CN205280584U - Element laser spectrum analytical equipment in liquid - Google Patents
Element laser spectrum analytical equipment in liquid Download PDFInfo
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- CN205280584U CN205280584U CN201520686938.3U CN201520686938U CN205280584U CN 205280584 U CN205280584 U CN 205280584U CN 201520686938 U CN201520686938 U CN 201520686938U CN 205280584 U CN205280584 U CN 205280584U
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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
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/718—Laser microanalysis, i.e. with formation of sample plasma
Abstract
The utility model relates to an element laser spectrum analytical equipment in liquid, support the cage including the leaded light, the leaded light supports the cage lower part and is provided with the support base, the leaded light supports the inside laser focusing lens that is provided with in cage upper end, the corresponding single -point that is provided with in laser focusing lens top swashs light reflector, the corresponding center -band hole baffle that is provided with in laser focusing lens below, the corresponding metal capillary that is provided with in center -band hole baffle below, leaded light between center -band hole baffle and the metal capillary supports cage one side and is provided with plasma spectra collection reservation window, it collects the battery of lens still to be provided with spectrum in the plasma spectra collection reservation window, the metal capillary links to each other with the peristaltic pump, the sample cell that the peristaltic pump passes through silicone tube and the setting of leaded light support cage one side links to each other, the leaded light supports the cage upper end and is provided with industry CCD camera, and the laser beam in pulsed laser source supports the cage through swashing light reflector entering leaded light, and industry CCD camera and pulsed laser source link to each other with digital delay generator, and the spectrum appearance links to each other with digital delay generator, and the spectrum appearance connects plasma spectra to collect the reservation window through optic fibre and draws forth the end. Its stability and precision of utilizing laser induction to puncture in the spectrum technical analysis liquid element and content effectively improves analysis efficiency, quick qualitative, the quantitative analysis of realization element in to liquid.
Description
Technical field
This utility model relates to the use of the quantitative elementary analysis technical field that LIBS is carried out in solution, especially relates to element laser spectral analysis device in a kind of liquid.
Background technology
Quickly the element in detection analytical solution and content thereof are for environmental monitoring, the improvement of water pollution, exploit resources of salt lakes, and exploration of ocean resources has great importance. At present, conventional analysis method mainly has: spark direct emission spectrometer method, atomic absorption spectrography (AAS) (AAS), X-ray fluorescence spectroscopy (XRF), inductively coupled plasma (ICP) spectrum, inductivity coupled plasma mass spectrometry (ICP-MS), inorganic mass spectrometer, organic mass spectrometer, chemical colorimetry and electrochemical analysis method etc.
Although these traditional methods have higher accuracy and sensitivity, but, these methods need to take back sample test in laboratory analysis mostly, some just can be analyzed after also needing to sample is carried out the pretreatment of complexity, sample morphology, institute's analytical element kind etc. all had bigger restriction, and detection process and interpretation of result consuming time longer, this makes the ageing not strong of detection, it is difficult to meet water pollution monitor in real time, the application demand of the aspect such as ocean and salt lake Minerals resource exploration on a large scale.
LIBS (LIBS) technology is to utilize light laser to focus on sample surfaces to form plasma, analyzes the analysis means of elemental composition in sample by measuring the characteristic spectral line in plasma emission spectroscopy. Good effect is achieved in the qualitative and quantitative analysis applied research of the method trace element in the solid samples such as metal. Compared with traditional analysis, the maximum feature of LIBS technology is with little need for preparation, sample broke is little, sensitivity high, and owing to this analysis method only has contacting of light beam and target target, thus multielement, in-situ study can be realized.
Elementary analysis in fluid sample is an important application target of LIBS technology. Generally, utilize LIBS technology to carry out fluid sample analysis, adopt pulse laser directly to focus on liquid level in container attached, liquid breakdown is produced plasma, and then collects plasma spectrometry. Although this metering system is very simple, but the shock wave owing to producing in plasma generation process can cause liquid level to sputter, and laser focusing lens can quickly be polluted and then cause that laser energy is significantly decayed, it is difficult to test constantly. On the other hand, owing to plasma stock wave can cause that liquid level significantly vibrates so that the laser power density acted on liquid varies widely, thus causing measurement result poor repeatability, error is big, which also limits the detection limit of LIBS. In recent researches, main research institution attempts by reducing laser repetition rate, the methods such as liquid fast setting, Adsorption of Filter Paper, liquid jet method improving LIBS technology to the analysis ability of element in liquid in the world. But, these methods all to reduce LIBS technical Analysis efficiency or to increase sample pretreatment process etc. for cost, weaken LIBS technology quickly, the advantage of in-situ study, and effect is also desirable not to the utmost.
Summary of the invention
The purpose of this utility model is in that to avoid the defect of prior art to provide a kind of element laser spectral analysis device and method in liquid, efficiently solves prior art Problems existing.
For achieving the above object, the technical scheme that this utility model is taked is: element laser spectral analysis device in described a kind of liquid, it is characterized in that including guide-lighting support cages, guide-lighting support cages bottom is provided with support base, guide-lighting support cages upper end is internally provided with laser focusing lens, single-point laser reflecting mirror it is correspondingly arranged on above laser focusing lens, center baffle of porous baffle it is correspondingly arranged on below laser focusing lens, it is correspondingly arranged on metal capillary below the baffle of porous baffle of center, guide-lighting support cages side between center baffle of porous baffle and metal capillary is provided with plasma spectrum and collects reserved window, plasma spectrum is collected in reserved window and is additionally provided with spectral collection battery of lens, metal capillary is connected with peristaltic pump, the sample cell that peristaltic pump is arranged with guide-lighting support cages side by silica gel tube is connected, guide-lighting support cages upper end is provided with industrial CCD camera, the laser beam of pulsed laser source enters guide-lighting support cages by laser mirror, industrial CCD camera is connected with digital delay generator with pulsed laser source, spectrogrph is connected with digital delay generator, and spectrogrph connects plasma spectrum by optical fiber and collects reserved window exit.
Described metal capillary is arranged through guide-lighting support cages, laser target spot is arranged on guide-lighting support cages axis and the center of plasma spectrum collection reserved window Axis Cross, to ensure that the plasma plume emission spectrum that laser ablation produces is collected in optical fiber efficiently.
Described metal capillary is inlaid in guide-lighting support cages with the relative support lorhumb line angle less than 45 degree, and the center-hole diameter of described center baffle of porous baffle is less than 5mm; Described spectrogrph, pulsed laser source and industrial CCD trigger by digital delay generator and control, it is ensured that precise synchronization or reconcile time delay, and described industrial CCD camera is placed on guide-lighting support cages axis, is used for monitoring laser target position.
The signal output part of described digital delay generator is connected with pulsed laser source, spectrogrph and industrial CCD camera respectively by cable, regulates the time delay accurately controlling between laser pulse and spectrometer collection by digital delay generator time delay. Just can optimize spectral measurement signal to noise ratio further, improve element detection sensitivity.
The beneficial effects of the utility model are: element laser spectral analysis device and method in described a kind of liquid, it adopts peristaltic pump circulation fluid sample, metal capillary transmission liquid also retrains plasma stock wave, nanosecond laser ablation sample, spectrometer measurement plasma spectrometry, pulse signal chronotron controls to measure sequential etc., can realize the fast qualitative of element in liquid, quantitative analysis, and without sample preparation, do not reduce laser repetition rate etc., thus polluting for Heavy Metals in Waters, nuclear waste in situ detection, lake, ocean Mineral Resource Efficient Explorations etc. provide new tool. it utilizes LIBS to analyze stability and the precision of element and content thereof in liquid, greatly reduces detection limit, the laser pulse utilizing high repetition frequency can be realized as ablative light sources, analysis efficiency can be effectively improved, liquid splash is avoided to pollute optics, it is ensured that equipment long-play stability.
Accompanying drawing explanation
Fig. 1 is structural principle schematic diagram of the present utility model;
Fig. 2 adopts Cr concentration of element curve in method volumetric solution of the present utility model.
Shown in figure: 1. pulsed laser source, 2. laser beam, 3. laser mirror, 4. single-point laser reflecting mirror, 5. industrial CCD camera, 6. laser focusing lens, 7. guide-lighting support cages, 8. center baffle of porous baffle, 9. plasma spectrum collects reserved window, 10. spectral collection battery of lens; 11. optical fiber; 12. spectrogrph; 13. peristaltic pump; 14. silica gel tube; 15. metal capillary; 16. plasma plume; 17. support base; 18. sample cell; 19. digital delay generator.
Detailed description of the invention
Below in conjunction with accompanying drawing, principle of the present utility model and feature being described, example is served only for explaining this utility model, is not intended to limit scope of the present utility model.
As shown in Figure 1, element laser spectral analysis device in described a kind of liquid, it is characterized in including guide-lighting support cages 7, guide-lighting support cages 7 bottom is provided with support base 17, guide-lighting support cages 7 upper end is internally provided with laser focusing lens 6, single-point laser reflecting mirror 4 it is correspondingly arranged on above laser focusing lens 6, center baffle of porous baffle 8 it is correspondingly arranged on below laser focusing lens 6, metal capillary 15 it is correspondingly arranged on below center baffle of porous baffle 8, guide-lighting support cages 7 side between center baffle of porous baffle 8 and metal capillary 15 is provided with plasma spectrum and collects reserved window 9, plasma spectrum is collected in reserved window 9 and is additionally provided with spectral collection battery of lens 10, metal capillary 15 is connected with peristaltic pump 13, the sample cell 18 that peristaltic pump 13 is arranged with guide-lighting support cages 7 side by silica gel tube 14 is connected, guide-lighting support cages 7 upper end is provided with industrial CCD camera 5, the laser beam 2 of pulsed laser source 1 enters guide-lighting support cages 7 by laser mirror 3, industrial CCD camera 5 is connected with digital delay generator 19 with pulsed laser source 1, digital delay generator 19 is connected with spectrogrph 12, and spectrogrph 12 connects plasma spectrum by optical fiber 11 and collects reserved window 9 exit.
Further, described metal capillary 15 is arranged through guide-lighting support cages 7, laser target spot is arranged on guide-lighting support cages 7 axis and the center of plasma spectrum collection reserved window 9 Axis Cross, to ensure that plasma plume 16 emission spectrum that laser ablation produces is collected in optical fiber 11 efficiently.
Further, described metal capillary 15 is to be inlaid in guide-lighting support cages 7 relative to the support cages axis angle less than 45 degree, and the center-hole diameter of described center baffle of porous baffle 8 is less than 5mm; Described spectrogrph 12, pulsed laser source 1 and industrial CCD camera 5 control by digital delay generator 19, it is ensured that precise synchronization or reconcile time delay, and described industrial CCD camera 5 is placed on guide-lighting support cages 7 axis, is used for monitoring laser target position.
Further, the signal output part of described digital delay generator 19 is connected with pulsed laser source 1, spectrogrph 12 and industrial CCD camera 5 respectively by cable, regulate the time delay accurately controlled between laser pulse and spectrogrph 12 collection by digital delay generator 19 time delay, just can optimize spectral measurement signal to noise ratio further, improve element detection sensitivity.
Element laser spectroscopic analysis methods in a kind of liquid, it is characterized in that including described metal capillary 15 transmits the target solution in sample cell 18, target solution is passed through silica gel hose 14 pump to place of laser action district from sample cell 18 by peristaltic pump 13, the laser beam 2 launched by laser instrument focuses on after metal capillary pipe 15 wall ablation penetrates by laser focusing lens 6, laser beam 2 directly acts in the solution surface in pipe, the plasma spectrometry that target liq is formed is launched by forming plasma plume 16, plasma spectrometry is transmitted to spectrogrph 12 through optical fiber 11 after being collected by spectral collection battery of lens and carries out characteristic spectrum analysis.
Further, the method that described metal capillary 15 is changed in spectral-analysis process is: first do circulation solution with ultra-pure water, utilize the continuous ablation metal capillary of pulse laser, and utilize spectrogrph 12 real-time synchronization monitoring spectrum, do not observe in any non-ultra-pure water till the spectral signal of intrinsic element until spectrogrph 12, to avoid the element interference to measurement result in metal capillary; Then target solution is changed, start the measurement analysis of element in target solution, measured by standard solution and demarcate containing discharge curve, both unknown solution can be carried out quantitative measurement analysis, after changing capillary tube every time, all need to utilize industrial CCD simultaneous observation laser target position, confirm that capillary tube installation site is consistent with initial position.
Element laser spectral analysis device and method in described a kind of liquid, it is launched laser beam 2 and after laser mirror 3 and single-point wavelength laser reflecting mirror 4 reflect by laser instrument 1, focus on through laser focusing lens 6, laser beam spot diameter meeting rapid decrement after focusing, metal capillary 15 near surface is acted on through tilted-putted center baffle of porous baffle 8 after laser beam size is less than 5mm, liquid sample can be placed in sample cell 18, the metal capillary 15 connected by silica gel tube 14 pump to silica gel tube by peristaltic pump 13, metal capillary 15 is inclined and mounted in guide-lighting support cages 7, sample cell 18 can be flowed back to by the liquid of metal capillary, a small amount of liquid so can be only utilized to be circulated analysis. when measuring first, it is necessary to first with ultra-pure water by cycles samples system, meanwhile, laser ablation metal capillary forms the diameter aperture less than 1 millimeter, till the spectral line of intrinsic element during spectrometer measurement is less than any non-ultra-pure water. then the ultra-pure water in all pipelines and sample cell is emptied, and testing sample is put into sample cell be circulated, laser can be ablated to testing sample by the aperture of 1 millimeter and form plasma plume 16, plasma emission spectroscopy is collected in optical fiber 11 by battery of lens 10, and transmit to spectrogrph 12, the element in testing sample and content information thereof can be obtained by optic spectrum line analysis. owing to metal capillary is placed with 45 degree of directions, and the tilting centre bore center baffle of porous baffle 8 less than 5mm above it, and the sputtering of laser ablation product is all along body surface normal direction, therefore liquid splash product Hui Bei center baffle of porous baffle 8 shields, avoid the pollution of laser focusing lens 6, it is ensured that instrument works long hours stability. in measurement process, the shock wave that laser ablation liquid produces is retrained by metal capillary, does not result in liquid level and significantly vibrates, thereby ensure that the stability of laser ablation target spot, improves the repeatability measured, and then puies forward high measurement sensitivity. owing to can be prevented effectively from liquid level vibration, therefore using the analyser of the method that the laser pulse of high repetition frequency can be adopted to carry out experiment measuring, this can substantially increase measurement efficiency.
Element laser spectral analysis device and method in described a kind of liquid, the shock wave that laser ablation liquid produces in measurement process is retrained by capillary tube, do not result in liquid level significantly to vibrate, thereby ensure that the stability of laser ablation target spot, improve the repeatability and precision measured, and then put forward high measurement sensitivity, and adopt metal capillary constraint plasma stock wave to effectively reduce liquid level vibration, and the laser pulse that can adopt high repetition frequency carries out experiment measuring, and this can substantially increase measurement efficiency. Owing to adopting silica gel software to draw solution to be measured, therefore, the to be measured solution limited to sample size, can place it in sample cell 18 and recycle, and for in-situ study demand, silica gel hose one end can be directly accessed in testing liquid source, for instance the waste water mouth of pipe, river, lake, ocean etc., owing to whole equipment is very small and exquisite, the demand of element in site measurement in liquid therefore can be met. This measuring method without carrying out any process to sample, and the time of measuring, at several tens of seconds, therefore further increases the efficiency of measurement, all shows obvious advantage relative to existing various measuring method before.
Actual measurement example 1: utilize constituent content in high repetition frequency laser quantitative analysis solution
When utilizing LIBS to analyze element in liquid, generally utilize the direct ablation liquid level of laser. While laser plasma is formed, forming shock wave and evoke liquid level vibration, this can cause liquid level to have relatively macrorelief, thus the laser power density focusing on liquid surface varies widely, and the spectral signal intensity that extreme influence measurement is arrived. This makes liquid measure result poor repeatability, and detectivity is low. Adopt element laser spectrum analysis new method in liquid described in the utility model, peristaltic pump is utilized to coordinate silica gel tube by solution pump to be measured to metal capillary, utilize and form 1 grade aperture in the middle part of the direct ablation metal capillary of the repetitive frequency pulsed laser of 10Hz, then laser direct ablation target solution from aperture forms plasma, plasma spectrometry enters spectrogrph by optical fiber and carries out spectrum analysis, can realize the analysis of element in target solution. Owing to adopting metal capillary transmission solution, and laser ablation target spot is in capillary midsection, therefore the shock wave formed during laser ablation liquid can by metal capillary operative constraint, thus avoiding liquid level to vibrate, make the spectral results repeatability utilizing LIBS measurement fluid sample better, put forward high measurement sensitivity, and laser repetition rate need not be reduced. Fig. 2 is Cr concentration of element calibration curve in the aqueous solution using this method to obtain, it can be seen that measure obtained concentration curve linear fit R2Reach 0.9982, typical case's measurement error < 5%.
Actual measurement example 2: avoid liquid splash to pollute optics
When utilizing LIBS to analyze element in liquid, generally utilize the direct ablation liquid level of laser. While laser plasma is formed, forming shock wave and evoke liquid level vibration, this can cause liquid level to have relatively macrorelief, thus the laser power density focusing on liquid surface varies widely, and the spectral signal intensity that extreme influence measurement is arrived. This makes liquid measure result poor repeatability, and detectivity is low. But, utilize element laser spectrum analysis new method in liquid described in the utility model, peristaltic pump is utilized to coordinate silica gel tube by solution pump to be measured to metal capillary, utilize formation submillimeter level aperture in the middle part of the direct ablation metal capillary of pulse laser, then laser direct ablation target solution from aperture forms plasma, utilizes spectrogrph directly to measure plasma spectrometry and can realize the analysis of element in target solution. Owing to adopting metal capillary transmission solution, and laser ablation target spot is in capillary midsection, therefore the shock wave formed during laser ablation liquid can by metal capillary operative constraint, thus avoiding liquid level to vibrate, make the spectral results repeatability utilizing LIBS measurement fluid sample better, put forward high measurement sensitivity, and laser repetition rate need not be reduced.
The foregoing is only preferred embodiment of the present utility model, not in order to limit this utility model, all within spirit of the present utility model and principle, any amendment of making, equivalent replacement, improvement etc., should be included within protection domain of the present utility model.
Claims (4)
1. element laser spectral analysis device in a liquid, it is characterized in that including guide-lighting support cages, guide-lighting support cages bottom is provided with support base, guide-lighting support cages upper end is internally provided with laser focusing lens, single-point laser reflecting mirror it is correspondingly arranged on above laser focusing lens, center baffle of porous baffle it is correspondingly arranged on below laser focusing lens, it is correspondingly arranged on metal capillary below the baffle of porous baffle of center, guide-lighting support cages side between center baffle of porous baffle and metal capillary is provided with plasma spectrum and collects reserved window, plasma spectrum is collected in reserved window and is additionally provided with spectral collection battery of lens, metal capillary is connected with peristaltic pump, the sample cell that peristaltic pump is arranged with guide-lighting support cages side by silica gel tube is connected, guide-lighting support cages upper end is provided with industrial CCD camera, the laser beam of pulsed laser source enters guide-lighting support cages by laser mirror, industrial CCD camera is connected with digital delay generator with pulsed laser source, spectrogrph is connected with digital delay generator, and spectrogrph connects plasma spectrum by optical fiber and collects reserved window exit.
2. element laser spectral analysis device in a kind of liquid as claimed in claim 1, it is characterized in that: described metal capillary is arranged through guide-lighting support cages, laser target spot is arranged on guide-lighting support cages axis and the center of plasma spectrum collection reserved window Axis Cross, to ensure that the plasma plume emission spectrum that laser ablation produces is collected in optical fiber efficiently.
3. element laser spectral analysis device in a kind of liquid as claimed in claim 1, it is characterized in that: described metal capillary is inlaid in guide-lighting support cages with the relative support lorhumb line angle less than 45 degree, and the center-hole diameter of described center baffle of porous baffle is less than 5mm; Described spectrogrph, pulsed laser source and industrial CCD trigger by digital delay generator and control, it is ensured that precise synchronization or reconcile time delay, and described industrial CCD camera is placed on guide-lighting support cages axis, is used for monitoring laser target position.
4. element laser spectral analysis device in a kind of liquid as claimed in claim 1, it is characterized in that: the signal output part of described digital delay generator is connected with pulsed laser source, spectrogrph and industrial CCD camera respectively by cable, regulate the time delay accurately controlling between laser pulse and spectrometer collection by digital delay generator time delay.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201520686938.3U CN205280584U (en) | 2015-09-07 | 2015-09-07 | Element laser spectrum analytical equipment in liquid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201520686938.3U CN205280584U (en) | 2015-09-07 | 2015-09-07 | Element laser spectrum analytical equipment in liquid |
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| CN205280584U true CN205280584U (en) | 2016-06-01 |
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