CN105651742A - Laser-induced breakdown spectroscopy based explosive real-time remote detection method - Google Patents
Laser-induced breakdown spectroscopy based explosive real-time remote detection method Download PDFInfo
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- CN105651742A CN105651742A CN201610013800.6A CN201610013800A CN105651742A CN 105651742 A CN105651742 A CN 105651742A CN 201610013800 A CN201610013800 A CN 201610013800A CN 105651742 A CN105651742 A CN 105651742A
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- G—PHYSICS
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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
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
Abstract
The invention relates to a laser-induced breakdown spectroscopy based explosive real-time remote detection method, belonging to the field of the spectrum detection technology. The method comprises the steps of: measuring different regions of a sample to be detected by a laser-induced breakdown spectroscopy based measurement system to obtain a spectrum; performing normalization processing to the spectral line intensity and the intensity ratio; taking the preprocessed characteristic spectral line intensity and ratio thereof as input variables, judging by a supervised learning method or a non-supervised learning method and determining whether the sample to be detected contains an explosive. According to the method, the detection efficiency is improved, the detection process is simplified, close and remote real-time detection can be realized simultaneously, a PLS-DA (partial least squares discriminant analysis) or K mean value sorting method is used to correctly judge the explosive when the processing elements constitute a substance similar to the explosive, the detection accuracy is effectively improved, and the method can be applied to airports, railway security checking and anti-terrorist and actual battlefields.
Description
Technical field
The present invention relates to a kind of explosive real-time remote detection method based on LIBS, belong to spectrographic detection technical field.
Background technology
High energy explosive plays an important role in fields such as military, Aero-Space and capital constructions, and along with the extension of application, the safety in production of high energy explosive increasingly comes into one's own with supervision. On the other hand, along with the spreading unchecked of terrorism in world wide, reply car bomb, mail bomb and body bombs etc. threaten the event of common people's safety, also in the urgent need to a kind of method that can detect explosive in real time on certain safe distance.
Anti-terrorism is the hot issue of the world today, due to disguise and the emergentness of the attack of terrorism, causes cannot carrying out early warning timely and effectively, brings loss to the person of people and property. How in real time the effective high energy explosive differentiating that terrified personnel carry, takes preventive measures in time, make harm that the attack of terrorism produces near minimum be Homeland Security and the subject matter defending field face. At present, the detection method of explosive is mainly included ion mobility spectrometry, gas chromatography, THz spectrographic method, Raman spectroscopy, surface acoustic wave method, mass spectrography and fluorescence detection etc. These methods are long due to analysis time, rate of false alarm is high, the sample preparation processes of detection is complicated, it is impossible to be applied to airport densely populated, that amount of flow is big, station and subway, therefore in the urgent need to a kind of can in real time, the explosives detection methods of accurate, early detection.
LIBS (is called for short LIBS), and technology is a kind of emerging spectrum detection technique, its principle is to utilize high energy density laser pulse ablation tested sample surface, sample is made to gasify rapidly within the time of several microseconds, ionization, producing high temperature, high-density plasma, tested sample is analyzed by spectrometer collection plasma spectrometry. Compared with other traditional analysis means, LIBS technology has many significant advantages: 1) can analyze solid-state, gaseous state and liquid sample; 2) without sample preprocessing, in situ detection can be realized;3) loss of sample is little; 4) remote remote measurement analysis can be realized; 5) response time is short, can detect by real-time synchronization; 6) there is the detection limit of ppm level.
Summary of the invention
It is an object of the invention to provide a kind of explosive real-time remote detection method based on LIBS, it is fast that the method has detection speed, can the advantage such as early detection, it is adaptable to the explosive of Homeland Security and explosive wastewater analysis field detects in real time.
Present disclosure is achieved through the following technical solutions.
Based on the explosive real-time remote detection method of LIBS, specifically comprise the following steps that
Step one, LIBS spectra collection: utilize LIBS to measure system and tested sample zones of different is measured, obtain the LIBS spectrum of tested sample.
Step 2, LIBS Pretreated spectra: the characteristic spectral line selecting explosive identification to adopt in the spectrum that step one gathers, give up other element spectral lines; Calculate the intensity rate between different characteristic spectral line, the intensity of spectral line and intensity ratio are normalized.
Step 3, LIBS spectral matching factor: will through the pretreated characteristic spectral line intensity of step 2 and ratio thereof as input variable, unsupervised learning method is utilized to carry out differentiation process, when analyzing, explosive spectrum is inputted in grader with non-explosive spectrum together with determinand spectrum and carry out cluster analysis, if determinand spectrum and explosive spectrum are polymerized to a class, then illustrate that determinand is explosive; If determinand spectrum and non-explosive spectrum are polymerized to a class, then illustrate that determinand is non-explosive.
Differentiation processing method described in step 3 can also adopt supervised learning method to differentiate explosive; When utilizing supervised learning method to process, it is necessary to setting up discrimination model in advance, tested sample LIBS spectrum is processed by recycling discrimination model.
Offset minimum binary-discriminant analysis (PLS-DA) algorithm conventional in supervised learning method, illustrates the process utilizing supervised learning method to differentiate explosive.
A () PLS-DA discrimination model sets up process as follows:
With known different types of sample for class, characteristic spectral line intensity that the LIBS spectrum of known sample step one gathered obtains through step 2 pretreatment and ratio thereof are as the independent variable matrix X of training sample, set classified variable matrix Y, with PLS homing method, the independent variable matrix X and classification matrix Y of training sample are decomposed, making the main constituent at utmost linear correlation of X and Y, model is:
X=TPT+E
Y=UQT+F
The wherein score matrix of T and U respectively X and Y, the loading matrix of P and Q respectively X and Y, the residual matrix of E and F respectively X and Y, subscript T representing matrix transposition computing;
T and U is made linear regression, U=TB, wherein regression vectors B=(TTT)-1TTY;
(b) discriminant analysis
During prediction unknown sample, the characteristic spectral line intensity through pretreatment and the ratio thereof that unknown sample are obtained according to step 2 are input in the model established, and obtain the score vector t of unknown sample x according to P, and foundation following formula calculates predictive value y;
Y=tBQ
The classification of unknown sample is judged by the value according to y.
LIBS spectral measurement system described in step one, it is possible to be close-in measurement system, it is also possible to be remote measuring system. Implement and can adopt following several ways.
Mode one is one closely pulse LIBS spectral measurement system, including laser instrument, spectroscope, collecting lens, reception lens, all band fiber optic high-resolution bundle, spectrogrph, CCD camera.The annexation of each several part is: laser instrument, spectroscope, collecting lens are sequentially placed; Spectroscope is between laser instrument and collecting lens, and its effect is to incide on collecting lens by the light beam steering 90 �� that laser instrument is launched; Collecting lens is between spectroscope and sample object stage, and its effect is by the laser beam focusing of dichroic mirror to tested sample surface; CCD camera and another sheet collecting lens are positioned at above spectroscope, and sample surface is reflected light and focuses in CCD camera after spectroscope transmission by this collecting lens, it is therefore an objective to the situation of Real Time Observation laser focusing; Receiving lens and be positioned at from sample surface correct position place, its effect is that the plasma resonance on tested sample surface converges to all band fiber optic high-resolution bundle incident end face; The other end of all band fiber optic high-resolution bundle is connected with spectrogrph; Spectrogrph utilizes data wire to be connected with computer.
Mode two is one closely dipulse LIBS spectral measurement system, including 2, laser instrument, pulse delay controller, spectroscope, collecting lens, reception lens, all band fiber optic high-resolution bundle, spectrogrph, CCD camera. The annexation of each several part is: First laser instrument, spectroscope, collecting lens are sequentially placed; Spectroscope is between laser instrument and collecting lens, and its effect is to incide on collecting lens by the light beam steering 90 �� that laser instrument is launched; Collecting lens is between spectroscope and sample, and its effect is to tested sample surface by the laser beam focusing of dichroic mirror, forms plasma on tested sample surface; Second laser instrument, collecting lens and sample are horizontal positioned, and collecting lens is between laser instrument and sample, and the concentrated lens focus of laser beam that second laser instrument sends is to the plasma produced by the tested sample surface of vertical direction beam excitation; Two laser instrument are connected with pulse delay controller, and pulse delay controller controls the pulse laser that two laser instrument produce to have certain time delay; CCD camera and another sheet collecting lens are positioned at above spectroscope, and sample surface is reflected light and focuses in CCD camera after spectroscope transmission by this collecting lens, it is therefore an objective to the situation of Real Time Observation laser focusing; Receiving lens and be positioned at from sample surface correct position place, its effect is that the plasma resonance on tested sample surface converges to all band fiber optic high-resolution bundle incident end face; The other end of all band fiber optic high-resolution bundle is connected with spectrogrph; Spectrogrph utilizes data wire to be connected with computer.
Mode three is a kind of remote LIBS spectral measurement system, including laser instrument, beam expanding lens, collecting lens, dichroic mirror, jam-Green's telescope, rotates reflecting mirror, CCD camera, all band fiber optic high-resolution bundle, spectrogrph. The annexation of each several part is: laser instrument, beam expanding lens, and collecting lens is sequentially placed in vertical jam-Green's telescope major axes orientation; Beam expanding lens and collecting lens are between laser instrument and dichroic mirror; Dichroic mirror is placed in jam-Green's telescope major axes orientation with 45 degree of angles, is positioned over jam-Green telescope principal reflection mirror rear and rotates between reflecting mirror; Rotate reflecting mirror between dichroic mirror and CCD camera, rotate reflecting mirror and 45 degree of angles can be placed in jam-Green's telescope major axes orientation, major axes orientation light beam steering 90 �� to CCD camera is received, it is also possible to pack up that the light beam making major axes orientation is unscreened incides all band fiber optic high-resolution bundle end face;The other end of all band fiber optic high-resolution bundle is connected with spectrogrph; Spectrogrph utilizes data wire to be connected with computer.
Mode four is a kind of compound LIBS spectral measurement system of the reflective excitation/collection of aspheric surface, including laser instrument; Attenuator; Parabolic mirror; Sampler chamber; Off axis paraboloid mirror collectiong focusing mirror; All band fiber optic high-resolution bundle; Spectrogrph; Computer.
The annexation of each ingredient is: laser instrument transmitting laser pulse is parallel after attenuator is decayed to be incided on parabolic mirror, focusing on, after parabolic mirror reflects, the sample to be tested surface being placed in sampler chamber being placed on its focal point F place, ablation sample produces the microplasma light radiation of high temperature high electron density. This radiant light is collimated into directional light after being reflected by parabolic mirror, incide on off axis paraboloid mirror collectiong focusing mirror, focus on after reflecting then through off axis paraboloid mirror collectiong focusing mirror and be placed on its focal point F ' on the incident end face of all band fiber optic high-resolution bundle at place, it is input in spectrogrph after all band fiber optic high-resolution bundle transmits. Spectrogrph plasma light radiation carries out light splitting and collection, and the spectroscopic data of generation is input in computer and processs and displays.
The laser instrument of described various wavelength can be the laser instrument of an output single wavelength laser, it is also possible to be a laser instrument exporting several different wave length laser. When exporting several different wave length laser, it is possible to be the window output altogether of several wavelength, it is also possible to be split window output; Can being that several wavelength exports simultaneously, it is also possible to be according to certain sequential relationship timesharing output, Main Function be to produce high energy laser pulse ablation sample surface to produce plasma.
Described spectroscope is surface coating spectroscope, is 1:1 to wavelength 190-1100nm scope luminous reflectance transmittance.
The laser instrument of described mode three is high-energy N d:YAG pulse laser, and individual pulse energy is joule level, and Main Function is to produce high energy laser pulse ablation sample surface to produce plasma.
Beam expanding lens in described mode three is plano-concave quartz lens, it is therefore an objective to the light beam sent by laser instrument expands, and the parameter of lens is according to jam-Green's telescope principal reflection mirror and secondary reflection mirror parameter.
Collimating mirror in described mode three is plano-convex quartz lens, it is therefore an objective to the light beam sent by beam expanding lens expands further, and the parameter of lens is according to jam-Green's telescope principal reflection mirror and secondary reflection mirror and beam expanding lens parameter.
Dichroic mirror in described mode three is that 1064nm �� 120nm wave band has high reflectance, and its all band is had high absorbance.
Jam in described mode three-Green's telescope is classical jam-Green's telescope, and principal reflection mirror is parabolic mirror, and secondary reflection mirror is hyperboloidal mirror, and principal reflection mirror and secondary reflection mirror surface are plated with ultraviolet highly reflecting films. Telescope plays and the high energy laser expanded focuses on sample surface generation plasma and the dual function that isoionic radiation collection focuses on all band fiber optic high-resolution bundle end face. Principal reflection mirror and secondary reflection distance between mirrors scalable, it is therefore an objective to adjust the position that high energy laser focuses on, by whether CCD camera Real Time Observation laser correctly focuses on sample surface.
Rotation in described mode three is reflected into surface-coated mirror, and wavelength 190-1100nm scope light is had high reflectance.Rotate reflecting mirror one end to fix, can rotate to jam-Green's telescope major axes orientation, be 45 degree with main shaft, it is also possible to pack up consistent with major axes orientation, after packing up, major axes orientation light beam is unobstructed.
CCD camera in described mode three is high-resolution camera, and resolution is 1024 �� 1024 pixels. Purpose is whether Real Time Observation laser correctly focuses on sample surface.
Described spectrogrph can adopt echelle spectrometer, fiber spectrometer or other form spectrogrphs, and its effect is to gather plasma spectrometry produced by high energy laser ablation sample surface.
Beneficial effect
The present invention utilizes LIBS that explosive is detected, and greatly improves the efficiency of detection, simplifies detection process; The present invention can realize closely detecting in real time with remote simultaneously, solves a difficult problem for different distance detection explosive; When the present invention utilizes PLS-DA or K average sorting technique to processing element composition with explosive similar substance, it is possible to correctly distinguish explosive, be effectively improved the accuracy of detection, can apply to airport, railway safety check and actual battlefield in the future.
Accompanying drawing explanation
Fig. 1Signal is constituted for one closely pulse LIBS spectral measurement systemFigure;
Fig. 2Signal is constituted for the remote LIBS spectral measurement system of oneFigure;
Fig. 3Signal is constituted for a kind of compound LIBS spectral measurement system of the reflective excitation/collection of aspheric surfaceFigure;
Fig. 4For K mean algorithm flow processFigure;
Fig. 5For embodiment K Mean Method recognition result, in circle is known explosive and non-explosive sample;
Fig. 6Utilize PLS-DA method to the non-explosive sample classification result in TNT and 7 kind for embodiment.
Wherein, 1 is the laser instrument of various wavelength, 2 is various rotary attenuator, 3 share parabolic mirror for excitation/collection, 4 is grab sampling room, 5 is off axis paraboloid mirror collectiong focusing mirror, 6 is all band fiber optic high-resolution bundle, 7 is spectrogrph, 8 is computer, 9 is spectroscope, 10 is collecting lens, 11 for receiving lens, 12 control device for pulse delay, 13 is beam expanding lens, 14 is dichroic mirror, 15 is principal reflection mirror, 16 is secondary reflection mirror, 17 for rotating reflecting mirror, 18 is CCD camera, the 1064nm laser that 19 is outgoing, 20 plasma optical emission for receiving.
Detailed description of the invention
In order to objects and advantages of the present invention are better described, below in conjunction withAccompanying drawingWith embodiment, present invention is described further.
Embodiment 1
For K average, illustrate that unsupervised learning is for the process of explosive identification in airfield detection. Owing to explosive is often infected with on suitcase, and suitcase is typically made of a plastic. Therefore, the sample of selection is three kinds of explosives (respectively CL-20, RDX, HMX) and two kinds of plastics (respectively ABS and Nylon). It is embodied as being divided into following 3 steps.
Step one, collection spectrum
Gather LIBS light time spectrum, make a call to 12 laser pulses in the everywhere of sample, front two hairs in cleaning sample surface, so remove need not, latter 10 are averaged as a spectrumFigure. Renew position afterwards and continue to obtain the LIBS spectrum of sample. Every kind of sample obtains 50 spectrumsFigure, 5 kinds of samples obtain altogether 250 spectrumsFigure��
Described one closely dipulse LIBS spectral measurement system, including laser instrument 1, pulse delay controller 12, spectroscope 9, collecting lens 10, receives lens 11, all band fiber optic high-resolution bundle 6, spectrogrph 7, CCD camera 18.The annexation of each several part is: First laser instrument 1, spectroscope 9, collecting lens 10 are sequentially placed; Spectroscope 9 is between laser instrument 1 and collecting lens 10, and its effect is that the light beam steering 90 �� launched by laser instrument 1 is incided on collecting lens 10; Collecting lens 10 between spectroscope 9 and sample, its effect be the laser beam focusing that spectroscope 9 is reflected to tested sample surface, tested sample surface formation plasma; Second laser instrument 1, collecting lens 10 are horizontal positioned with sample, collecting lens 10 is between laser instrument 1 and sample, and the concentrated lens 10 of laser beam that second laser instrument 1 sends focus on the plasma produced by the tested sample surface of vertical direction beam excitation; Two laser instrument are connected with pulse delay controller 12, and pulse delay controller 12 controls the pulse laser that two laser instrument produce to have certain time delay; CCD camera 18 and another sheet collecting lens 10 are positioned at above spectroscope 9, and sample surface is reflected light and focuses in CCD camera 18 after spectroscope 9 transmission by this collecting lens 10, it is therefore an objective to the situation of Real Time Observation laser focusing; Receiving lens 11 and be positioned at from sample surface correct position place, its effect is that the plasma resonance on tested sample surface converges to all band fiber optic high-resolution bundle 6 incident end face; The other end of all band fiber optic high-resolution bundle 6 is connected with spectrogrph 7; Spectrogrph 7 utilizes data wire to be connected with computer 8.
Step 2, LIBS Pretreated spectra: selected characteristic spectral line, utilize area-method calculate the intensity of spectral line and be normalized. 7 characteristic spectral lines chosen are shown inTable 1��
Table 1Element corresponding to characteristic spectral line and wavelength value
Step 3, using the characteristic spectral line intensity that processes through step 2 as input variable, utilize K-average unsupervised learning method differentiates in sample whether contain explosive.
Using 1 CL-20 and 1 ABS sample as known explosive and non-explosive spectrum, and the determinand spectrum the being previously obtained input together as K mean analysis, carry out K mean analysis. K mean analysis flow process is shown inFig. 4, detailed step is as follows:
What a () determined two classes initially represents a little so that the distance between they these two classes maximizes. The method of realization is, first making whole sample is a cluster, and its representative point is the grand mean of sample, then using the grand mean of this clustering with apart from its point furthest representative point as this two class;
B () representative point is selected after, remaining point is classified according to nearest principle;
C () determines preliminary classification after, cluster �� by first1In a sample y from ��1Move into second cluster ��2, sample average and error sum of squares can be brought certain impact. N1��N2It is the 1st, the 2nd cluster �� respectively1����2Number of samples, m1And m2It it is the two cluster sample average. If from ��1Set after middle removal y is ��1', the average of its correspondence is m1����m1And m1' be calculated as follows:
If ��2Accepting the set after y is ��2', the average of its correspondence is m2',
If (d)
Illustrate that sample is from ��1It is moved into ��2Error sum of squares will be made to reduce (only when y is from m2Distance than from m1Distance closer to time just meet above-mentioned inequality), then by y from ��1Move on to ��2In. Wherein | | y-m | | represents the 2-norm seeking y-m, the i.e. distance of y and m.
E () recalculates m1And m2Value, and calculate error sum of squares Je. The mobile error sum of squares J that can affect this two class of y1��J2��Je��J1And J2Be calculated as follows:
Total error sum of squares JeBe calculated as follows:
Je=J1+J2(7)
If (f) subsequent iteration n times JeDo not change, then stop, otherwise forward (d) to.
G () is identified result. If sample to be tested and explosive divide in a class, then belong to explosive; If dividing in a class with non-explosive, then belong to non-explosive.
The result that discriminant analysis obtainsSuch as Fig. 5Shown in, it is a class that CL-20, HMX and RDX and known CL-20 sample gather, and illustrates that they are explosives; It is a class that ABS and Nylon and known ABS sample gather, and illustrates that they are non-explosive. Thus having reached the purpose of explosive detection.
Embodiment 2
For PLS-DA, the supervised learning process for explosive identification is described. Select explosive TNT and 7 kinds of non-explosive ABS, HDPE, PET, PMMA, PP, PS, PVC as sample. Utilize LIBS to measure system and sample above is carried out spectra collection, 100 spectrum of every kind of sample collection.
Specifically comprise the following steps that
Step one, utilizing LIBS to measure system tested sample zones of different to be measured, has often gathered a spectrum, mobile tested sample, at a new station acquisition next one spectrum.
The LIBS that the present invention uses measures systemSuch as Fig. 3Shown in, share parabolic mirror 3, grab sampling room 4, off axis paraboloid mirror collectiong focusing mirror 5, all band fiber optic high-resolution bundle 6, spectrogrph 7 and computer 8 including the laser instrument 1 of various wavelength, attenuator 2, excitation/collection. Laser instrument 1 is launched laser pulse and parallel is incided on parabolic mirror 3 after attenuator 2 is decayed, focusing on the sample to be tested surface in the sampler chamber 4 being placed on its focal point F place after parabolic mirror 3 reflects, ablation sample produces the microplasma light radiation of high temperature high electron density. This radiant light is by being collimated into directional light after parabolic mirror 3 reflection, incide on off-axis parabolic mirror 5, focus on after reflecting then through off-axis parabolic mirror 5 and be placed on its focal point F ' on the incident end face of the all-wave fiber bundle 6 at place, it is input in spectrogrph 7 after fibre bundle 6 transmits. Spectrogrph 7 plasma light radiation carries out light splitting and collection, and the spectroscopic data of generation is input in computer 8 and processs and displays.
Selecting laser instrument in the present embodiment is Nd:YAG Q-switched pulse laser, and pulsed laser energy 84mJ, repetition rate 10Hz, pulsewidth 13ns, the operation wavelength of laser instrument can select in tri-kinds of wavelength of 1064nm, 532nm, 266nm. Metal (or compound) material is selected to make parabolic mirror, boreFocal distance f1��=100mm, leaving a bore for the ease of processing and installation center isCircular hole. Spot sampling room is placed on the near focal point of parabolic mirror, and the input end face distance from optical fiber is H1=60mm. The bore of off axis paraboloidal mirror isFocal length is f2��=168mm, off-axis amount is H2=30mm, the distance from parabolic reflecting mirror is H3=300mm. The input end face of optical fiber is positioned off the focal point of axis paraboloidal mirror. Spectrogrph (AvaSpec) spectral region 200-1100nm, resolution 0.3nm. In order to obtain the test effect of the best, LIBS being measured system pulses time delay, spectrogrph time of integration etc., test parameter was optimized.
Step 2, carry out Pretreated spectra. Selected characteristic spectral line, utilizes area-method calculate the intensity of spectral line and be normalized. 21 characteristic spectral lines chosen are shown inTable 2��
Table 2Element corresponding to characteristic spectral line and wavelength value
Step 3, using the characteristic spectral line intensity that processes through step 2 as input variable, utilize supervised learning method differentiates in sample whether contain explosive.
(1) adopting the PLS-DA method of supervised learning to differentiate, detailed process is as follows:
A (), by the 100 of every kind of sample spectrum, comes to 800 spectrum as modeling sample,
The independent variable matrix X and classified variable Y that utilize modeling sample set up regression model, the PLS predictive value judgment sample generic according to sample to be sorted. Differentiation process is: initially set up the classified variable of sample, then sets up the classified variable of sample and the PLS model of spectroscopic data, according to the model set up, calculates the classification predictive value of test set, and y value is a vector, and form is:
If sample belongs to explosive, then y=2;
If sample belongs to non-explosive, then y=0;
Utilizing PLS regression algorithm that the independent variable matrix X and classification matrix Y of sample are decomposed, make the main constituent at utmost linear correlation of X and Y, model is:
X=TPT+E
Y=UQT+F
The wherein score matrix of T and U respectively X and Y, the loading matrix of P and Q respectively X and Y, the residual matrix of E and F respectively X and Y, subscript T representing matrix transposition computing.
T and U is made linear regression, U=TB, wherein regression vectors B=(TTT)-1TTU��
(b) discriminant analysis
Select TNT and 7 kinds of plastics as sample to be tested, gather the spectrum of sample to be tested, 100 spectrum of every kind of sample collection according to step one method. According to step 2, the spectrum of sample to be tested done pretreatment, then the spectroscopic data after processing is input in the PLS-DA model of foundation as test sample x. Obtain the score vector t of test sample x according to P, calculate predictive value y according to y=tBQ. Concrete discriminant classification standard is: work as y>1 item judge that sample belongs to explosive; When y<1 judges that sample belongs to non-explosive. Classification resultsSuch as Fig. 6Shown in, TNT sample and 7 kinds of non-explosive samples are divided into two classes, be no matter modeling sample or test sample explosive TNT not and any 7 kinds of non-explosive sample cross, illustrating when TNT and 7 kind non-explosive sample component is similar, PLS-DA method can correctly distinguish explosive sample and non-explosive sample.
Above-described specific descriptions; the purpose of invention, technical scheme and beneficial effect have been further described; it is it should be understood that; the foregoing is only specific embodiments of the invention; for explaining the present invention, the protection domain being not intended to limit the present invention, all within the spirit and principles in the present invention; any amendment of being made, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (9)
1. based on the explosive real-time remote detection method of LIBS, it is characterised in that: specifically comprise the following steps that
Step one, LIBS spectra collection: utilize LIBS to measure system and sample zones of different is measured, obtain the LIBS spectrum of sample;
Step 2, LIBS Pretreated spectra: the characteristic spectral line selecting explosive identification to adopt in the spectrum that step one gathers, give up other element spectral lines; Calculate the intensity rate between intensity and the different characteristic spectral line of characteristic spectral line, the intensity of spectral line and intensity ratio are normalized;
Step 3, LIBS spectral matching factor: will through the pretreated characteristic spectral line intensity of step 2 and ratio thereof as input variable, unsupervised learning method is utilized to carry out differentiation process, when analyzing, explosive spectrum is inputted in grader with non-explosive spectrum together with determinand spectrum and carry out cluster analysis, if determinand spectrum and explosive spectrum are polymerized to a class, then illustrate that determinand is explosive; If determinand spectrum and non-explosive spectrum are polymerized to a class, then illustrate that determinand is non-explosive.
2.Such as claimThe explosive real-time remote detection method based on LIBS described in 1, it is characterised in that: the differentiation processing method described in step 3 differentiates explosive for adopting supervised learning method;When utilizing supervised learning method to process, it is necessary to setting up discrimination model in advance, sample LIBS spectrum is processed by recycling discrimination model.
3.Such as claimThe explosive real-time remote detection method based on LIBS described in 1 or 2, it is characterised in that: described supervised learning method is offset minimum binary-Discrimination Analysis Algorithm; Supervised learning method is utilized to differentiate the process of explosive;
A () PLS-DA discrimination model sets up process as follows:
With different types of sample for class, using through independent variable matrix X as training sample of the characteristic spectral line intensity of step 2 pretreatment and ratio thereof, set classified variable matrix Y, with PLS homing method, the independent variable matrix X and classification matrix Y of training sample are decomposed, making the main constituent at utmost linear correlation of X and Y, model is:
X=TPT+E
Y=UQT+F
The wherein score matrix of T and U respectively X and Y, the loading matrix of P and Q respectively X and Y, the residual matrix of E and F respectively X and Y, subscript T representing matrix transposition computing;
T and U is made linear regression, U=TB, wherein regression vectors B=(TTT)-1TTY;
(b) discriminant analysis
During prediction unknown sample, the LIBS spectrum of unknown sample step one gathered is through step 2 pretreatment, obtain characteristic spectral line intensity and ratio is input in the model established, obtain the score vector t of unknown sample x according to P, calculate predictive value y according to following formula;
Y=tBQ
The classification of unknown sample is judged by the value according to y.
4.Such as claimThe explosive real-time remote detection method based on LIBS described in 1, it is characterised in that: the LIBS spectral measurement system described in step one, for close-in measurement system, or remote measuring system; Including following several ways;
Mode one: one is pulse LIBS spectral measurement system closely, including laser instrument (1), spectroscope (9), collecting lens (10), receives lens (11), all band fiber optic high-resolution bundle (6), spectrogrph (7), CCD camera (18); The annexation of each several part is: laser instrument (1), spectroscope (9), collecting lens (10) are sequentially placed; Spectroscope (9) is positioned between laser instrument (1) and collecting lens (10), and its effect is that the light beam steering 90 �� launched by laser instrument (1) is incided on collecting lens (10); Collecting lens (10) is positioned between spectroscope (9) and sample stage, and its effect is that the laser beam focusing reflected by spectroscope (9) is to sample surface; CCD camera (18) and another sheet collecting lens (10) are positioned at spectroscope (9) top, sample surfaces is reflected light and focuses on after spectroscope (9) transmission in CCD camera (18) by this collecting lens (10), it is therefore an objective to the situation of Real Time Observation laser focusing; Receiving lens (11) and be positioned at from sample surfaces correct position place, its effect is that the plasma resonance on sample surface converges to all band fiber optic high-resolution bundle (6) incident end face; The other end of all band fiber optic high-resolution bundle (6) is connected with spectrogrph (7); Spectrogrph (7) utilizes data wire to be connected with computer (8);
Mode two: one is dipulse LIBS spectral measurement system closely, including (1) 2, laser instrument, pulse delay controller (12), spectroscope (9), collecting lens (10), receives lens (11), all band fiber optic high-resolution bundle (6), spectrogrph (7), CCD camera (18); The annexation of each several part is: First laser instrument (1), spectroscope (9), collecting lens (10) are sequentially placed;Spectroscope (9) is positioned between laser instrument (1) and collecting lens (10), and its effect is that the light beam steering 90 �� launched by laser instrument (1) is incided on collecting lens (10); Collecting lens (10) is positioned between spectroscope (9) and sample, its effect be the laser beam focusing that spectroscope (9) is reflected to sample surface, sample surface formation plasma; Second laser instrument (1), collecting lens (10) are horizontal positioned with sample, collecting lens (10) is positioned between laser instrument (1) and sample, and the concentrated lens of the laser beam (10) that second laser instrument (1) sends focuses on the plasma produced by the sample surface of vertical direction beam excitation; Two laser instrument are connected with pulse delay controller (12), and pulse delay controller (12) controls the pulse laser that two laser instrument produce to have certain time delay; CCD camera (18) and another sheet collecting lens (10) are positioned at spectroscope (9) top, sample surfaces is reflected light and focuses on after spectroscope (9) transmission in CCD camera (18) by this collecting lens (10), it is therefore an objective to the situation of Real Time Observation laser focusing; Receiving lens (11) and be positioned at from sample surfaces correct position place, its effect is that the plasma resonance on sample surface converges to all band fiber optic high-resolution bundle (6) incident end face; The other end of all band fiber optic high-resolution bundle (6) is connected with spectrogrph (7); Spectrogrph (7) utilizes data wire to be connected with computer (8);
Mode three: a kind of remote LIBS spectral measurement system, including laser instrument (1), beam expanding lens (13), collecting lens (10), dichroic mirror (14), jam-Green's telescope (15) (16), rotates reflecting mirror (17), CCD camera (18), all band fiber optic high-resolution bundle (6), spectrogrph (7); The annexation of each several part is: laser instrument (1), beam expanding lens (13), and collecting lens (10) is sequentially placed in vertical jam-Green's telescope major axes orientation; Beam expanding lens (13) and collecting lens (10) are positioned between laser instrument (1) and dichroic mirror (14); Dichroic mirror (14) is placed in jam-Green's telescope major axes orientation with 45 degree of angles, is positioned over jam-Green's telescope principal reflection mirror (15) rear and rotates between reflecting mirror (17); Rotate reflecting mirror (17) and be positioned between dichroic mirror (14) and CCD camera (18), rotate reflecting mirror (17) and 45 degree of angles can be placed in jam-Green's telescope major axes orientation, major axes orientation light beam steering 90 �� to CCD camera (18) is received, it is also possible to pack up that the light beam making major axes orientation is unscreened incides all band fiber optic high-resolution bundle (6) end face; The other end of all band fiber optic high-resolution bundle (6) is connected with spectrogrph (7); Spectrogrph (7) utilizes data wire to be connected with computer;
Mode four: a kind of compound LIBS spectral measurement system of the reflective excitation/collection of aspheric surface, including laser instrument (1); Attenuator (2); Parabolic mirror (3); Sampler chamber (4); Off axis paraboloid mirror collectiong focusing mirror (5); All band fiber optic high-resolution bundle (6); Spectrogrph (7); Computer (8); The annexation of each ingredient is: laser instrument (1) transmitting laser pulse is parallel after attenuator (2) is decayed to be incided on parabolic mirror (3), focusing on, after parabolic mirror (3) reflects, the testing sample surface being placed in sampler chamber (4) being placed on its focal point F place, ablation sample produces the microplasma light radiation of high temperature high electron density; This radiant light is by being collimated into directional light after parabolic mirror (3) reflection, incide on off axis paraboloid mirror collectiong focusing mirror (5), focus on after reflecting then through off axis paraboloid mirror collectiong focusing mirror (5) and be placed on its focal point F ' on the incident end face of all band fiber optic high-resolution bundle (6) at place, it is input in spectrogrph (7) after all band fiber optic high-resolution bundle (6) transmits;Spectrogrph (7) plasma light radiation carries out light splitting and collection, and the spectroscopic data of generation is input in computer (8) and processs and displays.
5.Such as claimThe explosive real-time remote detection method based on LIBS described in 1 or 4, it is characterised in that: described laser instrument is the laser instrument of an output single wavelength laser, or a laser instrument exporting several different wave length laser.
6.Such as claimThe explosive real-time remote detection method based on LIBS described in 5, it is characterised in that: when described laser instrument is for exporting several different wave length laser, several wavelength are window output altogether, or split window output.
7.Such as claimThe explosive real-time remote detection method based on LIBS described in 4, it is characterised in that: described spectroscope is surface coating spectroscope, is 1:1 to wavelength 190-1100nm scope luminous reflectance transmittance.
8.Such as claimThe explosive real-time remote detection method based on LIBS described in 4, it is characterized in that: the laser instrument of described mode three is high-energy N d:YAG pulse laser, individual pulse energy is joule level, and Main Function is to produce high energy laser pulse ablation sample surfaces to produce plasma; Beam expanding lens in described mode three is plano-concave quartz lens, it is therefore an objective to the light beam sent by laser instrument expands, and the parameter of lens is according to jam-Green's telescope principal reflection mirror and secondary reflection mirror parameter; Collimating mirror in described mode three is plano-convex quartz lens, it is therefore an objective to the light beam sent by beam expanding lens expands further, and the parameter of lens is according to jam-Green's telescope principal reflection mirror and secondary reflection mirror and beam expanding lens parameter; Dichroic mirror in described mode three is that 1064nm �� 120nm wave band has high reflectance, and its all band has high absorbance; Jam in described mode three-Green's telescope is classical jam-Green's telescope, and principal reflection mirror is parabolic mirror, and secondary reflection mirror is hyperboloidal mirror, and principal reflection mirror and secondary reflection mirror surface are plated with ultraviolet highly reflecting films; Telescope plays and the high energy laser expanded focuses on sample surfaces generation plasma and the dual function that isoionic radiation collection focuses on all band fiber optic high-resolution bundle end face; Principal reflection mirror and secondary reflection distance between mirrors scalable, it is therefore an objective to adjust the position that high energy laser focuses on, by whether CCD camera Real Time Observation laser correctly focuses on sample surfaces; Rotation in described mode three is reflected into surface-coated mirror, and wavelength 190-1100nm scope light is had high reflectance; Rotate reflecting mirror one end to fix, can rotate to jam-Green's telescope major axes orientation, be 45 degree with main shaft, it is also possible to pack up consistent with major axes orientation, after packing up, major axes orientation light beam is unobstructed; CCD camera in described mode three is high-resolution camera, and resolution is 1024 �� 1024 pixels; Purpose is whether Real Time Observation laser correctly focuses on sample surfaces.
9.Such as claimThe explosive real-time remote detection method based on LIBS described in 4, it is characterized in that: described spectrogrph includes echelle spectrometer, fiber spectrometer or other form spectrogrphs, its effect is to gather plasma spectrometry produced by high energy laser ablation sample surfaces.
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| CN106442471A (en) * | 2016-10-28 | 2017-02-22 | 段忆翔 | Remote measuring device based on LIBS (laser-induced breakdown spectroscopy) technology |
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