CN101067603A - Double-path resonance enhanced laser guidence breakdown spectral trace element analyser and method - Google Patents
Double-path resonance enhanced laser guidence breakdown spectral trace element analyser and method Download PDFInfo
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- CN101067603A CN101067603A CN 200710028438 CN200710028438A CN101067603A CN 101067603 A CN101067603 A CN 101067603A CN 200710028438 CN200710028438 CN 200710028438 CN 200710028438 A CN200710028438 A CN 200710028438A CN 101067603 A CN101067603 A CN 101067603A
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Abstract
The invention discloses a double channel resonance enhancement laser induction penetrate spectrum trace element analyzer, which includes the laser, the monochromator, the photo detector, the oscilloscope and the computer, the states laser through the beam-splitting piece BS connects the sample channel and the photo source channel light signal; there is lens L1, the resonance photo source, coupling lens assembly L3 and L4 in turn installs on the photo source channel; there is reflector RM1, lens L2 in turn on the sample channel; the sample channel and photo source channel connect with the sample light signal, the sample through the light gather system connects the monochromator light signal, the monochromator connects the photo detector, the photo detector connects the oscillograph, the oscillograph connects the computer. The invention also discloses an analysis method of the double channel resonance enhancement laser induction penetrate spectrum trace element analyzer. The analyzer has simple structure and low cost, greatly enhanced the analysis sensitivity and reduced the examination limit.
Description
Technical field
The present invention relates to use atomic spectroscopy, use laser spectroscopy and atomic spectroscopic analysis technical field, particularly a kind of double-path resonance enhanced laser guidence breakdown spectral trace element analyser and method.
Background technology
Laser-induced Breakdown Spectroscopy (Laser-Induced Breakdown Spectroscopy, LIBS) technology is a kind of novel atomic spectroscopic analysis technology, the intense pulse laser that its utilize to focus on directly is excited into plasma with testing sample and luminous, realizes ultimate analysis to sample by analyzing atom in the plasma or ion spectra.Owing to need not the complicated sample set-up procedure, the characteristics that LIBS has fast and multielement is analyzed simultaneously, and can realize telemeasurement under field, real-time online and the rugged surroundings, thereby receive great concern, be widely used in the ultimate analysis of various different occasions.
The detectability of LIBS, the least concentration of its element that can analyze just, it is a very important techniques index, when being used for trace element analysis, its detectability is low more good more, need to take different means to reduce the detectability of LIBS for this reason, just improve the sensitivity for analysis of LIBS system.In real-life a lot of fields, all need some objectionable impurities is done the analysis of trace element, such as environmental sample (is comprised soil, water and atmosphere), the toxic heavy metal element (As, Hg, Cd, Cr, Pb etc.) in the Chinese herbal medicine, food, various commodity makes on-the-spot express-analysis, with the threat of avoiding causing, therefore have very important significance to health and life security because of these heavy metal elements.
The technology of at present existing in the world reduction LIBS detectability includes: one, adopt the dipulse excitation mode: adopt the dipulse excitation mode to need the double-pulse laser device of special development, this laser instrument price is than the single pulse laser costliness, or with two cover laser instruments, system is also relatively more expensive; Two, adopt resonance to strengthen excitation mode and LIBS and laser-induced fluorescence (LIF) (Laser-inducedfluorescence, LIF) coupling technique: adopt resonance enhancing excitation mode and LIBS-LIF coupling technique then to need two cover laser systems, not only expensive, and bulky, system complex; Three, adopt advanced Photoelectric Detection equipment: blazed grating spectrometer, ICCD (Intensified Charge-CoupledDevice), however have the LIBS system price costliness of ICCD, and ICCD data reading speed is slow, and is low etc. in ultraviolet region sensitivity.
Summary of the invention
The present invention is in order to overcome the deficiency that above prior art exists, provide a kind of simple in structure, cost is low, have the double-path resonance enhanced laser guidence breakdown spectral trace element analyser of higher sensitivity for analysis.
Another object of the present invention is to provide a kind of analytical approach of double-path resonance enhanced laser guidence breakdown spectral trace element analyser.
Purpose of the present invention realizes by following technical scheme: this double-path resonance enhanced laser guidence breakdown spectral trace element analyser, comprise laser instrument, monochromator, photodetector, oscillograph and computing machine, it is characterized in that: described laser instrument is connected with sample channel, light source passage light signal by beam splitting chip BS; On the light source passage, be disposed with lens L1, resonance light source, coupled lens group L3 and L4; On sample channel, be disposed with catoptron RM1, lens L2; Sample channel, light source passage are connected with the sample light signal, and sample is connected with the monochromator light signal by light collecting system, and monochromator is connected with photodetector, and photodetector is connected with oscillograph, and oscillograph is connected with computing machine.
Described light collecting system comprises lens L5, catoptron RM2 and lens L6; Light collecting system is connected with the entrance slit light signal of monochromator.
Described oscillograph is connected with computing machine by gpib interface.
Described laser instrument is electric-optically Q-switched Pulse Nd: YAG laser instrument (nanosecond (10
-9Second) pulsed laser), also can be psec (10
-12Second) or femtosecond (10
-15Second) pulsed laser.
Described resonance light source is the plasma source of induced with laser.
Described monochromator is a grating monochromator.
Described oscillograph is a digital storage oscilloscope.
Described photodetector is a photomultiplier.
The analytical approach of above-mentioned double-path resonance enhanced laser guidence breakdown spectral trace element analyser is characterized in that may further comprise the steps:
(1) laser that sends of described laser instrument is divided into two-way light through beam splitting chip BS and enters sample channel and light source passage respectively;
(2) focused on the resonance light source at described light source passage glazed thread by lens L1, produce strong laser induced plasma resonance optical radiation,, focus on sample through coupled lens group L3 and L4;
(3) focus on sample at described sample channel glazed thread by catoptron RM1 reflection and through lens L2;
(4) under the effect of the light of sample channel, the trace element to be analyzed in the described sample is dissociated out, and described then trace element is by described resonance optical radiation resonance excitation, and described trace element sends resonance and strengthens optical radiation;
(5) described resonance enhancing optical radiation is imaged on the monochromator by light collecting system;
(6) light signal of described monochromator is surveyed through photodetector, is converted to electric signal;
(7) described electric signal is sent to the oscillograph demonstration;
(8) described oscillograph sends data message to that computing machine is noted down and data processing.
The present invention has following advantage with respect to prior art: this double-path resonance enhanced laser guidence breakdown spectral trace element analyser, simple in structure, cost is low, is mainly used in various sample is done qualitative and quantitative ultimate analysis, especially trace element analysis.
This analysis instrument utilization resonance light source produces strong laser induced plasma resonance optical radiation.Under the effect of the light of sample channel, trace element to be analyzed in the sample is dissociated out, the trace element optical radiation resonance excitation that resonated then, trace element sends resonance and strengthens optical radiation, therefore make the sensitivity for analysis of Laser-induced Breakdown Spectroscopy trace element analysis instrument improve 1 to 2 order of magnitude, thereby make the trace element analysis that only just can realize various samples, need not to adopt expensive laser instrument and spectral instrument and Photoelectric Detection equipment with conventional laser instrument and analyser.The analytical approach of this analysis instrument has improved the sensitivity for analysis of analyser greatly, reduces detectability, is particularly useful for the analysis to trace element.
This analysis instrument can also realize that simultaneously resonance excitation is to reduce its detectability to two or more trace element, and this is difficult to realize with tunable laser source, because tunable laser source is difficult to be operated in simultaneously a plurality of wavelength.
Description of drawings
Fig. 1 is the structural representation of a kind of double-path resonance enhanced laser guidence breakdown spectral trace element analyser of the present invention.
Fig. 2 is the test findings figure that the analyser of employing Fig. 1 is tested.
Fig. 3 is the test findings figure that the analyser of employing Fig. 1 carries out another test.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Embodiment 1
A kind of double-path resonance enhanced laser guidence breakdown spectral trace element analyser as shown in Figure 1, Nd:YAG is electric-optically Q-switched Pulse Nd among the figure: YAG laser instrument (Beijing epoch Zhuo Yi, TurboLite), its output wavelength is 1064nm, pulsewidth is 10ns, repetition rate is 5Hz, the about 200mJ of pulse energy; BS (beam splitter) is a beam splitting chip; RM1 and RM2 (reflection mirror) are catoptron; L1～L6 is lens, and each focal length of lens is: L1, L2 and L3, f=10cm, L4 and L5, f=15cm, L6, f=25cm; PMT (photomultiplier tube) is photomultiplier (shore pine, a CR114 type).The resonance light source is the plasma source of the induced with laser of simple substance, compound or potpourri, looks different elements to be analyzed with different; Sample is a sample to be analyzed; Monochromator is grating monochromator (spectrum is opened up in Tianjin, the WDS-5 type), and focal length is 50cm; Oscillograph be the 250MHz digital storage oscilloscope (GWinstek, GDS-840C); Computing machine is desktop computer commonly used.
The analytical approach of the double-path resonance enhanced laser guidence breakdown spectral trace element analyser among Fig. 1 may further comprise the steps:
(1) laser that sends of laser instrument is divided into two-way light through beam splitting chip BS and enters sample channel and light source passage respectively;
(2) focused on the resonance light source at described light source passage glazed thread by lens L1, produce strong laser induced plasma resonance optical radiation,, focus on sample through coupled lens group L3 and L4;
(3) focus on sample at described sample channel glazed thread by catoptron RM1 reflection and through lens L2;
(4) under the effect of the light of sample channel, the trace element to be analyzed in the described sample is dissociated out, and described then trace element is by described resonance optical radiation resonance excitation, and described trace element sends resonance and strengthens optical radiation;
(5) described resonance strengthens optical radiation scioptics L5, catoptron RM2, lens L6 are imaged on the entrance slit of monochromator;
(6) light signal of described monochromator is surveyed through photomultiplier, is converted to electric signal;
(7) described electric signal is sent to the oscillograph demonstration;
(8) described oscillograph sends data message to by gpib interface that computing machine is noted down and data processing.
Embodiment 2
Fig. 2 is the test findings figure that the analyser of employing Fig. 1 is tested.
For observing the experiment effect of Na atom two-wire binary channels resonance enhanced laser induced breakdown spectroscopy, what sample was selected is the aluminium alloy that contains micro-Na atom, and the resonance light source in the light source passage is for soaking the wood chip of supersaturation NaCl solution.
Horizontal ordinate is wavelength (unit is a nanometer) among the figure, and ordinate is a luminous intensity.
(a) curve among the figure: sample channel is sheltered from, only remaining light source passage, be straight line this moment, the strong laser induced plasma resonance optical radiation that the light source that resonates has been described can not be collected into monochromator and cause background signal.
(b) curve among the figure: the light source passage is sheltered from, only remaining sample channel, this curve is the curve of prior art just.
(c) curve among the figure: light source passage and sample channel do not block, and observe Na atom two-wire in the aluminium alloy this moment, and (588.995, luminous intensity 589.592nm) has strengthened about 4 times with respect to curve (b).
If the Na atomic concentration further reduces in the aluminium alloy, the relative scale of its enhancing also can be bigger.
Fig. 3 is the test findings figure that the analyser of employing Fig. 1 carries out another test.
For observing the experiment effect of Cu atom and Zn atom binary channels resonance enhanced laser induced breakdown spectroscopy, what sample was selected is the aluminium alloy that contains micro Cu atom and Zn atom, and the resonance light source in the light source passage is Cu-Zn bianry alloy (brass).
Horizontal ordinate is wavelength (unit is a nanometer) among the figure, and ordinate is a luminous intensity.
(a) curve among the figure: sample channel is sheltered from, only remaining light source passage, be straight line this moment, the strong laser induced plasma resonance optical radiation that the light source that resonates has been described can not be collected into monochromator and cause background signal.
(b) curve among the figure: the light source passage is sheltered from, only remaining sample channel, this curve is the curve of prior art just.
(c) curve among the figure: light source passage and sample channel do not block, observe the Cu atomic spectrum line (324.75 in the aluminium alloy this moment, 327.40,330.80,333.80nm) and Zn atomic spectrum line (468.01,472.22 luminous intensity 481.05nm) has strengthened about 5 times simultaneously with respect to curve (b).
If the concentration of Cu atom and Zn atom further reduces in the aluminium alloy, the relative scale of its enhancing also can be bigger.
Above-mentioned embodiment is the preferred embodiments of the present invention; can not limit claim of the present invention; other any change or other equivalent substitute mode that does not deviate from technical scheme of the present invention and made is included within protection scope of the present invention.
Claims (9)
1, double-path resonance enhanced laser guidence breakdown spectral trace element analyser, comprise laser instrument, monochromator, photodetector, oscillograph and computing machine, it is characterized in that: described laser instrument is connected with sample channel, light source passage light signal by beam splitting chip (BS); On the light source passage, be disposed with lens (L1), resonance light source, coupled lens group (L3) and (L4); On sample channel, be disposed with catoptron (RM1), lens (L2); Sample channel, light source passage are connected with the sample light signal, and sample is connected with the monochromator light signal by light collecting system, and monochromator is connected with photodetector, and photodetector is connected with oscillograph, and oscillograph is connected with computing machine.
2, double-path resonance enhanced laser guidence breakdown spectral trace element analyser according to claim 1 is characterized in that: described light collecting system comprises lens (L5), catoptron (RM2) and lens (L6); Light collecting system is connected with the entrance slit light signal of monochromator.
3, double-path resonance enhanced laser guidence breakdown spectral trace element analyser according to claim 1, it is characterized in that: described oscillograph is connected with computing machine by gpib interface.
4, double-path resonance enhanced laser guidence breakdown spectral trace element analyser according to claim 1 is characterized in that: described laser instrument is electric-optically Q-switched Pulse Nd: the YAG laser instrument.
5, double-path resonance enhanced laser guidence breakdown spectral trace element analyser according to claim 1 is characterized in that: described resonance light source is the plasma source of induced with laser.
6, double-path resonance enhanced laser guidence breakdown spectral trace element analyser according to claim 1 is characterized in that: described monochromator is a grating monochromator.
7, double-path resonance enhanced laser guidence breakdown spectral trace element analyser according to claim 1 is characterized in that: described oscillograph is a digital storage oscilloscope.
8, double-path resonance enhanced laser guidence breakdown spectral trace element analyser according to claim 1 is characterized in that: described photodetector is a photomultiplier.
9, adopt the analytical approach of the described double-path resonance enhanced laser guidence breakdown spectral trace element analyser of claim 1, it is characterized in that may further comprise the steps:
(1) laser that sends of described laser instrument is divided into two-way light through beam splitting chip (BS) and enters sample channel and light source passage respectively;
(2) focused on the resonance light source at described light source passage glazed thread by lens (L1), produce strong laser induced plasma resonance optical radiation, through coupled lens group (L3) and (L4), focus on sample;
(3) focus on sample at described sample channel glazed thread by catoptron (RM1) reflection and through lens (L2);
(4) under the effect of the light of sample channel, the trace element to be analyzed in the described sample is dissociated out, and described then trace element is by described resonance optical radiation resonance excitation, and described trace element sends resonance and strengthens optical radiation;
(5) described resonance enhancing optical radiation is imaged on the monochromator by light collecting system;
(6) light signal of described monochromator is surveyed through photodetector, is converted to electric signal;
(7) described electric signal is sent to the oscillograph demonstration;
(8) described oscillograph sends data message to that computing machine is noted down and data processing.
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| 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 |
| CN103123320A (en) * | 2012-11-27 | 2013-05-29 | 四川大学 | Laser-induced breakdown spectroscopy analysis method and implementation device based on single-light beam splitting |
| CN103335986A (en) * | 2013-06-21 | 2013-10-02 | 中国科学院上海技术物理研究所 | Laser-induced breakdown spectroscopy (LIBS) system and method based on wavelength division multiplexing and time domain overlapping |
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| CN104931462A (en) * | 2014-03-17 | 2015-09-23 | 以恒科技(北京)有限公司 | Mixed light source focusing enhancing plasma detection system |
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| CN102313731B (en) * | 2010-07-09 | 2012-12-26 | 中国科学院沈阳自动化研究所 | Method for detecting content of component of unknown object on line |
| 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 |
| CN103123320A (en) * | 2012-11-27 | 2013-05-29 | 四川大学 | Laser-induced breakdown spectroscopy analysis method and implementation device based on single-light beam splitting |
| CN103335986A (en) * | 2013-06-21 | 2013-10-02 | 中国科学院上海技术物理研究所 | Laser-induced breakdown spectroscopy (LIBS) system and method based on wavelength division multiplexing and time domain overlapping |
| CN103335986B (en) * | 2013-06-21 | 2015-05-13 | 中国科学院上海技术物理研究所 | Laser-induced breakdown spectroscopy (LIBS) system and method based on wavelength division multiplexing and time domain overlapping |
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| CN103983619A (en) * | 2014-05-16 | 2014-08-13 | 四川大学 | Spatial resolution laser-induced breakdown spectroscopy analysis system and spatial resolution laser-induced breakdown spectroscopy analysis method |
| CN104897625B (en) * | 2015-06-02 | 2017-06-27 | 中国科学院上海技术物理研究所 | For the joint induced with laser spectroscopic system of active agent composition detection |
| CN104897625A (en) * | 2015-06-02 | 2015-09-09 | 中国科学院上海技术物理研究所 | Combined laser induced spectrum system for detecting Mars substance components |
| CN106093011A (en) * | 2016-07-12 | 2016-11-09 | 宝瑞激光科技（常州）有限公司 | The ature of coal laser detection analytical tool of coal quality detecting method and application thereof |
| CN106093011B (en) * | 2016-07-12 | 2019-06-04 | 宝瑞激光科技（常州）有限公司 | Coal quality detecting method and its coal quality laser detection analysis instrument of application |
| CN106706601A (en) * | 2016-12-13 | 2017-05-24 | 华中科技大学 | Laser-induced breakdown fluorescence spectrum analysis system based on optical fiber waveguide cyclic excitation |
| CN106706601B (en) * | 2016-12-13 | 2023-04-11 | 华中科技大学 | Laser-induced breakdown fluorescence spectrum analysis system based on optical fiber waveguide cyclic excitation |
| CN108827911A (en) * | 2018-06-13 | 2018-11-16 | 华中科技大学 | The micro- resonance laser induced breakdown spectroscopy detection method of one kind and system |
| CN108827911B (en) * | 2018-06-13 | 2023-12-19 | 华中科技大学 | Microscopic resonance laser-induced breakdown spectroscopy detection method and system |
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