quality control or condition diagnosing in various industrial process.But due to technology own characteristic, when carrying out repeated measure, sample
Spectroscopic data unstable, repeatability is poor, directly affects LIBS technology to the accuracy of sample repeated measure and reliability,
So it is particularly important to improve LIBS technology repeatability.
Content of the invention
It is an object of the invention to provide a kind of modification method of raising LIBS commercial measurement sample repeatability.Using air
Spectroscopic data (repeating to test new survey air spectrum and data base's Plays air spectroscopic data) carries out dependency recurrence, by
The correlation that returns arriving realizes the correction to sample spectra.
The technical scheme is that：
1. a kind of modification method of raising LIBS commercial measurement sample repeatability is it is characterised in that comprise the steps：
1) repeat measuring samples plasma spectrometry during experiment and with air plasma spectrum and record its data；
2) the air plasma spectroscopic data of new measurement is entered with data base's Plays air plasma spectroscopic data
Row dependency returns, and obtains returning correlation；
3) new test sample product plasma spectrometry is brought into 2) the recurrence correlation of gained obtains revised sample plasma
Body spectrum；
2. the modification method of a kind of raising LIBS commercial measurement sample repeatability according to claim 1, its feature
Be the 1st), 2) spectroscopic data described in step be the several points that transverse and longitudinal coordinate is respectively wavelength and peak intensity data set.
3. the modification method of a kind of raising LIBS commercial measurement sample repeatability according to claim 1, its feature
It is the 2nd) the air plasma spectrum that comprises standard of the data base described in step.
4. the modification method of a kind of raising LIBS commercial measurement sample repeatability according to claim 1, its feature
It is the 2nd) dependency described in step returns is returning of carrying out of the spectral intensity to the air plasma in same spectral range
Return.
5. the modification method of a kind of raising LIBS commercial measurement sample repeatability according to claim 1, its feature
It is the 2nd) dependency described in step returns is least square regression, and think that normal air spectrum is independent variable, newly survey air
Spectroscopic data is dependent variable.
6. the modification method of a kind of raising LIBS commercial measurement sample repeatability according to claim 1, its feature
It is the 2nd) the recurrence correlation described in step is linear or nonlinear equation.The invention has the advantages that：
The present invention passes through to be combined regression analyses in mathematical statisticss with LIBS, there is provided Yi Zhongti
The modification method of high LIBS commercial measurement sample repeatability, using air plasma middle-low alloy steels sample plasma spectrum
Simple and reliable, convenient and swift the spectroscopic data repeating to test can be modified, effectively improve the repeatability of LIBS technology, reproduce
Property, make data normalization.
Brief description
Fig. 1 is the flow chart of modification method of the present invention；
The linear equation that the recurrence of Fig. 2 air plasma spectroscopic data dependency obtains；
It is right after first time experiment, second experiment, correction that Fig. 3 Fig. 7 is embodied as Mg, Ca characteristic spectral line in case
Than.
Specific embodiment
In conjunction with the flow diagram shown in Fig. 1, a kind of raising LIBS commercial measurement sample repeatability proposed by the present invention
Modification method, includes following steps：
1) measure powder sample (in the present embodiment, particles used stream sample is different meshes powdered mineral quality sample)
80,100,150,200,325,400 mesh powder samples are gathered 200 data, then it are averaging by spectroscopic data respectively,
It is stored in data base.Air spectroscopic data, it is believed that normal air spectrum, gathers 100 and is averaging, be stored in data at that time for measurement
Storehouse.
2) carry out repeating to test (consistent with first time experiment condition).Equally measure and record 200 sample spectra respectively
Data is averaged, and 100 air spectroscopic datas are averaged.
3) quasi- for first time institute's mark air spectroscopic data is set to independent variable X, second surveyed air spectroscopic data is set to
Dependent variable Y, after dependency returns, (this example application linear regression) obtains equation of linear regression Y=-48.34736+1.12128X.
4) will second sample spectral data Y surveyed ' bring Y=-48.34736+1.12128X into and obtain corresponding X '
Be then revised sample spectral data, will for the first time surveyed sample spectra, sample light after second surveyed sample spectra, correction
Spectrum drawing (Fig. 3-Fig. 7) compares.Second surveyed sample spectra can be kept with surveyed sample spectra for the first time after revising
Extraordinary concordance, illustrates to effectively improve the repeatability of LIBS measurement by the correction of air plasma spectrum.
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention
Embodiment restriction.For those of ordinary skill in the field, can also make on the basis of the above description
The change of other multi-forms or variation.There is no need to be exhaustive to all of embodiment.All the present invention's
Any modification, equivalent and improvement made within spirit and principle etc., should be included in the protection of the claims in the present invention
Within the scope of.
Claims (6)
1. a kind of modification method of raising LIBS commercial measurement sample repeatability is it is characterised in that comprise the steps：
1) repeat measuring samples plasma spectrometry during experiment and with air plasma spectrum and record its data；
2) the air plasma spectroscopic data of new measurement is carried out phase with data base's Plays air plasma spectroscopic data
Closing property returns, and obtains returning correlation；
3) new test sample product plasma spectrometry is brought into 2) the recurrence correlation of gained obtains revised sample plasma light
Spectrum.
2. a kind of raising LIBS commercial measurement sample repeatability according to claim 1 modification method it is characterised in that
1st), 2) spectroscopic data described in step is the data set of the several points that transverse and longitudinal coordinate is respectively wavelength and peak intensity.
3. a kind of raising LIBS commercial measurement sample repeatability according to claim 1 modification method it is characterised in that
2nd) data base described in step comprises the air plasma spectrum of standard.
4. a kind of raising LIBS commercial measurement sample repeatability according to claim 1 modification method it is characterised in that
2nd) dependency described in step returns is the recurrence that the spectral intensity to the air plasma in same spectral range is carried out.
5. a kind of raising LIBS commercial measurement sample repeatability according to claim 1 modification method it is characterised in that
2nd) dependency described in step returns is least square regression, and thinks that normal air spectrum is independent variable, new survey air spectrum
Data is dependent variable.
6. a kind of raising LIBS commercial measurement sample repeatability according to claim 1 modification method it is characterised in that
2nd) the recurrence correlation described in step is linear or nonlinear equation.
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| CN106442431A true CN106442431A (en) | 2017-02-22 |
| CN106442431B CN106442431B (en) | 2019-05-17 |
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Citations (7)
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| CN101509872A (en) * | 2009-03-20 | 2009-08-19 | 清华大学 | Coal quality on-line detecting analytical method based on regression analysis |
| CN101949852A (en) * | 2010-07-30 | 2011-01-19 | 清华大学 | Spectral standardization-based coal quality on-line detection method |
| CN102507512A (en) * | 2011-11-07 | 2012-06-20 | 大连理工大学 | On-line in situ detecting method for infrared-ultraviolet double pulse laser induced breakdown spectroscopy |
| CN102830096A (en) * | 2012-08-29 | 2012-12-19 | 国电燃料有限公司 | Method for measuring element concentration and correcting error based on artificial neural network |
| CN103234944A (en) * | 2013-04-17 | 2013-08-07 | 清华大学 | Coal quality characteristic analysis method based on combination of dominant factors and partial least square method |
| CN104697966A (en) * | 2015-03-10 | 2015-06-10 | 西北大学 | Method for quantitatively analyzing chromium and manganese in steel based on least square support vector machine algorithm combined with laser-induced breakdown spectroscopy |
| CN105044050A (en) * | 2015-07-07 | 2015-11-11 | 中国农业大学 | Rapid quantitative analysis method for metallic elements in crop straw |
-
2016
- 2016-08-31 CN CN201610798296.5A patent/CN106442431B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101509872A (en) * | 2009-03-20 | 2009-08-19 | 清华大学 | Coal quality on-line detecting analytical method based on regression analysis |
| CN101949852A (en) * | 2010-07-30 | 2011-01-19 | 清华大学 | Spectral standardization-based coal quality on-line detection method |
| CN102507512A (en) * | 2011-11-07 | 2012-06-20 | 大连理工大学 | On-line in situ detecting method for infrared-ultraviolet double pulse laser induced breakdown spectroscopy |
| CN102830096A (en) * | 2012-08-29 | 2012-12-19 | 国电燃料有限公司 | Method for measuring element concentration and correcting error based on artificial neural network |
| CN103234944A (en) * | 2013-04-17 | 2013-08-07 | 清华大学 | Coal quality characteristic analysis method based on combination of dominant factors and partial least square method |
| CN104697966A (en) * | 2015-03-10 | 2015-06-10 | 西北大学 | Method for quantitatively analyzing chromium and manganese in steel based on least square support vector machine algorithm combined with laser-induced breakdown spectroscopy |
| CN105044050A (en) * | 2015-07-07 | 2015-11-11 | 中国农业大学 | Rapid quantitative analysis method for metallic elements in crop straw |
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