CN102680435A - Standard-sample-free quantitative analysis method for element components through laser-induced breakdown spectroscopy - Google Patents
Standard-sample-free quantitative analysis method for element components through laser-induced breakdown spectroscopy Download PDFInfo
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- CN102680435A CN102680435A CN2012101700030A CN201210170003A CN102680435A CN 102680435 A CN102680435 A CN 102680435A CN 2012101700030 A CN2012101700030 A CN 2012101700030A CN 201210170003 A CN201210170003 A CN 201210170003A CN 102680435 A CN102680435 A CN 102680435A
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- 238000002536 laser-induced breakdown spectroscopy Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 10
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 9
- 238000005259 measurement Methods 0.000 claims abstract description 14
- 230000005283 ground state Effects 0.000 claims description 19
- 230000005281 excited state Effects 0.000 claims description 14
- 238000012113 quantitative test Methods 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000005284 excitation Effects 0.000 abstract 2
- 210000002381 plasma Anatomy 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
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Abstract
The invention discloses a standard-sample-free quantitative analysis method for element components through a laser-induced breakdown spectroscopy. According to the invention, the energy of a pulse laser is controlled to ensure that plasmas have the same temperature during every time measurement, and therefore, the ratio of the stationary state intensity of each element to the excitation state intensity of each element is constant during every time measurement; and the atom number ratio of all the elements in a mixture is determined through comparing the stationary state peak intensities of the different elements, thus quantitative analysis is realized. The temperatures of the plasmas are controlled, i.e., the ratio of the stationary state peak of each element to the excitation state peak of each element is determined, and therefore, the comparability of each measurement result is remained, and a precise and repeated element component analysis result is obtained.
Description
Technical field
The present invention relates to the material analysis technical field of measurement and test, relate in particular to a kind of method of utilizing LIBS to carry out quantitative elementary analysis.
Background technology
LIBS be a kind of development in recent years rapidly based on the ultimate analysis method of testing of plasma emission spectroscopy, can carry out constituent analysis to solid-state, liquid state and gaseous sample, application is very wide.But as a kind of ultimate analysis instrument of practicality, laser induced breakdown spectrograph also has a lot of scientific problems to need to solve, and particularly its quantitative test also fundamentally is not resolved so far, has greatly restricted further developing of it.This is because the interaction process of laser and object is very complicated; It is very many to influence isoionic factor, and the atmosphere the when composition of the energy of laser pulse, multiplicity, wavelength, sample, the content of element to be measured, test, the factors such as focusing situation of laser all can produce very big influence to signal.Though can improve precision through Standard Method and complex mathematical computing, repeatability is very poor, and ratio error is still very big mutually with other ripe quantitative elementary analysis methods.
When sample during by powerful pulsed laser irradiation, temperature sharply raises near the sample surfaces of Stimulated Light irradiation area, near the irradiated area, forms plasma behind the atomic ionization.Pulsed laser power is different, and the temperature of plasma is also different, and then the ionized state of each element is also different.When plasma temperature was low, the emission peak of element ground state correspondence was stronger in the LIBS.On the contrary, when plasma temperature was higher, the emission peak of element excited state correspondence was stronger in the LIBS.Therefore,, just can't confirm the ionized state of element in the plasma, can't confirm the ratio of element ground state and each excited state in other words if do not control isoionic temperature when measuring.In this case, we can't obtain accurate quantitative analysis results through the intensity of measuring each some peak of element simply.
Summary of the invention
The present invention is directed to the deficiency of prior art, a kind of method that realizes that LIBS quantitative analysis of non-sampler element is formed is provided.
The technical scheme that technical solution problem of the present invention is taked is:
The temperature of plasma was identical when this method utilized the energy of gating pulse laser instrument to make each the measurement; The ground state of each element and the ratio of excited state intensity remain unchanged when guaranteeing each the measurement thus; Confirm each the element atom number ratio in the potpourri through contrasting different element ground state peak intensities, realize quantitative test.
Described gas ions is that element to be analyzed is through the laser-induced breakdown gained.
The invention has the beneficial effects as follows:, be equivalent to confirm the ratio at element ground state peak and excited state peak through the temperature of control plasma.The comparability that can keep each measurement result thus obtains accurate recursive elemental composition analysis result.
Description of drawings
Fig. 1: every pulse 100mJ, per second 5 subpulse laser energies excite down, the peak intensity ratio of AlI of Al element (ground state) and AlII (a certain excited state).
Fig. 2: be the strength ratio of Al II/Al I in tested five groups of samples.
Fig. 3: Ti/Al is than the relation of the ground state emission peak strength ratio of the concentration of Ti in the different samples and Ti and Al element.
Fig. 4: Zn/Al is than the relation of the ground state emission peak strength ratio of the concentration of Zn in the different samples and Zn and Al element.
Fig. 5: Zn/Fe is than the relation of the ground state emission peak strength ratio of the concentration of Zn in the different samples and Zn and Fe element.
Embodiment
The present invention is through the energy of the laser pulse of gating pulse laser instrument output, monitors the ratio at a certain common element ground state peak and a certain excited state peak in the testing sample simultaneously, and this ratio is the value confirmed when making each the measurement.Because the ratio of element ground state peak and excited state peak intensity is relevant with the temperature of plasma, so the ratio of having confirmed this element ground state peak and excited state peak has been equivalent to confirm the temperature of plasma.As long as keep the ratio of ground state and excited state peak intensity of this element constant during each the measurement, the ratio at the ground state peak of other elements and excited state peak also remains unchanged so.The present invention has not only improved the repeatability of laser induced breakdown spectrograph quantitative test greatly, and does not need standard specimen can obtain very high precision.
Specify the present invention according to specific embodiment below, it is more obvious that the object of the invention and effect will become.
Embodiment 1:
Analytical approach used in the present invention is applicable to the quantitative test of all elements, and specimen in use is TiO in this instance
2And Al
2O
3Potpourri, wherein, the molar percentage concentration of the relative Al of Ti is respectively 0.5%, 1%, 2%, 3%, 4%.The practical implementation step is following:
(1) opens spectrometer;
(2) open laser instrument;
(3) monitor the intensity of Al I (ground state) and Al II (a certain excited state) signal, and on screen, show both ratio in real time;
(4) the output energy of change laser instrument makes that the intensity of Al I and Al II signal is a determined value.In this example, the intensity rate of Al I and Al II signal is decided to be 2:1 (as shown in Figure 1);
(5) record LIBS at this moment;
(6) vary article, repeating step 3-5 guarantees when measuring that the strength ratio of Al I and Al II signal is constant at every turn, and the temperature of plasma is fixed value (as shown in Figure 2, the Al II/Al I strength ratio of five groups of samples is definite value) when guaranteeing every group of sample measurement;
(7) calculate the intensity at Ti I peak and Al I peak in each sample, both intensity rates are the ratio that corresponding element is formed, and the result is as shown in Figure 3.
Fig. 3 shows that there is simple linear relationship in the Ti I peak that above-mentioned steps obtains according to the present invention with the intensity rate at Al I peak, through match get that the Ti/Al composition compares and the peakedness ratio that measures between relation be:
Wherein
/
Represent Ti and Al atoms of elements number ratio,
I Ti / I Al Represent the strength ratio at Ti I peak and Al I peak.In method used in the present invention, do not add marker, only the induced with laser spectrum from potpourri self can obtain quantitative analysis results.TiO for arbitrary proportion
2And Al
2O
3Potpourri; As long as detect the strength ratio at its Ti I peak and Al I peak; Can from graph of a relation, perhaps utilize fitting formula directly to obtain Ti element and Al atoms of elements number ratio in the potpourri, analytical approach proposed by the invention can obtain reliable quantitative analysis results.
Embodiment 2:
Specimen in use is ZnO and Al in this instance
2O
3Potpourri, wherein, the molar percentage concentration of the relative Al of Zn is respectively 1%, 2%, 3%, 4%, 5%.The practical implementation step is following:
(1) opens spectrometer;
(2) open laser instrument;
(3) monitor the intensity of Al I (ground state) and Al II (a certain excited state) signal, and on screen, show both ratio in real time;
(4) the output energy of change laser instrument makes that the intensity of Al I and Al II signal is a determined value.In this example, the intensity rate of Al I and Al II signal is decided to be 2:1;
(5) record LIBS at this moment;
(6) vary article, repeating step 3-5 guarantees when measuring that the strength ratio of Al I and Al II signal is constant at every turn, and the temperature of plasma is a fixed value when guaranteeing every group of sample measurement;
(7) calculate the intensity at Zn I peak and Al I peak in each sample, both intensity rates are the ratio that corresponding element is formed, and the result is as shown in Figure 4.
Embodiment 3:
Specimen in use is ZnO and Fe in this instance
2O
3Potpourri, wherein, the molar percentage concentration of the relative Fe of Zn is respectively 1%, 2%, 3%, 4%, 5%.The practical implementation step is following:
(1) opens spectrometer;
(2) open laser instrument;
(3) monitor the intensity of Fe I (ground state) and Fe II (a certain excited state) signal, and on screen, show both ratio in real time;
(4) the output energy of change laser instrument makes that the intensity of Fe I and Fe II signal is a determined value.In this example, the intensity rate of Fe I and Fe II signal is decided to be 2:1;
(5) record LIBS at this moment;
(6) vary article, repeating step 3-5 guarantees when measuring that the strength ratio of Fe I and Fe II signal is constant at every turn, and the temperature of plasma is a fixed value when guaranteeing every group of sample measurement;
(7) calculate the intensity at Zn I peak and Fe I peak in each sample, both intensity rates are the ratio that corresponding element is formed, and the result is as shown in Figure 5.
Claims (1)
1. the method formed of a LIBS quantitative analysis of non-sampler element; It is characterized in that: the temperature of plasma was identical when this method utilized the energy of gating pulse laser instrument to make each the measurement; The ground state of each element and the ratio of excited state intensity remain unchanged when guaranteeing each the measurement thus; Confirm each the element atom number ratio in the potpourri through contrasting different element ground state peak intensities, realize quantitative test; Described gas ions is that element to be analyzed is through the laser-induced breakdown gained.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103234943A (en) * | 2013-04-09 | 2013-08-07 | 杭州电子科技大学 | Method for rapidly detecting metal thermal diffusion with laser-induced breakdown spectroscopy technology |
| CN104865228A (en) * | 2015-06-02 | 2015-08-26 | 中国科学院上海技术物理研究所 | Quantitative laser-induced breakdown spectroscopy (LIBS) detecting method based on fusion entropy optimization |
| WO2024068925A1 (en) * | 2022-09-30 | 2024-04-04 | Advanced Osteotomy Tools - Aot Ag | Biological tissue analysis device and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011130804A1 (en) * | 2010-04-23 | 2011-10-27 | Datatrace Dna Pty Limited | System and method for establishing the integrity of items using laser induced breakdown spectroscopy |
| CN102313731A (en) * | 2010-07-09 | 2012-01-11 | 中国科学院沈阳自动化研究所 | Method for detecting content of component in unknown object on line |
| CN102410993A (en) * | 2011-08-01 | 2012-04-11 | 清华大学 | Element measurement method based on laser-induced plasma emission spectral standardization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011130804A1 (en) * | 2010-04-23 | 2011-10-27 | Datatrace Dna Pty Limited | System and method for establishing the integrity of items using laser induced breakdown spectroscopy |
| CN102313731A (en) * | 2010-07-09 | 2012-01-11 | 中国科学院沈阳自动化研究所 | Method for detecting content of component in unknown object on line |
| CN102410993A (en) * | 2011-08-01 | 2012-04-11 | 清华大学 | Element measurement method based on laser-induced plasma emission spectral standardization |
Non-Patent Citations (1)
| Title |
|---|
| 季振国等: "激光诱导击穿光谱及其在元素分析中的应用", 《材料科学与工程学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103234943A (en) * | 2013-04-09 | 2013-08-07 | 杭州电子科技大学 | Method for rapidly detecting metal thermal diffusion with laser-induced breakdown spectroscopy technology |
| CN104865228A (en) * | 2015-06-02 | 2015-08-26 | 中国科学院上海技术物理研究所 | Quantitative laser-induced breakdown spectroscopy (LIBS) detecting method based on fusion entropy optimization |
| CN104865228B (en) * | 2015-06-02 | 2017-08-15 | 中国科学院上海技术物理研究所 | The quantitative LIBS detection method solved based on fusion entropy optimization |
| WO2024068925A1 (en) * | 2022-09-30 | 2024-04-04 | Advanced Osteotomy Tools - Aot Ag | Biological tissue analysis device and method |
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