CN102749309B - Laser-induced breakdown spectrograph for rapid analysis of metallurgical components and analysis method therefor - Google Patents
Laser-induced breakdown spectrograph for rapid analysis of metallurgical components and analysis method therefor Download PDFInfo
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Abstract
The invention discloses a laser-induced breakdown spectrograph for rapid analysis of metallurgical components and an analysis method therefor, and belongs to the technical field of metallurgical component analysis. The laser-induced breakdown spectrograph comprises a nanosecond laser, a multi-path photo-electric direct-reading spectrometer, a synchronous control device, a component analysis computer, a reflector, a focusing lens, a sample chamber, a sample container, an argon supply system, a collection lens and an optical fiber. The nanosecond laser and the component analysis computer are connected by a cable. The component analysis computer and the multi-path photo-electric direct-reading spectrometer are connected by a cable. The multi-path photo-electric direct-reading spectrometer and the synchronous control device are connected by a cable. The synchronous control device and the component analysis computer are connected by a cable. The analysis method comprises establishment of all non-matrix element working curves and measurement of all non-matrix element content values of unknown samples. The laser-induced breakdown spectrograph and the analysis method have the advantage that in detection analysis, accurate detection results can be obtained in 1 minute without pretreatment on a sample and the precision satisfies on-site analysis requirements.
Description
Technical field
The invention belongs to metallurgically analysis technical field, a kind of laser induced breakdown spectrograph and analytical approach of metallurgically express-analysis is particularly provided.
Background technology
In metal smelt process, in order to ensure the quality of products, must carry out repeatedly stokehold constituent analysis, conventional rapid analysis is mainly spark photoelectric direct reading spectrometry method and fluorescent spectrometry at present.For each analysis, all need sampling, sample presentation, grind away, test, need at the soonest just can obtain for 4 minutes result.Reduce like this efficiency of analyzing, increased energy consumption, be difficult to adapt to the modern requirement of producing of smelting.
For this reason, metallargist's development metallurgically rapid analysis, these rapid analysiss are all take Direct Analysis bath composition rather than solid constituent as starting point.
Aspect melt gases composition detection, document (Zhang Junying, Zhu Chengyi, Li Guangqiang. molten steel composition sensor and application progress [J] thereof. sensor world .2005 (10): 6-11.) and (Wan Yajing. modern metallurgical sensor [M]. Beijing: China Machine Press, 2009) summarized the detection present situation of O, N, H element.The existing practical online detection elemental gas O of metallurgy industry, the device of H, N at present, main probe (molten steel and the Tong Shui that uses electrochemical principle, O) or carrier gas probe (molten steel and aluminium water, H), analytical instrument is used apparatus for determination of oxygen (O), thermal conductance instrument (H) or mass spectrometer (O, H, N).In melt non-pneumatic element context of detection, the practical on-line measuring device of existing C, Si, S at present, sensor uses the sublance (C) of thermoelectric effect or determines carbon cup (C or C+Si), and the probe of electrochemical principle (S).Instrument uses millivolt signal detecting device.
Document (N.Ramaseder, J.Gruber, J.Heitz, D.Baeuerle. analyze continuously the novel VAI-CON Chem system [J] of molten steel chemical composition in metallurgical furnace. iron and steel .2002,37 (10): 19-22) reported that use Laser-induced Breakdown Spectroscopy technology (LIBS) carries out the online utility unit detecting of AOD stove molten steel Cr, Ni, Mn element.Its feature is to utilize air port to carry out continuous coverage, but can only measure near the composition of the point of fixity in air port in melt; In addition, because many smelting furnaces do not exist air port, therefore this measuring technique is not easy to be generalized to these type of furnaces.
Document (Lin Xiaomei, Cao Jiqing, Yin Qinghui, Liu Xiaoqing. the AOD stove silicone content on-line analysis [J] based on LIBS technology. ferroalloy .2009 (1): 41-44) reported and used LIBS technology to carry out the online utility unit detecting of AOD stove molten steel Si content, feature is, by designed, designed sampler, melt is picked and placeed to fire door sample pool, re-uses LIBS instrument melt is sampled and carries out composition.This goes a step further before for traditional sampling, liquid is measured rather than solid is measured, but for single-element measure rather than simultaneous determination of multielement.
Document (De Saro, R., Weisberg, A., Craparo, J., In Situ, Real Time Measurement ofAluminum, Steel, and Glass Melt Chemistries Using Laser Induced Breakdown Spectroscopy[C], 2005 ACEEE Summer Study on Energy Efficiency in Industry, West Point, NY July 19-22, 2005) reported that use LIBS technology carries out Al in industry spot aluminium alloy melt, Cu, Fe, Mg, Mn, Si, the utility unit of the online detection of Cr, its sensor is the probe (patent No. US6784429B2) that is immersed in melt.This characteristic sensor is to carry out the continuous coverage of aluminium alloy melt, there are no the report of measuring in molten steel (liquid steel temperature is generally than high 300 ~ 500 degree of aluminium alloy melt temperature).
Document (C.Aragon, J.A.Agulera, and J Campos. Determination of Carbon Content in Molten Steel Using Laser-Induced Brakdown Spectroscopy[J] .Applied Spectroscopy. 1993,47 (5): 606-608) in laboratory, use LIBS instrument and pop one's head in and carry out the research of small-sized coreless induction furnace molten steel C composition continuous coverage, there are no carrying out practical report in industry spot;
Document (Laszlo Peter, Volker Sturm, and Reinhard Noll. Liquid steel analysis with laser-induced brakdown spectrometry in the vacuum ultraviolet[J]. Applied Optics. 2003, 42 (30): 6199-6203) laboratory use LIBS instrument and probe carry out small intermediate frequency stove molten steel in multicomponent (C, S, P, Cr, Ni) continuous coverage, but probe need to add the particular design such as water-cooling system, for guaranteeing safety, sonde configuration complexity, therefore the use cost of popping one's head in is higher.There are no carrying out practical report in industry spot.
Described in summary, yet there are no a kind of device, can adapt to different melt temperature, can carry out simultaneous determination of multielement and the lower quick component measurement system in stokehold of use cost.The technology addressing this problem has two kinds: one is to use deflection type to pop one's head in and mate LIBS technology directly melt to be carried out to multielement measurement; One is that melt sampling is placed in instrument, makes probe and melt spaced apart, so that melt is measured.These two kinds of methods have reduced the complicacy of probe, have reduced use cost, are easy to use at the scene.The existing invention of front a kind of technology (" a kind of metallurgically on-line measuring device and method ") relates to.The present invention focuses on rear a kind of technology.
Summary of the invention
The object of the present invention is to provide a kind of laser induced breakdown spectrograph and analytical approach of metallurgically express-analysis.Use sample spoon from stove, to take out melt sample and put in sample container (such as crucible), the sample room that then sample container is put into instrument, then measures melt sample.It can obtain testing result accurately without sample is carried out to pre-treatment in one minute, and precision reaches the requirement of on-the site analysis.
Note: in analysis field, do not comprise the time of the typical curve of setting up the each element of sample detection time because Criterion curve can carry out in advance, and is just quoted calculating when measuring unknown sample constituent content.
For manufacture of iron and steel by melting, metallurgically of the present invention refers to C, Si, Mn, S, P, Cr, Ni, Al, Cu etc.; To smelting copper alloy, metallurgically of the present invention refers to Pb, Fe, Ni, Al, Mn, Sn, Si, P etc., and for aluminium alloy smelting, metallurgically of the present invention refers to Si, Cr, Mn, Fe, Al, Cu etc.;
The principle of this instrument is: the pulse laser beam of certain high energy converges at sample surface, makes the micro substance ionization gasification at convergent point place within the extremely short time, forms the plasma of High Temperature High Pressure, gives off plasma spectrometry.By analyzing the wavelength of atom and ion line, just can determine the kind of element; According to the signal intensity of spectral line, can calculate the content of element.
Laser induced breakdown spectrograph of the present invention comprises nanosecond laser 1, multiple tracks photo-electric direct reading spectrometer 2, sync control device 3, constituent analysis computing machine 4, catoptron 5, condenser lens 6, sample room 7, sample container 8, supplies ar system 9, collects lens 10, optical fiber 11.As shown in Figure 1.
Nanosecond laser 1 is connected by cable with constituent analysis computing machine 4, constituent analysis computing machine 4 is connected by cable with multiple tracks photo-electric direct reading spectrometer 2, multiple tracks photo-electric direct reading spectrometer 2 is connected by cable with sync control device 3, and sync control device 3 is connected by cable with constituent analysis computing machine 4;
The top of sample room 7 is installed with condenser lens 6 and collects lens 10, and one end of optical fiber 11 light inlets is also fixedly mounted in sample room 7, and the other end is connected with multiple tracks photo-electric direct reading spectrometer 2; Condenser lens and the collection V-shaped angle of lens 10, angle 15～30 degree; Condenser lens 6 adopts the convex lens of focal length 10～30cm, diameter 5～15cm; Collect the convex lens that lens 10 adopt focal length 10～30cm, diameter 5～15cm; Optical fiber 11 core diameter 400um, uvioresistant processing, armor encapsulation, 0.5～2 meter is long;
Sample container 8 can be placed in the bottom of sample room 7.Sample container 8, except having the aperture that a diameter is 5～20mm in upper end, is similar to the hollow cylinder container of a sealing made from fire resistive material, and the inside of sample container 8 can fill melt.The structure of sample container 8 guarantees when biography light-path is provided by aperture, makes the least possible radiation of in-built melt and conducts less heat to condenser lens 6 and collect lens 10.
There is lid the side of sample room 7, can open and close, for picking and placeing sample container 8; This cover strip has O-ring seal, for covering in closed condition Shi Shi sample room 7 in sealing state;
Sample room 7 is connected with confession ar system 9, and the argon gas providing for ar system 9 can be provided in sample room 7; Pressure for ar system 9 argon gas that provides is adjustable within the scope of 0.1～0.5MPa;
Nanosecond laser 1 is launched pulse laser and is arrived catoptron 5, arrive after reflection condenser lens 6, the sample surface reaching after line focus in sample container 8 produces plasma, the light of the cooling rear generation of plasma enters into optical fiber 11 through collecting lens 10, finally enters multiple tracks photo-electric direct reading spectrometer 2.
Nanosecond laser 1 adopts Nd:Yag Q-switched pulse laser, wavelength 532nm, and 1064nm, pulsewidth≤8ns, pulse energy 0～350mJ, with single-shot pattern (be trigger pip of every acceptance then just launch a bundle of pulsed laser) work, beam diameter 6mm;
Spectral limit 165～the 800nm of multiple tracks photo-electric direct reading spectrometer 2, resolution 0.01nm;
The delay time of sync control device 3 is that 10ns～10ms is adjustable;
Constituent analysis computing machine 4 possesses control, number is adopted and analytic function.Its control function refers to and can transmit control signal to sync control device 3 and nanosecond laser 1 simultaneously, to start sync control device 3 and nanosecond laser 1 is worked; It is the data that can gather multiple tracks photo-electric direct reading spectrometer 2 that its number is adopted function; Its analytic function refers to the content that can analyze by spectroscopic data element in sample;
Analytical approach of the present invention comprises measurement two parts of each non-matrix element content in the foundation, unknown sample of each non-matrix element working curve, and the matrix element here refers to Fe(iron and steel), or Cu(aldary), or Al(aluminium alloy):
The step of the foundation of each non-matrix element working curve is as follows:
(1) be ready to a set of standard sample for spectrochemical analysis, this cover standard specimen can be used spark photoelectric direct reading spectrometry standard specimen or fluorescence spectrophotometer standard specimen;
(2) open nanosecond laser 1, multiple tracks photo-electric direct reading spectrometer 2, sync control device 3, constituent analysis computing machine 4, make each parts in holding state;
(3) device operator is opened the side cover of sample room 7, by constituent analysis computing machine 4, start for ar system 9, to sample room 7, pass into argon gas 5 seconds, the side cover of then closing sample room 7, continues after air feed arrives the preset value within the scope of 0.1～0.5MPa no longer to inflate for ar system;
(4), to each piece standard specimen, carry out step below:
1) device operator is put into standard specimen in sample room 7;
2) device operator is controlled nanosecond laser 1, sync control device 3,2 co-ordinations of multiple tracks photo-electric direct reading spectrometer to measure the spectral intensity of each element particular spectral lines by constituent analysis computing machine 4.Concrete grammar is: constituent analysis computing machine 4 sends 200 pulse signals to nanosecond laser 1 with the 0.1s cycle, to start nanosecond laser 1 emission pulse laser, simultaneously, constituent analysis computing machine 4 sends to sync control device 3 by above-mentioned pulse signal, after sync control device 3 delay predetermined times, send to again multiple tracks photo-electric direct reading spectrometer 2, to start multiple tracks photo-electric direct reading spectrometer 2, analyze the light that optical fiber 11 transmits, multiple tracks photo-electric direct reading spectrometer 2 sends to constituent analysis computing machine 4 by the spectroscopic data analyzing subsequently, final component anacom 4 is selected each element particular spectral lines and (from Unite States Standard (USS) and the NIST of Institute for Research and Technology atomic spectra database, is selected from the spectroscopic data of above-mentioned predetermined quantity, select scope 165 ~ 800nm, lower with) corresponding spectral intensity carries out multi-point average processing and obtains the average spectrum intensity of each element particular spectral lines, the average spectrum intensity of each non-matrix element particular spectral lines is obtained to the normalization spectral intensity of each non-matrix element particular spectral lines divided by the average spectrum intensity of matrix element particular spectral lines,
3) device operator is taken out standard specimen from sample room 7;
(5) to each non-matrix element, the normalization spectral intensity of each sample and corresponding concentration are carried out curve fitting, obtain the working curve of this element;
(6) close nanosecond laser 1, multiple tracks photo-electric direct reading spectrometer 2, sync control device 3, constituent analysis computing machine 4.Working curve is set up complete.
In unknown sample, the step of the measurement of each non-matrix element content is as follows:
A, unlatching nanosecond laser 1, multiple tracks photo-electric direct reading spectrometer 2, sync control device 3, constituent analysis computing machine 4, make each parts in holding state;
B, device operator are opened the side cover of sample room 7, by constituent analysis computing machine 4, start for ar system 9, to sample room 7, pass into argon gas 5 seconds, the side cover of then closing sample room 7, continues after air feed arrives the preset value within the scope of 0.1～0.5MPa no longer to inflate for ar system; This process control is in 15 seconds;
C, device operator are in operation steps b, and sampling operation person is placed on sample container 8 by smelting furnace, use sample spoon from smelting furnace, to take out fast melt and import in sample container 8; This process control is in 15 seconds;
D, sampling operation person open the side cover of sample room 7, by clamp, sample container 8 are put in sample room 7 fast, and close rapidly the side cover of sample room 7; This process control is in 10 seconds;
E, device operator are controlled nanosecond laser 1, sync control device 3,2 co-ordinations of multiple tracks Photoelectric Spectrometer to carry out composition measurement by constituent analysis computing machine 4; This process control is in 25 seconds.Concrete grammar is: constituent analysis computing machine 4 sends 200 pulse signals to nanosecond laser 1 with the 0.1s cycle, to start nanosecond laser 1 emission pulse laser, simultaneously, constituent analysis computing machine 4 sends to sync control device 3 by above-mentioned pulse signal, after sync control device 3 delay predetermined times, send to again multiple tracks photo-electric direct reading spectrometer 2, to start multiple tracks photo-electric direct reading spectrometer 2, analyze the light that optical fiber 11 transmits, multiple tracks photo-electric direct reading spectrometer 2 sends to constituent analysis computing machine 4 by the spectroscopic data analyzing subsequently, next the spectral intensity that constituent analysis computing machine 4 is selected each element particular spectral lines from the spectroscopic data of above-mentioned predetermined quantity is carried out average spectrum intensity that multi-point average processing obtains each element particular spectral lines and obtains divided by the average spectrum intensity of matrix element particular spectral lines the normalization spectral intensity of each non-matrix element particular spectral lines, finally the normalization spectral intensity of each non-matrix element element-specific is updated to the working curve of this element, calculate corresponding content.
F, sampling operation person take out the sample in sample room 7, and this process control is in 7 seconds;
G, close nanosecond laser 1, multiple tracks photo-electric direct reading spectrometer 2, sync control device 3, constituent analysis computing machine 4.Measure and finish.
Accompanying drawing explanation
Fig. 1 is the structural representation of spectrometer of the present invention.Wherein, nanosecond laser 1, multiple tracks photo-electric direct reading spectrometer 2, sync control device 3, constituent analysis computing machine 4, catoptron 5, condenser lens 6, sample room 7, sample container 8, confession ar system 9, collection lens 10, optical fiber 11.
Fig. 2 is the working curve of C element.
Fig. 3 is the working curve of Mn element.
Embodiment
By apparatus and method of the present invention, analyze C in straight carbon steel and the content of two kinds of elements of Mn below.
Fig. 1 is a kind of embodiment of device of the present invention, wherein nanosecond laser 1, multiple tracks photo-electric direct reading spectrometer 2, sync control device 3, constituent analysis computing machine 4, catoptron 5, condenser lens 6, sample room 7, sample container 8, confession ar system 9, collection lens 10, optical fiber 11.
Nanosecond laser 1 adopts Nd:Yag Q-switched pulse laser, wavelength 1064nm, and pulsewidth≤8ns, pulse energy 150mJ, with single-shot work pattern, beam diameter 6mm;
The delay time of sync control device 3 is 1us;
Argon pressure for ar system 9 is 0.15MPa;
Optical fiber 11 core diameter 400um, uvioresistant processing, armor encapsulation, 1 meter is long;
Condenser lens 6 adopts the convex lens of focal length 30cm, diameter 7cm;
Collect the convex lens that lens 10 adopt focal length 30cm, diameter 7cm;
The angle of condenser lens 6 and collection lens 10 is 30 degree;
The embodiment of the method for the invention, is divided into two parts:
The foundation of Part I: C and Mn working curve
(1) be ready to a set of standard sample for spectrochemical analysis, the composition of C and Mn is as shown in table 1;
(2) open nanosecond laser 1, multiple tracks photo-electric direct reading spectrometer 2, sync control device 3, constituent analysis computing machine 4, make these equipment in holding state;
(3) device operator is opened sample room's 7 side covers, by constituent analysis computing machine 4, starts for ar system 9, to sample room 7, passes into argon gas 5 seconds, then closes sample room's 7 side covers, continues air feed arrival setting value no longer inflate for ar system;
(4), to each piece standard specimen, carry out step below:
1) device operator is put into standard specimen in sample room 7;
2) device operator is controlled nanosecond laser 1, sync control device 3, multichannel spectrometer 2 co-ordinations to measure the spectral intensity of each composition by constituent analysis computing machine 4.Concrete grammar is: constituent analysis computing machine 4 sends 200 pulse signals to nanosecond laser 1 with the 0.1s cycle, starts nanosecond laser 1 emission pulse laser, simultaneously, constituent analysis computing machine 4 also sends to sync control device 3 by above-mentioned pulse signal, after sync control device 3 delay predetermined times, send to again multiple tracks photo-electric direct reading spectrometer 2, to start multiple tracks photo-electric direct reading spectrometer 2, analyze the light that optical fiber 11 transmits, multiple tracks photo-electric direct reading spectrometer 2 sends to constituent analysis computing machine 4 by the spectroscopic data analyzing subsequently, final component anacom 4 is selected C(193.1nm from above-mentioned 200 groups of spectroscopic datas), Mn(293.3nm), Fe(187.7nm) corresponding spectral intensity is carried out multi-point average processing and obtains the average spectrum intensity of C and Mn, by C average spectrum intensity, divided by Fe average spectrum intensity, obtained again the normalization spectral intensity of C, by Mn average spectrum intensity, divided by Fe average spectrum intensity, obtained the normalization spectral intensity of Mn,
3) device operator is taken out standard specimen from sample room;
(5) the normalization spectral intensity of the C element of each sample and corresponding concentration are carried out curve fitting, obtain the working curve of C element, as shown in Figure 2; Similarly, obtain the working curve of Mn element, as shown in Figure 3.
Table 1 standard sample for spectrochemical analysis C and Mn component list
| Sequence number element | C | Mn |
| 1 | 0.289 | 0.557 |
| 2 | 0.490 | 0.195 |
| 3 | 0.935 | 1.197 |
| 4 | 1.311 | 0.228 |
| 5 | 0.750 | 1.677 |
(6) close nanosecond laser 1, multiple tracks photo-electric direct reading spectrometer 2, sync control device 3, constituent analysis computing machine 4.Working curve is set up complete.
Part II: the measurement of C and Mn content in unknown sample
A, open nanosecond laser 1, multiple tracks photo-electric direct reading spectrometer 2, sync control device 3, constituent analysis computing machine 4 in holding state;
B, device operator are opened the side cover of sample room 7, by constituent analysis computing machine 4, start for ar system 9, to sample room 7, pass into argon gas 5 seconds, the side cover of then closing sample room 7, continues after air feed arrives the preset value within the scope of 0.1～0.5MPa no longer to inflate for ar system; This process control is in 15 seconds;
C, device operator are in operation steps b, and sampling operation person is placed on sample container 8 by smelting furnace, use sample spoon from smelting furnace, to take out fast melt and import in sample container 8; This process control is in 15 seconds;
D, sampling operation person open the side cover of sample room 7, by clamp, sample container 8 are put in sample room 7 fast, and are closed rapidly the side cover of sample room 7; This process control is in 10 seconds;
E, device operator are controlled nanosecond laser 1, sync control device 3, multichannel spectrometer 2 co-ordinations to carry out composition measurement by constituent analysis computing machine 4; This process control is in 25 seconds.Concrete grammar is: constituent analysis computing machine 4 sends 200 pulse signals to nanosecond laser 1 with the 0.1s cycle, starts nanosecond laser 1 emission pulse laser, simultaneously, constituent analysis computing machine 4 also sends to sync control device 3 by above-mentioned pulse signal, after sync control device 3 delay predetermined times, send to again multiple tracks photo-electric direct reading spectrometer 2, to start multiple tracks photo-electric direct reading spectrometer 2, analyze the light that optical fiber 11 transmits, multiple tracks photo-electric direct reading spectrometer 2 sends to constituent analysis computing machine 4 by the spectroscopic data analyzing subsequently, next constituent analysis computing machine 4 is selected C(193.1nm from above-mentioned 200 groups of spectroscopic datas), Mn(293.3nm), Fe(187.7nm) corresponding spectral intensity is carried out multi-point average processing and obtains the average spectrum intensity of each composition, by C average spectrum intensity, divided by Fe average spectrum intensity, obtained again the normalization spectral intensity of C, by Mn average spectrum intensity, divided by Fe average spectrum intensity, obtained the normalization spectral intensity of Mn, finally, by the normalization spectral intensity substitution working curve of C and Mn, calculate corresponding component content.
In test, the normalization spectral intensity of C and Mn is respectively 20,0.25, and the composition that calculates C and Mn is respectively 0.8%, 0.75%.
F, sampling operation person take out the sample in sample room 7, and this process control is in 7 seconds.
G, close nanosecond laser 1, multiple tracks photo-electric direct reading spectrometer 2, sync control device 3, constituent analysis computing machine 4; Measure and finish.
Claims (2)
1. one kind adopts laser induced breakdown spectrograph component analyzing method, it is characterized in that, comprise measurement two parts of each non-matrix element content in the foundation, unknown sample of each non-matrix element working curve, the matrix element here refers to Fe, or Cu, or Al;
The step of the foundation of each non-matrix element working curve is as follows:
1) be ready to a set of standard sample for spectrochemical analysis, this cover is spark photoelectric direct reading spectrometry standard specimen or fluorescence spectrophotometer standard specimen for standard specimen;
2) open nanosecond laser (1), multiple tracks photo-electric direct reading spectrometer (2), sync control device (3), constituent analysis computing machine (4), make each parts in holding state;
3) open the side cover of sample room (7), by constituent analysis computing machine (4), start for ar system (9), to sample room (7), pass into argon gas 5 seconds, then close the side cover of sample room (7), for ar system (9), continue after air feed arrives the preset value within the scope of 0.1～0.5MPa no longer to inflate;
4), to each piece standard specimen, carry out step below:
A, device operator are put into standard specimen in sample room (7);
B, by constituent analysis computing machine (4), control nanosecond laser (1), sync control device (3), multiple tracks photo-electric direct reading spectrometer (2) co-ordination to measure the spectral intensity of each element particular spectral lines, concrete steps are: constituent analysis computing machine (4) sends 200 pulse signals to nanosecond laser (1) with the 0.1s cycle, to start nanosecond laser (1) emission pulse laser, simultaneously, constituent analysis computing machine (4) sends to sync control device (3) by above-mentioned pulse signal, after sync control device (3) delay predetermined time, send to again multiple tracks photo-electric direct reading spectrometer (2), to start multiple tracks photo-electric direct reading spectrometer (2), analyze the light that optical fiber (11) transmits, multiple tracks photo-electric direct reading spectrometer (2) sends to constituent analysis computing machine (4) by the spectroscopic data analyzing subsequently, the average spectrum intensity of each element particular spectral lines selected spectral intensity corresponding to each element particular spectral lines and carries out multi-point average processing and obtain by final component anacom (4) from above-mentioned spectroscopic data, the average spectrum intensity of each non-matrix element particular spectral lines is obtained to the normalization spectral intensity of each non-matrix element particular spectral lines divided by the average spectrum intensity of matrix element particular spectral lines,
C, device operator are taken out standard specimen from sample room (7);
5) to each non-matrix element, the normalization spectral intensity of each sample and corresponding concentration are carried out curve fitting, obtain the working curve of this element;
6) device operator is closed nanosecond laser (1), multiple tracks photo-electric direct reading spectrometer (2), sync control device (3), constituent analysis computing machine (4); Working curve is set up complete;
In unknown sample, the step of the measurement of each non-matrix element content is as follows:
A, device operator are opened nanosecond laser (1), multiple tracks photo-electric direct reading spectrometer (2), sync control device (3), constituent analysis computing machine (4), make each parts in holding state;
B, device operator are opened the side cover of sample room (7), by constituent analysis computing machine (4), start for ar system (9), to sample room (7), pass into argon gas 5 seconds, then close the side cover of sample room (7), for ar system, continue after air feed arrives the preset value within the scope of 0.1～0.5MPa no longer to inflate; This process control is in 15 seconds;
C, device operator are in operation steps b, and sampling operation person is placed on sample container (8) by smelting furnace, use sample spoon from smelting furnace, to take out fast melt and import in sample container (8); This process control is in 15 seconds;
D, sampling operation person open the side cover of sample room (7), by clamp, sample container (8) be put in sample room (7) fast, and the side cover of closing sample room (7); This process control is in 10 seconds;
E, device operator are controlled nanosecond laser (1), sync control device (3), multiple tracks photo-electric direct reading spectrometer (2) co-ordination to carry out composition measurement by constituent analysis computing machine (4), this process control is in 25 seconds, concrete steps are: constituent analysis computing machine (4) sends 200 pulse signals to nanosecond laser (1) with the 0.1s cycle, to start nanosecond laser (1) emission pulse laser, simultaneously, constituent analysis computing machine (4) sends to sync control device (3) by above-mentioned pulse signal, after sync control device (3) delay predetermined time, send to again multiple tracks photo-electric direct reading spectrometer (2), to start multiple tracks photo-electric direct reading spectrometer (2), analyze the light that optical fiber (11) transmits, multiple tracks photo-electric direct reading spectrometer (2) sends to constituent analysis computing machine (4) by the spectroscopic data analyzing subsequently, next the spectral intensity that constituent analysis computing machine (4) is selected each element particular spectral lines from above-mentioned spectroscopic data is carried out multi-point average processing and obtains the average spectrum intensity of each element particular spectral lines, and then the average spectrum intensity of each non-matrix element particular spectral lines is obtained to the normalization spectral intensity of each non-matrix element particular spectral lines divided by the average spectrum intensity of matrix element particular spectral lines, finally the normalization spectral intensity of each non-matrix element element-specific is updated to the working curve of this element, calculate corresponding content,
F, sampling operation person take out the sample in sample room (7), and this process control is in 7 seconds;
G, close nanosecond laser (1), multiple tracks photo-electric direct reading spectrometer (2), sync control device (3), constituent analysis computing machine (4); Measure and finish;
Described laser induced breakdown spectrograph comprises nanosecond laser (1), multiple tracks photo-electric direct reading spectrometer (2), sync control device (3), constituent analysis computing machine (4), catoptron (5), condenser lens (6), sample room (7), sample container (8), supplies ar system (9), collects lens (10), optical fiber (11).
2. method according to claim 1, is characterized in that, described particular spectral lines is to select from Unite States Standard (USS) and the NIST of Institute for Research and Technology atomic spectra database, selects scope 165～800nm.
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| CN114720454A (en) * | 2022-06-10 | 2022-07-08 | 合肥金星智控科技股份有限公司 | Melt component detection system, method and medium for strong flue gas dust environment |
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| CN102359953A (en) * | 2011-09-21 | 2012-02-22 | 冶金自动化研究设计院 | Ordinary brass full-elemental analysis apparatus based on laser-induced breakdown spectroscopy, and method thereof |
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| CN102359953A (en) * | 2011-09-21 | 2012-02-22 | 冶金自动化研究设计院 | Ordinary brass full-elemental analysis apparatus based on laser-induced breakdown spectroscopy, and method thereof |
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| 一种用于冶金炉前快速分析的新仪器——激光诱导击穿光谱仪;姚宁娟等;《光谱学与光谱分析》;20070731;第27卷(第7期);第1452-1454页 * |
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