CN102590157A - 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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- CN102590157A CN102590157A CN2012100381574A CN201210038157A CN102590157A CN 102590157 A CN102590157 A CN 102590157A CN 2012100381574 A CN2012100381574 A CN 2012100381574A CN 201210038157 A CN201210038157 A CN 201210038157A CN 102590157 A CN102590157 A CN 102590157A
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- 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 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 range, be specifically related to a kind of element spectrum analysis method and adopt the laser element exploring equipment of this method.
Background technology
In commercial production, scientific research, usually to carry out qualitative, quantitative check and analysis to the chemical element of associated materials and mineral.Traditional material, ore detect and analytic approach mainly contains chemical assay method, atomic absorption method and inductively coupled plasma emission spectrography.Wherein, chemical analysis and atomic absorption method need need long analysis time and loaded down with trivial details running program from the field acquisition sample, and are prone to form secondary pollution, so only limit to lab analysis; Inductively coupled plasma emission spectrography is highly sensitive, can measure simultaneously multiple element, but need carry out complicated pretreatment to sample, and reagent dosage is also bigger, and the plasma torch pipe is stain easily.Explore at the scene both at home and abroad at present that prevailing method is x ray fluorescence spectrometry (XRF) in the industry, adopt X fluorescent energy chromatic dispersion or wavelength dispersion principle, measure accurately, need not take a sample and destroy testing sample; Can on-the-spot carry out direct check and analysis to composition of ores, but its in air ambient to light element (like Mg, Al; Si, P, S etc.) a little less than the distinguishing ability; To atomic weight is that elements are contained below 23 then need be matched helium charging unit, and must directly contact with sample when measuring, and cannot realize remote measurement; X ray has radiation hazard in addition, and long-term use causes all kinds of diseases easily, more than all limited the further popularization of this method.
LIBS method (laser induced breakdown spectroscopy) is called for short LIBS; It is a kind of laser ablation spectral analysis technique; But have the sample pretreatment of need not, measuring speed fast, highly sensitive, to the little multielement of sample destructiveness analyze simultaneously, to light element (like Mg, Al, Si; P, S etc.) but advantages such as distinguishing ability is strong, the radiationless remote measurement of safety.The LIBS method is based on pulsed laser technique; With the surface of a branch of high-octane laser focusing to material to be analyzed; Focusing place part material ablation back is produced high-temperature plasma, and plasma temperature rises to several thousand degree, produces more charged ion.The ionizing radiation of each element forms continuous background spectral line, this process need hundreds of nanosecond in the plasma; Form each atoms of elements spectral line of emission in the plasma afterwards; Atomic emission line has comprised the characteristic information of each element; Different element correspondence atomic emission lines separately; Line strength and concentration of element are approximated to direct ratio, and this process continues several microseconds, are 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 the sample; Ratio through analyzing the intensity between each spectral line gets final product the relative content that quantitative test goes out each element in the sample.The free scaling method that adopts the industry to know when element is carried out quantitative test, promptly directly according to the relative intensity of the atomic emission line that obtains, normalization calculates each component concentrations, the interference that can avoid different types of ore substrate variations to bring like this.When calculating the relative intensity of spectral line, adopt the spectral line peak height as the spectral line relative intensity.
When said quantitative analysis method utilizes free scaling method analytical element concentration, through improving the measuring accuracy that relevant intermediate computations CALCULATION OF PARAMETERS accuracy (plasma temperature, electron density, line strength etc.) improves free scaling method.During the calculating plasma temperature, utilize Saha-Boltzmann multiple chart method replacement Boltzmann oblique line method commonly used, pass through the variation of Saha equation, do oblique line and confirm temperature with the monovalent ion spectrum and the neutral atom spectrum of identity element.Because select the spectral line of emission for use, and their last energy level has bigger energy level difference, so temperature calculation is had higher accuracy from the different electric amorph.Carry out the Saha conversion and need measure plasma electron density, calculate electron density through the Stark broadening of analyzing the spectral line of emission here.It is the Lorentzian type that spectral line Stark widens main line style, adopts Lorentzian profile linear fitting that the spectral line line style is revised, and can avoid spectral line that the overlapping interference that causes is arranged, and improves the computational accuracy of spectrum peak width, improves measuring accuracy indirectly.
At present the qualitative analysis method that also need detect by an unaided eye of element is sought atomic emissions spectrum peak, search and compare through the atomic spectra database of the abbreviation NIST of National Institute of Standards and Technology (National Institute of Standards and Technology) again; Since usually not accurate enough to the judgement of position, peak, make and can't realize qualitative analysis accurately unknown mineral samplers; Adopt the spectrum peak height to represent the relative intensity of atomic emission line in the quantitative test, cause analysis result reliable inadequately; The LIBS detection system of using at present exists laser intensity stable inadequately, and the laser of launching is when ablating to sample, and the atomic emission line intensity that the plasma resonance that causes sample to produce goes out is unstable equally, has influenced the accuracy of quantitative test; The LIBS detection system of moulding at present generally is made up of accent Q formula Nd:YAG laser instrument, spectrometer, signal generator, data acquisition and the signal processing system etc. of xenon flash lamp pumping; Volume is bigger; And need the 220V mains-supplied; Limited its movability, carried when being not easy to field work or site inspection.
Summary of the invention
The present invention exists defective to cause analysis result inaccurate in order to solve at present for atoms of elements emission spectrographic analysis method; And the LASER Light Source insufficient strength on the present used laser element exploring equipment is stable and carry inadequately technical matters easily, a kind of element spectrum analysis method is provided and adopts the laser element exploring equipment of this method.
Element spectrum analysis method according to the invention has adopted following technical scheme to realize: a kind of element spectrum analysis method comprises method for qualitative analysis that atomic emission line carried out and the quantitative analysis method of adopting free scaling method to testing sample; Said method for qualitative analysis may further comprise the steps: (a) atomic emission line of sample is asked second derivative; (b), judge the minimum point after the difference quotient according to the stimulus threshold criterion of following regulation for the result behind the spectral line second derivative:
Only keep behind the second derivative less than the point of threshold value, said standard deviation is the standard deviation of gained data behind the spectral line second derivative; (c) to point less than threshold value, adopt triangle test to confirm 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 peak area, adopt the influence of LIBS spectral line modification method innovation spectrum line broadening.
In the said method for qualitative analysis, the LIBS spectral line that collects is asked second derivative, shown in Fig. 1 (b), according to the character of second derivative, the location, peak is positioned at the minimal value place.For the suprabasil weak peak of former spectral line, comparatively slow because of its variation, can become very little peak of amplitude or sweep after the second order difference quotient.Set a threshold value,, be regarded as that suprabasil gradual ghost peak causes, do not consider greater than the minimum point of threshold value; Only consider that second order leads the part less than threshold value, like Fig. 1 (c); Confirm its minimum point with triangle test, be the location, peak of former spectral line, shown in Fig. 1 (d).In order to suppress in the substrate insignificant ghost peak to greatest extent and don't to miss real peak, need to select appropriate threshold, could obtain the good peak effect of looking for.Threshold value is low excessively, can find out upward 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 bases of a large amount of tests, and (Stanard Deviation is SD) for reference to fluctuating with the standard deviation of data for the threshold value of selection.Find that through experiment when the standard deviation of data was big, getting standard deviation was that threshold value can suppress ghost peak to greatest extent and don't miss real peak; When standard deviation hour, need suitably increase threshold value in order to avoid suprabasil ghost peak is known by mistake, and SD is more little, the multiple that needs to increase is big more, could obtain the good peak effect of looking for.Adopt this method to can be good at eliminating the influence of ground unrest, improve the precision of qualitative analysis.Said triangle test is widely used in the signal analysis field, is those skilled in the art's common practise.
Element is carried out the free scaling method that quantitative test adopts the industry to know, when calculating the relative intensity of the spectral line of emission, represent with the spectrum peak area without its peak height.The peak height that only relies on than traditional is judged the analytical approach of peak strength, and this method can effectively improve precision of analysis.When but this method is applied to the analysis of atomic emission line intensity; Following problems can occur, promptly the broadening of indivedual spectral lines can cause the change of spectrum peak area, like a, b spectral line among Fig. 2; The peak height of a line is less than the b line; But because broadening, the peak area of a line causes measurement result inaccurate greater than the peak area of b line.Therefore when calculating peak area, need adopt the influence 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 to adopt following technical scheme to realize: 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; Said laser source system comprises laser head, the Laser Power Devices that are connected with laser head, the trigger that is connected with Laser Power Devices and the power supply that is connected with trigger; The spectra collection system comprises miniature focusing system, through the spectrometer that optical fiber and miniature focusing system are connected and are connected with power supply, said optical fiber is connected with the input end of spectrometer; Be provided with the condenser lens of adjustable angle along the light path of laser head; The spectrometer output terminal is connected with the input end of photoelectric commutator; The computer system output terminal is connected with display screen; Computer system in the signal processing module adopts described element spectrum analysis method that the atomic emission line that is collected is analyzed, and exports analysis result to display screen under the support of corresponding software.
Described laser element exploring equipment also comprises closed loop energy negative feedback laser energy systems stabilisation; Said closed loop energy negative feedback laser energy systems stabilisation comprises the Amici prism that is arranged on the adjustable angle between laser head and the condenser lens, the sniffer that matches with Amici prism, the feedback circuit that is connected with sniffer; Feedback circuit is connected with Laser Power Devices, and sniffer comprises thermopile detector and the computer control system that is 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; Said closed loop energy negative feedback laser energy systems stabilisation adopts following method that 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 converts the light signal of the pulse laser that collects electric signal into and inputs to computer control system; Computer control system is carried out intensity to the pulsed laser energy that is converted into electric signal that collects and is calculated under the support of corresponding software; The integrated intensity of the spectrum peak area of employing pulse laser comes the energy intensity of indicating impulse laser during calculating; And the numerical value of the specified laser intensity of result of calculation and laser head output compared; The electric signal that computer control system will compare back gained difference inputs to feedback circuit, and 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 that is connected with the hand-held fuselage; Laser head, miniature focusing system, condenser lens and sniffer are arranged on the hand-held fuselage interior; Laser Power Devices, signal processing module, feedback circuit, trigger, power supply, spectrometer are arranged on suitcase inside; Said power supply is an accumulator, and optical fiber is arranged on integral body inside, and the hand-held fuselage is provided with the taper measuring head along an end of laser head light path, and miniature focusing system is arranged near the taper measuring head; Said display screen is miniature display screen and is arranged on the hand-held fuselage outer side that the hand-held fuselage outer side also is 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; Be provided with accumulator in the computer system, can be whole signal processing module power supply.During work, laser head is aimed at sample, through the flip-flop toggle Laser Power Devices; Laser Power Devices control laser head sends pulse laser; Pulse laser line focus lens focus, and shine the testing sample surface makes sample focus on the position generation plasma that is excited; The atomic emission line of this plasma institute radiation is received by miniature focusing system and reaches in the spectrometer through an optical fiber; By spectrometer it is carried out beam split, and with spectral signal input signal processing module, the photoelectric commutator in the signal processing module converts light signal to corresponding electric signal; Computer system adopts element spectrum analysis method that the spectral signal that converts electric signal to is carried out the qualitative and quantitative analysis under the support of corresponding software, and analysis result is presented on the display screen.Present technique field personnel's element spectrum analysis method disclosed according to the present invention is easy to write out easily corresponding software.
When utilization LIBS carries out the element exploration; The instability of laser energy and eyeglass the plasma that the influence of factor can cause pulse laser to produce such as are stained and are had certain fluctuation; Difference can appear in the intensity of spectral signal, thereby can influence 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 in the laser emitting light path, having placed Amici prism and having matched with Amici prism; Amici prism with a part of laser-bounce to sniffer; Sniffer is used for detecting the size of the pulsed laser energy of output; And the corresponding feedback signal is input in the feedback circuit, the pumping voltage of adjusting in real time in the Laser Power Devices through feedback circuit makes the outgoing pulsed laser energy stable.Form a closed-loop control system between said laser source system, sniffer, the feedback circuit.Feedback circuit can have multiple structure to realize, relevant technology is known in those skilled in the art.Be provided with accumulator in the sniffer in the computer control system, be whole sniffer power supply; When electric heating heap detector was gathered laser energy, sampling rate was 200000S/s, is the pulse energy signal that collects like Fig. 4.When the paired pulses laser energy calculates; For improving computational accuracy; Adopt the integrated intensity of peak area to come the energy of indicating impulse laser without its peak height; Be the poor of dash area area and background signal area occupied among Fig. 4, the intensity of background signal can by spectrum both sides, peak comparatively the mean value of flat portions represent.To the pulse energy that calculates with this kind method with record the result through power meter and make comparisons, the result is as shown in Figure 5.Visible by Fig. 5, almost linear between the two, the degree of correlation is higher.Thermopile detector is to input to computer control system, the intensity level I of the pulsed laser energy that converts electric signal into that computer control system will be imported behind the electric signal under the support of corresponding software with the pulsed laser energy conversion of signals that detects
RealSpecified pulse laser output intensity I with used laser source system
VolumeCompare, and will reflect I
RealWith I
VolumeThe electric signal of difference input to feedback circuit; Feedback circuit is adjusted according to the pumping voltage of the difference Signals in Laser power supply of input in real time; If the laser intensity of output is greater than ratings; The pumping voltage of feedback circuit control Laser Power Devices reduces, and the laser intensity of laser head output is reduced, up near ratings; The laser intensity of output is during less than ratings, and the pumping voltage of feedback circuit control Laser Power Devices raises, and the laser intensity of laser head output is strengthened, up near ratings.The present invention can be controlled at the instability of pulsed laser output energy ± 2% in.Fig. 6 has shown under the 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.From Fig. 6, can see, the stable stability that can significantly promote laser output energy of the closed loop energy negative feedback laser energy that the present invention adopts, thus improve the precision and the stability of quantitative test.
Each parts of LIBS detection system are arranged on integral body inside, and are that trigger and spectrometer are supplied power through accumulator, convenient in the open air 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); The integral body outside is provided with the switch of inner each parts of control, convenient controlling entire equipment; Handle be provided with the assurance that is beneficial to operating personnel.Adopt the taper measuring head to help to make fuselage to aim at sample; Power supply adopts accumulator, discharges and recharges very easyly, and can change at any time, has made things convenient for carrying when going out operation; Miniature display screen timely display analysis result when reducing equipment volume.
Laser source system of the present invention, spectra collection system, signal processing module and sniffer are existing known technology, multiple structure and relevant model can be arranged for you to choose, are easy on the market buy.
The peak-seeking that similar approach existed before method for qualitative analysis disclosed by the invention had overcome inadequately precisely, analytic process is slow and the inaccurate problem of result; Adopt the spectrum peak area to represent relative intensity in the quantitative analysis method, when calculating peak area, need adopt the influence 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 that is adopted makes that the laser source system emitted laser is more stable, and the spectrum of the plasma emission that produces during sampling is more stable, has improved the reliability of quantitative analysis results.The present invention is because its volume is little, in light weight, and display result is fit to the field condition operation very much in real time.
Description of drawings
Fig. 1 method for qualitative analysis synoptic diagram.Figure a is the sample atoms spectral line of emission that spectrometer records; Figure b is for asking the result behind the second derivative to the spectrum that records; Figure c is for to remove the peak that stays behind the point greater than threshold value according to stimulus threshold criterion; Figure d is the location, peak of the former spectral line that finds according to triangle test, and solid dot is represented the location, peak among the figure.
The influence that broadening caused at peak when Fig. 2 calculates peak area.
Fig. 3 laser element according to the invention exploring equipment structural representation.
The pulsed laser energy signal that Fig. 4 thermopile detector collects and the area integral synoptic diagram of laser energy.
Fig. 5 adopts relatively synoptic diagram of result that laser intensity that the integrated intensity of peak area calculates and power meter record.Solid dot is represented the laser intensity that power meter records and the corresponding relation of respective peaks area among the figure, and oblique line is represented the integrated intensity of peak area and the corresponding relation of laser intensity.
Fig. 6 uses before and after the 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 using, and figure b is for after using.The energy intensity of the pulse laser that solid dot is represented to record.
Fig. 7 the present invention is to four kinds of test result of samples.Figure a is a brass, and figure b is an aluminium sheet, and figure c is the solar power silicon plate, and figure d is the antifungin compressing tablet.
The 1-laser head, 2-sniffer, 3-Amici prism, 4-condenser lens, 5-taper measuring head, the miniature focusing system of 6-, 7-optical fiber, the miniature display screen of 8-, 9-handle, 10-signal processing module, 11-power supply, 12-feedback circuit; The 13-Laser Power Devices, 14-trigger, 15-spectrometer, 16-hand-held fuselage, 17-suitcase, 18-sample.
Embodiment
A kind of element spectrum analysis method comprises method for qualitative analysis that atomic emission line carried out and the quantitative analysis method of adopting free scaling method to testing sample; Said method for qualitative analysis may further comprise the steps: (a) atomic emission line of sample is asked second derivative; (b), judge the minimum point after the difference quotient according to the stimulus threshold criterion of following regulation for the result behind the spectral line second derivative:
Only keep behind the second derivative less than the point of threshold value, said standard deviation is the standard deviation of gained data behind the spectral line second derivative; (c) to point less than threshold value, adopt triangle test to confirm 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 peak area, adopt the influence of LIBS spectral line modification method innovation spectrum line broadening.
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 10 of photoelectric commutator and computer system; The output terminal of photoelectric commutator is connected with the input end of computer system; Said laser source system comprises laser head 1, the Laser Power Devices 13 that are connected with laser head 1, the trigger 14 that is connected with Laser Power Devices 13 and the power supply 11 that is connected with trigger 14; The spectra collection system comprises miniature focusing system 6, through the spectrometer 15 that optical fiber 7 and miniature focusing system 6 are connected and are connected with power supply 11, said optical fiber 7 is connected with the input end of spectrometer 15; Be provided with the condenser lens 4 of adjustable angle along the light path of laser head 1; Spectrometer 15 output terminals are connected with the input end of photoelectric commutator; The computer system output terminal is connected with display screen 8; Computer system in the signal processing module 10 adopts described element spectrum analysis method that the atomic emission line that is collected is analyzed, and exports analysis result to display screen 8 under the support of corresponding software.Also comprise closed loop energy negative feedback laser energy systems stabilisation; Said closed loop energy negative feedback laser energy systems stabilisation comprises the Amici prism 3 that is arranged on the adjustable angle between laser head 1 and the condenser lens 4, the sniffer 2 that matches with Amici prism 3, the feedback circuit 12 that 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 that is 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; Said closed loop energy negative feedback laser energy systems stabilisation adopts following method that 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 converts the light signal of the pulse laser that collects electric signal into and inputs to computer control system; Computer control system is carried out intensity to the pulsed laser energy that is converted into electric signal that collects and is calculated under the support of corresponding software; The integrated intensity of the spectrum peak area of employing pulse laser comes the energy intensity of indicating impulse laser during calculating; And the numerical value of the specified laser intensity of result of calculation and laser head 1 compared; The electric signal that computer control system will compare back gained difference inputs to feedback circuit 12, and 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 that is 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; Said power supply 11 is an accumulator, and optical fiber 7 is arranged on integral body inside, and hand-held fuselage 16 is provided with taper measuring head 5 along an end of laser head light path, and miniature focusing system 6 is arranged near the taper measuring head 5; Said display screen 8 is for miniature display screen and be arranged on the hand-held fuselage outer side, and hand-held fuselage 16 outsides also are provided with handle 9.Hand-held fuselage 16 and suitcase 17 are connected through threaded line pipe.Laser head 1 is a high pressure trigger-type laser head.Computer system in the signal processing module 10 adopts miniature notebook computer.Accumulator is the 12V accumulator.
Hand-held fuselage 16 and suitcase 17 are connected through threaded line pipe, can make things convenient for the activity of hand-held fuselage, and sample aims at the mark when helping surveying; Computer system adopts miniature notebook computer, has further reduced the volume of this equipment; 12V accumulator volume is small and exquisite, and charging fast; Advantages such as high pressure trigger-type laser head has the reliability height, and standby current is little.
During practical implementation, used laser source system is portable high power Nd: the YAG Optical Maser System, and the model that laser head 1 wherein adopts is the high pressure trigger-type laser head of LMS-367; Trigger 14 used models are MK-367HC; Laser Power Devices 13 used models are MK-106.20; The Avantes AvaSpec-2048-USB2 spectrometer that the Dutch Avantes of spectrometer 15 employings company produces; The total silicon optical fiber that the Dutch Avantes of optical fiber 7 employings company produces, numerical aperture 0.22,600 microns of fiber core diameters.
Fig. 7 specifically is applied to the analysis result that the miniature display screen 8 in actual exploration back is shown for the present invention.The peak value of each the atoms of elements spectral line of emission in the sample 18 that each solid dot representation signal processing module analyzes among the figure.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 method for qualitative analysis that atomic emission line carried out and the quantitative analysis method of adopting free scaling method to testing sample; It is characterized in that said method for qualitative analysis may further comprise the steps: (a) atomic emission line of sample is asked second derivative; (b), judge the minimum point after the difference quotient according to the stimulus threshold criterion of following regulation for the result behind the spectral line second derivative:
Only keep behind the second derivative less than the point of threshold value, said standard deviation is the standard deviation of gained data behind the spectral line second derivative; (c) to point less than threshold value, adopt triangle test to confirm 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 peak area, adopt the influence of LIBS spectral line modification method innovation spectrum line broadening.
2. one kind is adopted the laser element exploring equipment of element spectrum analysis method according to claim 1, comprises laser source system, spectra collection system, includes 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; Said laser source system comprises laser head (1), the Laser Power Devices (13) that are connected with laser head (1), the trigger (14) that is connected with Laser Power Devices (13) and the power supply (11) that is connected with trigger (14); The spectra collection system comprises miniature focusing system (6), through the spectrometer (15) that optical fiber (7) is connected and is connected with power supply (11) with miniature focusing system (6), said optical fiber (7) is connected with the input end of spectrometer (15); Be provided with the condenser lens (4) of adjustable angle along the light path of laser head (1); Spectrometer (15) output terminal is connected with the input end of photoelectric commutator; The computer system output terminal is connected with display screen (8); It is characterized in that the computer system in the signal processing module (10) adopts described element spectrum analysis method that the atomic emission line that is collected is analyzed, and exports analysis result to display screen (8) under the support of corresponding software.
3. laser element exploring equipment as claimed in claim 2; It is characterized in that also comprising closed loop energy negative feedback laser energy systems stabilisation; Said closed loop energy negative feedback laser energy systems stabilisation comprises the Amici prism (3) that is arranged on the adjustable angle between laser head (1) and the condenser lens (4), the sniffer (2) that matches with Amici prism (3), the feedback circuit (12) that 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 that is 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); Said closed loop energy negative feedback laser energy systems stabilisation adopts following method that 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) converts the light signal of the pulse laser that collects electric signal into and inputs to computer control system; Computer control system is carried out intensity to the pulsed laser energy that is converted into electric signal that collects and is calculated under the support of corresponding software; The integrated intensity of the spectrum peak area of employing pulse laser comes the energy intensity of indicating impulse laser during calculating; And the numerical value of the specified laser intensity of result of calculation and laser head (1) compared; The electric signal that computer control system will compare back gained difference inputs to feedback circuit (12), and 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 is characterized in that also comprising an integral body, and integral body comprises hand-held fuselage (16) and the suitcase (17) that is 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; Said power supply (11) is an accumulator, and optical fiber (7) is arranged on integral body inside, and hand-held fuselage (16) is provided with taper measuring head (5) along an end of laser head (1) light path, and miniature focusing system (6) is arranged near the taper measuring head (5); Said display screen (8) is for miniature display screen and be arranged on the hand-held fuselage outer side, and hand-held fuselage (16) outside also is provided with handle (9).
5. laser element exploring equipment as claimed in claim 4 is characterized in that hand-held fuselage (16) is connected through threaded line pipe with suitcase (17).
6. like claim 2 or 3 described laser element exploring equipments, it is characterized in that said laser head (1) is a high pressure trigger-type laser head.
7. laser element exploring equipment as claimed in claim 4 is characterized in that said laser head (1) is a high pressure trigger-type laser head.
8. like claim 2 or 3 described laser element exploring equipments, it is characterized in that the computer system in the said signal processing module (10) adopts miniature notebook computer.
9. laser element exploring equipment as claimed in claim 4 is characterized in that the computer system in the said signal processing module (10) adopts miniature notebook computer.
10. laser element exploring equipment as claimed in claim 4 is characterized in that said accumulator is the 12V accumulator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210038157.4A CN102590157B (en) | 2012-02-20 | 2012-02-20 | Element spectrum analysis method and laser element exploration equipment adopting same |
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| CN108872074A (en) * | 2018-06-08 | 2018-11-23 | 北京农业智能装备技术研究中心 | A kind of soil nutrient elements detection system and method |
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| CN117451671A (en) * | 2023-12-22 | 2024-01-26 | 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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