CN102590157B - Element spectrum analysis method and laser element exploration equipment adopting same - Google Patents
Element spectrum analysis method and laser element exploration equipment adopting same Download PDFInfo
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Abstract
The invention belongs to the field of spectrum analysis and detection, particularly relates to an element spectrum analysis method and laser element exploration equipment adopting the method, and aiming at overcoming the defects of the atomic emission spectrum analysis method for elements and solve the technical problems that a laser source on laser element exploration equipment used at present is not stable, and the laser element exploration equipment cannot be carried conveniently, the invention provides the element spectrum analysis method and the laser element exploration equipment adopting the method. The element spectrum analysis method comprises a qualitative analysis method and a quantitative analysis method for the atomic emission spectrum of a sample to be tested. The laser element exploration equipment comprises a laser source system, a spectrum collection system and a signal processing module. The element spectrum analysis method disclosed by the invention overcomes the defects of the original analysis method. The equipment disclosed by the invention can output the laser with stable energy intensity, is small in volume, light in weight and very suitable for field site operation.
Description
Technical field
The invention belongs to spectral analysis and detection field, be specifically related to the laser element exploring equipment of a kind of element spectrum analysis method and employing the method.
Background technology
In commercial production, scientific research, usually to carry out qualitative, quantitative detection analysis to the chemical element of associated materials and mineral.Traditional material, ore determination and analysis method mainly contain chemical assay method, atomic absorption method and inductively coupled plasma emission spectrography.Wherein, chemical analysis and atomic absorption method need to be from field acquisition samples, analysis time that need to be longer and loaded down with trivial details running program, and easily form secondary pollution, so only limit to lab analysis; Inductively coupled plasma emission spectrography is highly sensitive, can measure multiple element simultaneously, but need to carry out complicated pre-service to sample, and reagent dosage is also larger, and plasma torch pipe is easily stain.Exploring at the scene at present prevailing method in industry is both at home and abroad x ray fluorescence spectrometry (XRF), adopt X-fluorescence energy dispersion or wavelength dispersion principle, measure accurately, do not need sampling and destroy testing sample, can on-the-spot to composition of ores, carry out direct-detection analysis, but its in air ambient to light element (as Mg, Al, Si, P, S etc.) a little less than distinguishing ability, to atomic weight, be that elements are contained below 23 needs to match helium charging unit, and must directly contact with sample while measuring, cannot realize remote measurement, X ray has radiation hazard in addition, long-term use easily causes various diseases, below all limited the further popularization of the method.
Laser-induced Breakdown Spectroscopy method (laser induced breakdown spectroscopy) is called for short LIBS, it is a kind of laser ablation spectral analysis technique, have fast, highly sensitive, little to sample destructiveness without sample pretreatment, measuring speed, can multielement analyze simultaneously, to light element (as Mg, Al, Si, P, S etc.) distinguishing ability is strong, safety is radiationless, can remote measurement etc. advantage.Laser-induced Breakdown Spectroscopy method is based on pulsed laser technique, surface by a branch of high-octane Laser Focusing to material to be analyzed, to after the ablation of focal position part material, produce high-temperature plasma, plasma temperature rises to several thousand degree, produces more charged ion.In plasma, the ionizing radiation of each element forms continuous background spectral line, this process need hundreds of nanosecond; Form afterwards the atomic emission line of each element in plasma, the characteristic information that atomic emission line has comprised each element, different element correspondences atomic emission line separately, line strength and concentration of element are approximated to direct ratio, this process continues several microseconds, is to carry out the particularly important step of quantitative test of qualitative elementary analysis.Analyze atomic emission line and can judge the kind of contained element in sample; By the intensity ratio of analyzing between each spectral line, get final product the relative content that quantitative test goes out each element in sample.When element is carried out to quantitative test, adopt the known free scaling method of the industry,, directly according to the relative intensity of the atomic emission line obtaining, normalization calculates the concentration of each component, the interference that can avoid so different types of ore substrate variations to bring.While calculating the relative intensity of spectral line, adopt spectral line peak height as spectral line relative intensity.
During the free scaling method analytical element of described quantitative analysis method utilization concentration, by improving the calculating accuracy (plasma temperature, electron density, line strength etc.) of relevant intermediate computations parameter, improve the measuring accuracy of free scaling method.During calculating plasma temperature, utilize Saha-Boltzmann multiple chart method to replace conventional Boltzmann oblique line method, by monovalent ion spectrum and the neutral atom spectrum of identity element, by Saha equation, change, do oblique line and determine temperature.Because select the spectral line of emission from different states of ionization, and their upper energy level has larger energy level difference, so the calculating of temperature is had to higher accuracy.Carry out Saha conversion and need to measure the electron density of plasma, by analyzing the Stark broadening of the spectral line of emission, calculate electron density here.It is Lorentzian type that spectral line Stark widens main line style, adopts Lorentzian profile linear fitting to revise spectral line line style, can avoid spectral line to have the overlapping interference causing, and improves the computational accuracy of spectrum peak width, indirectly improves measuring accuracy.
At present the qualitative analysis of the element method that also needs to detect by an unaided eye is found to atomic emissions spectrum peak, then search and compare by the atomic spectra database of the abbreviation NIST of National Institute of Standards and Technology (National Institute of Standards and Technology); Due to usually not accurate enough to the judgement of position, peak, make to realize the qualitative analysis accurately to unknown mineral sample; In quantitative test, adopt spectrum peak height to represent the relative intensity of atomic emission line, cause analysis result reliable not; The LIBS detection system of using at present exists laser intensity stable not, and the laser of launching is when carrying out ablation to sample, and the atomic emission line intensity that causes plasma resonance that sample produces to go out is unstable equally, has affected the accuracy of quantitative test; The LIBS detection system of moulding at present is generally comprised of tune Q formula Nd:YAG laser instrument, spectrometer, signal generator, data acquisition and the signal processing system etc. of xenon flash lamp pumping, volume is larger, and need 220V mains-supplied, limited its movability, while being not easy to field work or site inspection, carried.
Summary of the invention
The present invention exists defect to cause analysis result inaccurate in order to solve the current Atomic Emission Spectral Analysis method for element, and the LASER Light Source insufficient strength on current laser element exploring equipment used is stable and carry technical matters not easily, provide the laser element exploring equipment of a kind of element spectrum analysis method and employing the method.
Element spectrum analysis method of the present invention has adopted following technical scheme to realize: a kind of element spectrum analysis method, comprises the method for qualitative analysis that the atomic emission line of testing sample is carried out and the quantitative analysis method that adopts free scaling method; Described method for qualitative analysis comprises the following steps: (a) atomic emission line of sample is asked to second derivative; (b), for the result after spectral line second derivative, according to the stimulus threshold criterion of following regulation, judge the minimum point after difference quotient:
Only retain the point that is less than threshold value after second derivative, described standard deviation is the standard deviation of the data obtained after spectral line second derivative; (c) to being less than the point of threshold value, adopt triangle test to determine minimum point wherein, this minimum point is the characteristic peak of corresponding former spectral line; (d) characteristic peak of selecting and NIST atomic emission spectrum database are compared, the element kind that each spectral line is corresponding is demarcated; Adopt the quantitative analysis method of free scaling method when calculating the relative intensity of the spectral line of emission, to adopt the integrated intensity of spectrum peak area to represent relative intensity, when calculating spectrum peak area, adopt the impact of LIBS spectral line modification method innovation spectrum line broadening.
In described method for qualitative analysis, the LIBS spectral line collecting is asked to second derivative, as shown in Fig. 1 (b), according to the character of second derivative, location, peak is positioned at minimal value place.For the suprabasil weak peak of former spectral line, comparatively slow because of its variation, after second order difference quotient, can become peak or sweep that amplitude is very little.Set a threshold value, be greater than the minimum point of threshold value, be considered as that suprabasil gradual ghost peak causes, do not consider; Only Consideration of Second Order is led the part that is less than threshold value, as Fig. 1 (c); With triangle test, determine its minimum point, be the location, peak of former spectral line, as shown in Figure 1 (d) shows.In order to suppress to greatest extent in substrate insignificant ghost peak and don't to miss real peak, need to select suitable threshold value, could obtain the good peak effect of looking for.Threshold value is too low, can find out the upper insignificant peak of many suprabasil ghost peaks or statistics; And threshold value is excessive, can miss significant real peak again.This method is on the basis of lot of experiments, and the threshold value of selection be take the standard deviation (Stanard Deviation, SD) of data as with reference to fluctuating.Through experiment, find, when the standard deviation of data is larger, getting standard deviation is that threshold value can suppress to greatest extent ghost peak and don't miss real peak; When standard deviation hour, need to suitably increase threshold value in order to avoid suprabasil ghost peak is known by mistake, and SD is less, need the multiple that increases larger, could obtain the good peak effect of looking for.Adopt this method to can be good at eliminating the impact of ground unrest, improve the precision of qualitative analysis.Described triangle test is widely used in signal analysis field, is those skilled in the art's common practise.
Element is carried out to quantitative test and adopt the known free scaling method of the industry, while calculating the relative intensity of the spectral line of emission, without its peak height, with spectrum peak area, represent.Than traditional peak height that only relies on, judge the analytical approach of peak strength, this method can effectively improve precision of analysis.When but this method is applied to the analysis of atomic emission line intensity, there will be following problems, the broadening that is indivedual spectral lines can cause the change of composing peak area, as a, b spectral line in Fig. 2, the peak height of a line is less than b line, but due to broadening, the peak area of a line is greater than the peak area of b line, causes measurement result inaccurate.Therefore when calculating spectrum peak area, need adopt the impact of LIBS spectral line modification method innovation spectrum line broadening, improve the calculating accuracy of spectral line relative intensity.
Laser element exploring equipment disclosed by the invention is realized by the following technical solutions: a kind of laser element exploring equipment that adopts element spectrum analysis method, comprises laser source system, spectra collection system, includes the signal processing module of photoelectric commutator and computer system; The output terminal of photoelectric commutator is connected with the input end of computer system; Described laser source system comprises laser head, the Laser Power Devices that are connected with laser head, the trigger being connected with Laser Power Devices and the power supply being connected with trigger; Spectra collection system comprises miniature focusing system, the spectrometer that is connected and is connected with power supply with miniature focusing system by optical fiber, and described optical fiber is connected with the input end of spectrometer; Light path along laser head is provided with the adjustable condenser lens of angle; Spectrometer output terminal is connected with the input end of photoelectric commutator; Computer system output terminal is connected with display screen; Computer system in signal processing module, under the support of corresponding software, adopts described element spectrum analysis method to analyze collected atomic emission line, and exports analysis result to display screen.
Described laser element exploring equipment also comprises closed loop energy negative feedback laser energy systems stabilisation, described closed loop energy negative feedback laser energy systems stabilisation comprises the feedback circuit that is arranged on the laser head Amici prism adjustable with angle between condenser lens, the sniffer matching with Amici prism, is connected with sniffer, feedback circuit is connected with Laser Power Devices, and sniffer comprises thermopile detector and the computer control system being connected with thermopile detector, the signal output part of thermopile detector is connected with the signal input part of computer control system, and the signal output part of computer control system is connected with feedback circuit, described closed loop energy negative feedback laser energy systems stabilisation is adopted with the following method the pulse laser intensity of laser head output is controlled: the partial pulse laser that laser head sends reflexes to thermopile detector through Amici prism, thermopile detector is converted to the light signal of the pulse laser collecting electric signal and inputs to computer control system, computer control system is carried out intensity calculating to the pulsed laser energy that is converted into electric signal collecting under the support of corresponding software, during calculating, adopt the integrated intensity of the spectrum peak area of pulse laser to carry out the energy intensity of indicating impulse laser, and the numerical value of the specified laser intensity of result of calculation and laser head output is compared, computer control system inputs to feedback circuit by the electric signal of relatively rear gained difference, feedback circuit is adjusted the pumping voltage of Laser Power Devices so that pulsed laser energy is stable automatically according to the difference signal of input.
Described laser element exploring equipment also comprises an integral body, and integral body comprises hand-held fuselage and the suitcase being connected with hand-held fuselage; Laser head, miniature focusing system, condenser lens and sniffer are arranged on hand-held fuselage interior; Laser Power Devices, signal processing module, feedback circuit, trigger, power supply, spectrometer are arranged on suitcase inside; Described power supply is accumulator, and optical fiber is arranged on integral body inside, and hand-held fuselage is provided with taper measuring head along one end of laser head light path, and miniature focusing system is arranged near taper measuring head; Described display screen is miniature display screen and is arranged on hand-held fuselage outer side, and hand-held fuselage outer side is also provided with handle.
Power supply is trigger and spectrometer power supply, and trigger is used for controlling the pumping voltage of Laser Power Devices, plays the effect of switch; In computer system, being provided with accumulator, can be whole signal processing module power supply.During work, laser head is aimed to sample, by flip-flop toggle Laser Power Devices, Laser Power Devices are controlled laser head and are sent pulse laser, pulse laser line focus lens focus, and be irradiated to testing sample surface, make sample focus on the position generation plasma that is excited, the atomic emission line of this plasma institute radiation by miniature focusing system, received and through an optical fiber transmission to spectrometer, by spectrometer, it is carried out to light splitting, and by spectral signal input signal processing module, photoelectric commutator in signal processing module converts light signal to corresponding electric signal, computer system adopts element spectrum analysis method to carry out qualitative and quantitative analysis to converting the spectral signal of electric signal under the support of corresponding software, and analysis result is presented on display screen.The art personnel's element spectrum analysis method disclosed according to the present invention is easy to easily write out corresponding software.
When using LIBS to carry out element exploration, unstable and the eyeglass of laser energy the plasma that the impact of factor can cause pulse laser to produce such as is stained and is had certain fluctuation, the intensity of spectral signal there will be difference, thereby can affect the accuracy of quantitative test greatly.For overcoming this shortcoming, designed closed loop energy negative feedback laser energy systems stabilisation, can pulsed laser energy is stable.Specific embodiments is: the sniffer of having placed Amici prism and having matched with Amici prism in laser emitting light path, Amici prism by a part of laser reflection to sniffer, sniffer is used for detecting the size of the pulsed laser energy of exporting, and corresponding feedback signal is input in feedback circuit, the pumping voltage of adjusting in real time in Laser Power Devices by feedback circuit makes outgoing pulsed laser energy stable.Between described laser source system, sniffer, feedback circuit, form a closed-loop control system.Feedback circuit can have various structures to realize, and relevant technology is known in those skilled in the art.In sniffer computer control system, being provided with accumulator, is whole sniffer power supply; When electricity thermopile detector gathers laser energy, sampling rate is 200000S/s, if Fig. 4 is the pulse energy signal collecting.When paired pulses laser energy calculates, for improving computational accuracy, without its peak height, adopt the integrated intensity of spectrum peak area to carry out the energy of indicating impulse laser, be the poor of dash area area and background signal area occupied in Fig. 4, the intensity of background signal can be represented by the mean value of the comparatively smooth part in spectrum both sides, peak.To the pulse energy calculating by this kind of method with by power meter, record result and make comparisons, result is as shown in Figure 5.As seen from Figure 5, almost linear between the two, the degree of correlation is higher.Thermopile detector inputs to computer control system after the pulsed laser energy signal detecting is converted to electric signal, computer control system under the support of corresponding software by the intensity level I of the pulsed laser energy that is converted to electric signal of input
realspecified pulse laser output intensity I with laser source system used
volumecompare, and will reflect I
realwith I
volumethe electric signal of difference input to feedback circuit, feedback circuit is adjusted in real time according to the pumping voltage of the difference Signals in Laser power supply of input, if the laser intensity of output is greater than ratings, feedback circuit is controlled the pumping lower voltage of Laser Power Devices, the laser intensity of laser head output is reduced, until approach ratings; When the laser intensity of output is less than ratings, the pumping voltage that feedback circuit is controlled Laser Power Devices raises, and the laser intensity of laser head output is strengthened, until approach ratings.The present invention can be controlled at the instability of pulsed laser output energy ± 2% in.Fig. 6 has shown under equal parameter, is using closed loop energy negative feedback laser energy systems stabilisation front and back, the stability test figure of pulse energy during 100 continuous laser pulses of laser instrument output.As can be seen from Figure 6, the stability of the stable significantly improving laser output of the closed loop energy negative feedback laser energy energy that the present invention adopts, thus improve the precision and stability of quantitative test.
The all parts of LIBS detection system is arranged on to integral body inside, and is that trigger and spectrometer are powered by accumulator, convenient in the wild or carry during field survey; The condenser lens of hand-held fuselage interior and the angle of miniature focusing system are all fine-tuning, guarantee that shoot laser line focus lens can defocused focus be positioned at taper measuring head center, make sample be provoked into plasma, and make miniature focusing system can receive the sufficiently high atomic emission line of signal to noise ratio (S/N ratio); Integral body outside is provided with the switch of controlling inner each parts, convenient controlling whole equipment; Handle be provided with the assurance that is beneficial to operating personnel.Adopt taper measuring head to contribute to make fuselage to aim at sample; Power supply adopts accumulator, discharges and recharges very easyly, and can change at any time, has facilitated carrying while going out operation; Miniature display screen display analysis result in time when reducing equipment volume.
Laser source system of the present invention, spectra collection system, signal processing module and sniffer are existing known technology, can have various structures and relevant model for you to choose, are easy to buy on market.
The peak-seeking that before method for qualitative analysis disclosed by the invention has overcome, similar approach exists not precisely, analytic process is slow and the inaccurate problem of result; In quantitative analysis method, adopt spectrum peak area to represent relative intensity, when calculating spectrum peak area, need adopt the impact of LIBS spectral line modification method innovation spectrum line broadening, improved the accuracy of quantitative analysis results.The closed loop energy negative feedback laser energy systems stabilisation adopting makes the laser of laser source system transmitting more stable, and the spectrum of the plasma emission producing during sampling is more stable, has improved the reliability of quantitative analysis results.The present invention is because its volume is little, lightweight, can show in real time result, is applicable to very much field condition operation.
Accompanying drawing explanation
Fig. 1 method for qualitative analysis schematic diagram.Figure a is the sample atoms spectral line of emission that spectrometer records; Figure b is for to ask the result after second derivative to the spectrum recording; Figure c is for to remove according to stimulus threshold criterion the peak staying after the point that is greater than threshold value; The location, peak that figure d is the former spectral line that finds according to triangle test, in figure, solid dot represents location, peak.
The impact that when Fig. 2 calculates spectrum peak area, the broadening at peak causes.
Fig. 3 laser element of the present invention exploring equipment structural representation.
The pulsed laser energy signal that Fig. 4 thermopile detector collects and the area integral schematic diagram of laser energy.
The result comparison schematic diagram that the laser intensity that calculates of integrated intensity that Fig. 5 adopts spectrum peak area and power meter record.In figure, solid dot represents laser intensity that power meter records and the corresponding relation of respective peaks area, and oblique line represents the integrated intensity of peak area and the corresponding relation of laser intensity.
Fig. 6 is used before and after closed loop energy negative feedback laser energy systems stabilisation, the stability test figure of pulse energy during 100 continuous laser pulses of laser instrument output.Figure a is for before being used, and figure b is for after being used.Solid dot represents the energy intensity of the pulse laser that records.
The testing result of Fig. 7 the present invention to four kinds of samples.Figure a is brass, and figure b is aluminium sheet, and figure c is solar power silicon plate, and figure d is antifungin compressing tablet.
1-laser head, 2-sniffer, 3-Amici prism, 4-condenser lens, 5-taper measuring head, the miniature focusing system of 6-, 7-optical fiber, 8-miniature display screen, 9-handle, 10-signal processing module, 11-power supply, 12-feedback circuit; 13-Laser Power Devices, 14-trigger, 15-spectrometer, 16-hand-held fuselage, 17-suitcase, 18-sample.
Embodiment
An element spectrum analysis method, comprises the method for qualitative analysis that the atomic emission line of testing sample is carried out and the quantitative analysis method that adopts free scaling method; Described method for qualitative analysis comprises the following steps: (a) atomic emission line of sample is asked to second derivative; (b), for the result after spectral line second derivative, according to the stimulus threshold criterion of following regulation, judge the minimum point after difference quotient:
Only retain the point that is less than threshold value after second derivative, described standard deviation is the standard deviation of the data obtained after spectral line second derivative; (c) to being less than the point of threshold value, adopt triangle test to determine minimum point wherein, this minimum point is the characteristic peak of corresponding former spectral line; (d) characteristic peak of selecting and NIST atomic emission spectrum database are compared, the element kind that each spectral line is corresponding is demarcated; Adopt the quantitative analysis method of free scaling method when calculating the relative intensity of the spectral line of emission, to adopt the integrated intensity of spectrum peak area to represent relative intensity, when calculating spectrum peak area, adopt the impact of LIBS spectral line modification method innovation spectrum line broadening.
Adopt a laser element exploring equipment for element spectrum analysis method, comprise laser source system, spectra collection system, include the signal processing module 10 of photoelectric commutator and computer system; The output terminal of photoelectric commutator is connected with the input end of computer system; Described laser source system comprises laser head 1, the Laser Power Devices 13 that are connected with laser head 1, the trigger 14 being connected with Laser Power Devices 13 and the power supply 11 being connected with trigger 14; Spectra collection system comprises miniature focusing system 6, the spectrometer 15 that is connected and is connected with power supply 11 with miniature focusing system 6 by optical fiber 7, and described optical fiber 7 is connected with the input end of spectrometer 15; Light path along laser head 1 is provided with the adjustable condenser lens of angle 4; Spectrometer 15 output terminals are connected with the input end of photoelectric commutator; Computer system output terminal is connected with display screen 8; Computer system in signal processing module 10, under the support of corresponding software, adopts described element spectrum analysis method to analyze collected atomic emission line, and exports analysis result to display screen 8.Also comprise closed loop energy negative feedback laser energy systems stabilisation, described closed loop energy negative feedback laser energy systems stabilisation comprises the feedback circuit 12 that is arranged on laser head 1 Amici prism 3 adjustable with angle between condenser lens 4, the sniffer 2 matching with Amici prism 3, is connected with sniffer 2, and feedback circuit 12 is connected with Laser Power Devices 13, sniffer 2 comprises thermopile detector and the computer control system being connected with thermopile detector, the signal output part of thermopile detector is connected with the signal input part of computer control system, and the signal output part of computer control system is connected with feedback circuit 12, described closed loop energy negative feedback laser energy systems stabilisation is adopted with the following method the pulse laser intensity of laser head 1 output is controlled: the partial pulse laser that laser head 1 sends reflexes to thermopile detector 2 through Amici prism 3, thermopile detector 2 is converted to the light signal of the pulse laser collecting electric signal and inputs to computer control system, computer control system is carried out intensity calculating to the pulsed laser energy that is converted into electric signal collecting under the support of corresponding software, during calculating, adopt the integrated intensity of the spectrum peak area of pulse laser to carry out the energy intensity of indicating impulse laser, and the numerical value of the specified laser intensity of result of calculation and laser head 1 is compared, computer control system inputs to feedback circuit 12 by the electric signal of relatively rear gained difference, feedback circuit 12 is adjusted the pumping voltage of Laser Power Devices 13 so that pulsed laser energy is stable automatically according to the difference signal of input.Also comprise an integral body, integral body comprises hand-held fuselage 16 and the suitcase 17 being connected with hand-held fuselage 16; Laser head 1, miniature focusing system 6, condenser lens 4 and sniffer 2 are arranged on hand-held fuselage 16 inside; Laser Power Devices 13, signal processing module 10, feedback circuit 12, trigger 14, power supply 11, spectrometer 15 are arranged on suitcase 17 inside; Described power supply 11 is accumulator, and optical fiber 7 is arranged on integral body inside, and hand-held fuselage 16 is provided with taper measuring head 5 along one end of laser head light path, and miniature focusing system 6 is arranged near taper measuring head 5; Described display screen 8 is for miniature display screen and be arranged on hand-held fuselage outer side, and hand-held fuselage 16 outsides are also provided with handle 9.Hand-held fuselage 16 is connected by threaded line pipe with suitcase 17.Laser head 1 is high pressure trigger-type laser head.Computer system in signal processing module 10 adopts mini-notebook computer.Accumulator is 12V accumulator.
Hand-held fuselage 16 is connected by threaded line pipe with suitcase 17, can facilitate the activity of hand-held fuselage, and sample aims at the mark while being conducive to survey; Computer system adopts mini-notebook computer, has further reduced the volume of this equipment; 12V accumulator volume is small and exquisite, and charging fast; The advantages such as it is high that high pressure trigger-type laser head has reliability, and standby current is little.
During concrete enforcement, laser source system used is portable high power Nd:YAG Optical Maser System, the high pressure trigger-type laser head that the model that laser head 1 wherein adopts is LMS-367; Trigger 14 model used is MK-367HC; Laser Power Devices 13 model used is MK-106.20, the Avantes AvaSpec-2048-USB2 spectrometer that the Dutch Avantes of spectrometer 15 employing company produces, the total silicon optical fiber that the Dutch Avantes of optical fiber 7 employing company produces, numerical aperture 0.22,600 microns of fiber core diameters.
Fig. 7 is that the present invention is specifically applied to the rear shown analysis result of miniature display screen 8 of actual exploration.The peak value of the atomic emission line of each element in the sample 18 that in figure, each solid dot representation signal processing module analyzes.The present invention can analyze the composition of sample accurately, and provides the component of contained each element of sample.
Claims (10)
1. an element spectrum analysis method, comprises the method for qualitative analysis that the atomic emission line of testing sample is carried out and the quantitative analysis method that adopts free scaling method; It is characterized in that, described method for qualitative analysis comprises the following steps: (a) atomic emission line of sample is asked to second derivative; (b), for the result after spectral line second derivative, according to the stimulus threshold criterion of following regulation, judge the minimum point after difference quotient:
Only retain the point that is less than threshold value after second derivative, described standard deviation is the standard deviation of the data obtained after spectral line second derivative; (c) to being less than the point of threshold value, adopt triangle test to determine minimum point wherein, this minimum point is the characteristic peak of corresponding former spectral line; (d) characteristic peak of selecting and NIST atomic emission spectrum database are compared, the element kind that each spectral line is corresponding is demarcated; Adopt the quantitative analysis method of free scaling method when calculating the relative intensity of the spectral line of emission, to adopt the integrated intensity of spectrum peak area to represent relative intensity, when calculating spectrum peak area, adopt the impact of LIBS spectral line modification method innovation spectrum line broadening.
2. adopt a laser element exploring equipment for element spectrum analysis method as claimed in claim 1, comprise laser source system, spectra collection system, include the signal processing module (10) of photoelectric commutator and computer system; The output terminal of photoelectric commutator is connected with the input end of computer system; Described laser source system comprises laser head (1), the Laser Power Devices (13) that are connected with laser head (1), the trigger (14) being connected with Laser Power Devices (13) and the power supply (11) being connected with trigger (14); Spectra collection system comprises miniature focusing system (6), the spectrometer (15) that is connected and is connected with power supply (11) with miniature focusing system (6) by optical fiber (7), and described optical fiber (7) is connected with the input end of spectrometer (15); Light path along laser head (1) is provided with the adjustable condenser lens of angle (4); Spectrometer (15) output terminal is connected with the input end of photoelectric commutator; Computer system output terminal is connected with display screen (8); It is characterized in that, the computer system in signal processing module (10), under the support of corresponding software, adopts described element spectrum analysis method to analyze collected atomic emission line, and exports analysis result to display screen (8).
3. laser element exploring equipment as claimed in claim 2, characterized by further comprising closed loop energy negative feedback laser energy systems stabilisation, described closed loop energy negative feedback laser energy systems stabilisation comprises the feedback circuit (12) that is arranged on laser head (1) Amici prism (3) adjustable with angle between condenser lens (4), the sniffer (2) matching with Amici prism (3), is connected with sniffer (2), and feedback circuit (12) is connected with Laser Power Devices (13), sniffer (2) comprises thermopile detector and the computer control system being connected with thermopile detector, the signal output part of thermopile detector is connected with the signal input part of computer control system, and the signal output part of computer control system is connected with feedback circuit (12), described closed loop energy negative feedback laser energy systems stabilisation is adopted with the following method the pulse laser intensity of laser head (1) output is controlled: the partial pulse laser that laser head (1) sends reflexes to thermopile detector (2) through Amici prism (3), thermopile detector (2) is converted to the light signal of the pulse laser collecting electric signal and inputs to computer control system, computer control system is carried out intensity calculating to the pulsed laser energy that is converted into electric signal collecting under the support of corresponding software, during calculating, adopt the integrated intensity of the spectrum peak area of pulse laser to carry out the energy intensity of indicating impulse laser, and the numerical value of the specified laser intensity of result of calculation and laser head (1) is compared, computer control system inputs to feedback circuit (12) by the electric signal of relatively rear gained difference, feedback circuit (12) is adjusted the pumping voltage of Laser Power Devices (13) so that pulsed laser energy is stable automatically according to the difference signal of input.
4. laser element exploring equipment as claimed in claim 3, characterized by further comprising an integral body, and integral body comprises hand-held fuselage (16) and the suitcase (17) being connected with hand-held fuselage (16); Laser head (1), miniature focusing system (6), condenser lens (4) and sniffer (2) are arranged on hand-held fuselage (16) inside; Laser Power Devices (13), signal processing module (10), feedback circuit (12), trigger (14), power supply (11), spectrometer (15) are arranged on suitcase (17) inside; Described power supply (11) is accumulator, and optical fiber (7) is arranged on integral body inside, and hand-held fuselage (16) is provided with taper measuring head (5) along one end of laser head (1) light path, and miniature focusing system (6) is arranged near taper measuring head (5); Described display screen (8) is for miniature display screen and be arranged on hand-held fuselage outer side, and hand-held fuselage (16) outside is also provided with handle (9).
5. laser element exploring equipment as claimed in claim 4, is characterized in that hand-held fuselage (16) is connected by threaded line pipe with suitcase (17).
6. laser element exploring equipment as claimed in claim 2 or claim 3, is characterized in that described laser head (1) is high pressure trigger-type laser head.
7. laser element exploring equipment as claimed in claim 4, is characterized in that described laser head (1) is high pressure trigger-type laser head.
8. laser element exploring equipment as claimed in claim 2 or claim 3, is characterized in that the computer system in described signal processing module (10) adopts mini-notebook computer.
9. laser element exploring equipment as claimed in claim 4, is characterized in that the computer system in described signal processing module (10) adopts mini-notebook computer.
10. laser element exploring equipment as claimed in claim 4, is characterized in that described accumulator is 12V accumulator.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3215828A4 (en) * | 2014-11-07 | 2018-06-06 | National Research Council of Canada | Compact apparatus for laser induced breakdown spectroscopy and method therefor |
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| DE102013009962B3 (en) * | 2013-06-14 | 2014-11-06 | K+S Aktiengesellschaft | LIBS viewing tube |
| CN103616351A (en) * | 2013-11-26 | 2014-03-05 | 中国科学院广州地球化学研究所 | Laser-induced breakdown spectroscopy analyzer and laser-induced breakdown spectroscopy analysis method |
| RU2677417C2 (en) * | 2014-11-25 | 2019-01-16 | Хэллибертон Энерджи Сервисиз, Инк. | Fluid characterization of porous materials using laser-induced breakdown spectroscopy |
| CN105390078B (en) * | 2015-11-24 | 2019-02-12 | 国术科技(北京)有限公司 | A kind of ore identifies exhibition teaching system and method |
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| CN117451671B (en) * | 2023-12-22 | 2024-05-14 | 四川泓宝润业工程技术有限公司 | Method and device for inverting gas concentration, storage medium and electronic equipment |
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| CN1243233C (en) * | 2003-07-18 | 2006-02-22 | 华中科技大学 | Analyser for spark through spectrum medium by laser induced |
| US7760352B2 (en) * | 2008-03-18 | 2010-07-20 | Itt Manufacturing Enterprises, Inc. | Dual pulse single event Raman spectroscopy |
| CN101666746B (en) * | 2009-09-30 | 2010-10-27 | 太原市海通自动化技术有限公司 | Laser induced spectrum data processing method based on wavelet analysis |
| WO2012005775A1 (en) * | 2010-07-09 | 2012-01-12 | Los Alamos National Security, Llc | Laser induced breakdown spetroscopy instrumentation for real-time elemental analysis |
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