A standard sample preparation and calibration device for laser induced breakdown spectroscopy analysis

Abstract

The invention discloses a standard sample preparation and calibration device for laser induced breakdown spectroscopy analysis, comprising an in-situ calibrator, a three-dimensional adjustment platform, a heating furnace, a laser generating mechanism, a spectrum analysis mechanism, an air pressure regulating mechanism and a sample preparation mechanism; the in-situ calibrator is arranged on the three-dimensional adjustment platform; the three-dimensional adjustment platform is used to adjust the movement and alignment of the in-situ calibrator; the heating furnace is surrounded by the in-situ calibrator, and the heating furnace is used to heat the in-situ calibrator; the laser generating mechanism is used to generate laser light to irradiate the in-situ calibrator; the spectrum analysis mechanism is used to collect spectrum from the in-situ calibrator for analysis; the air pressure regulating mechanism is connected to the inside of the in-situ calibrator, and the air pressure regulating mechanism is used to adjust the air pressure in the in-situ calibrator; the sample preparation mechanism is used to prepare samples in the in-situ calibrator; that is, the invention combines the standard sample preparation function and the LIBS calibration function in one device, not only realizing the standard sample preparation, but also realizing the in-situ calibration and the anti-pollution of the standard sample.

Description

Technical Field

[0001] The invention relates to the technical field of material analysis, and in particular to a standard sample preparation and calibration device for laser induced breakdown spectroscopy analysis. Background Art

[0002] Laser Induced Breakdown Spectroscopy (LIBS) analysis technology is a new elemental analysis technology. Its principle is to use high-power pulsed laser to focus and bombard the surface of the sample to be tested to generate plasma. During the plasma excitation process, characteristic spectral lines of the corresponding elements are generated. Through the spectrometer and ICCD, the time is precisely controlled and the characteristic spectral line analysis is performed, so that the elements in the sample to be tested can be qualitatively and quantitatively analyzed. This analysis method has the characteristics of short time response, remote control, non-destructive or minimally destructive measurement, and real-time, in-situ and micro-area analysis.

[0003] At present, for the detection of element types in the sample to be tested, the element spectral lines in the LIBS spectrum can be directly read out for identification by comparing the element spectral line wavelength information in the standard data; however, in practical applications, it is also necessary to quantitatively measure the element content. The accurate content cannot be directly obtained by only using the intensity of different element spectral lines in a single set of LIBS spectra. The LIBS analysis must be calibrated with standard samples before it can be applied to the analysis and testing of samples with unknown content.

[0004] The existing technology uses the internal calibration method, also called the relative intensity method, which uses a set of standard samples to calibrate the LIBS analysis, and then compares it with the measured spectral data to obtain accurate quantitative analysis results of the element content. This method can reduce the impact of spectral intensity instability caused by external conditions on quantitative analysis, but it requires a set of reliable standard samples, which puts high demands on the preparation and calibration process of the standard samples.

[0005] One of the existing methods of standard sample preparation and LIBS calibration is to prepare a quantitative powder standard sample in a preparation device, then take out the sample for tableting, and then put it on the calibration device for LIBS calibration test. Generally, the standard sample preparation device and the LIBS calibration device are two separate devices. In the above process, there is a problem that the prepared standard sample is easily contaminated by the environment, resulting in inaccurate LIBS calibration. Summary of the invention

[0006] The object of the present invention is to provide a standard sample preparation and calibration device for laser induced breakdown spectroscopy analysis, so as to solve the problem that the standard sample is easily polluted by the environment and thus causes inaccurate LIBS calibration.

[0007] In order to solve the above technical problems, the present invention provides a standard sample preparation and calibration device for laser induced breakdown spectroscopy analysis, including an in-situ calibrator, a three-dimensional adjustment platform, a heating furnace, a laser generating mechanism, a spectral analysis mechanism, an air pressure regulating mechanism and a sample preparation mechanism; the in-situ calibrator is arranged on the three-dimensional adjustment platform; the three-dimensional adjustment platform is used to adjust the movement and alignment of the in-situ calibrator; the heating furnace is surrounded by the in-situ calibrator, and the heating furnace is used to heat the in-situ calibrator; the laser generating mechanism is used to generate laser light to irradiate the in-situ calibrator; the spectral analysis mechanism is used to collect spectrum from the in-situ calibrator for analysis; the air pressure regulating mechanism is connected to the inside of the in-situ calibrator, and the air pressure regulating mechanism is used to adjust the air pressure in the in-situ calibrator; the sample preparation mechanism is used to prepare samples in the in-situ calibrator.

[0008] In one embodiment, the sample preparation mechanism includes a metering bottle with controllable opening and closing, a preparation barometer with controllable opening and closing at the monitoring end, multiple gas storage bottles with controllable opening and closing, and multiple air intake pipes with controllable opening and closing; the air pressure regulating mechanism, the metering bottle, the preparation barometer and the multiple gas storage bottles are connected in parallel to the inside of the in-situ calibrator; the multiple air intake pipes are respectively connected to the multiple gas storage bottles.

[0009] In one embodiment, the sample preparation mechanism further includes an ultrasonic vibrator, and the ultrasonic vibrator is detachably mounted on the bottom of the in-situ calibrator.

[0010] In one embodiment, the sample preparation mechanism includes an ultrasonic vibrator, and the ultrasonic vibrator is detachably mounted on the bottom of the in-situ calibrator.

[0011] In one embodiment, a powder filter is connected between the in-situ calibrator and the air pressure regulating mechanism.

[0012] In one of the embodiments, a vacuum bellows is connected between the in-situ calibrator and the air pressure regulating mechanism.

[0013] In one of the embodiments, the in-situ calibrator includes a receiving tube and a flip cover; the receiving tube is placed in the space surrounded by the heating furnace, the flip cover is rotatably connected to the end opening of the receiving tube in a flip-able manner, and a side flange is provided on the side of the receiving tube, and the side flange is connected to the interior of the receiving tube and the air pressure regulating mechanism; a quartz glass window is provided at the through-hole of the flip cover, and the quartz glass window is used to cover the end opening of the receiving tube.

[0014] In one embodiment, the laser generating mechanism includes a laser, a laser reflector and a focusing mirror. The reflecting surface of the laser reflector is arranged opposite to the emitting end of the laser and the focusing mirror. The focusing mirror is arranged between the laser reflector and the quartz glass window.

[0015] In one embodiment, the spectral analysis mechanism includes a spectrometer and an analysis reflector, and the reflection surface of the analysis reflector is arranged opposite to the receiving end of the spectrometer and the quartz glass window.

[0016] In one of the embodiments, the air pressure regulating mechanism includes a molecular pump whose opening and closing can be controlled at the exhaust end, a mechanical pump whose opening and closing can be controlled at the exhaust end, a pressure-regulating barometer whose opening and closing can be controlled at the monitoring end, and a vacuum gauge whose opening and closing can be controlled at the monitoring end; the exhaust end of the molecular pump is connected to the exhaust end of the mechanical pump in a controllable manner, and the exhaust end of the molecular pump, the exhaust end of the mechanical pump, the pressure-regulating barometer and the vacuum gauge are connected in parallel to the inside of the in-situ calibrator.

[0017] The beneficial effects of the present invention are as follows:

[0018] Since the sample preparation mechanism is used to prepare samples in the in-situ calibrator, the laser generating mechanism is used to generate laser light to irradiate into the in-situ calibrator, and the spectrum analysis mechanism is used to collect spectrum from the in-situ calibrator for analysis, that is, the present invention combines the standard sample preparation function and the LIBS calibration function in one device. Compared with the prior art using discrete devices, the device not only realizes the preparation of standard samples mixed with different material states formed by elements in different proportions, but also can avoid the problem of standard sample contamination to a limited extent, and realizes in-situ LIBS calibration after the standard sample is prepared, thereby solving the problem that the prior art cannot perform in-situ calibration, and greatly improves and improves the test stability and reliability of laser induced breakdown spectroscopy. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the technical solution of the present invention, the drawings required for use in the implementation mode will be briefly introduced below. Obviously, the drawings described below are only some implementation modes of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0020] Figure 1 It is a structural schematic diagram provided by the first embodiment of the present invention;

[0021] Figure 2 yes Figure 1 Schematic diagram of the structure of the in-situ calibrator;

[0022] Figure 3 yes Figure 2 A schematic diagram of a top view structure;

[0023] Figure 4 is a structural schematic diagram provided by a second embodiment of the present invention;

[0024] Figure 5 It is a structural diagram provided by the third embodiment of the present invention.

[0025] The reference numerals are as follows:

[0026] 10. In-situ calibrator; 11. Receiving tube; 12. Flip cover; 13. Side flange; 14. Quartz glass window; 15. Locking bolt; 16. Locking nut; 17. Mounting plate;

[0027] 20. Three-dimensional adjustment table;

[0028] 30. Heating furnace;

[0029] 40. Laser generating mechanism; 41. Laser; 42. Reflecting mirror for laser; 43. Focusing mirror;

[0030] 50. Spectral analysis mechanism; 51. Spectral analyzer; 52. Reflector for analysis;

[0031] 60. Air pressure regulating mechanism; 61. Molecular pump; 611. Needle valve; 62. Mechanical pump; 621. Control valve; 63. Pressure regulating barometer; 631. Needle valve; 64. Vacuum gauge; 641. Needle valve; 65. Control valve; 66. Needle valve; 67. Needle valve; 68. Vacuum bellows;

[0032] 70. Sample preparation mechanism; 71. Measuring bottle; 711. Needle valve; 72. Preparation barometer; 721. Needle valve; 73. Gas storage bottle; 731. Needle valve; 732. Needle valve; 74. Air inlet pipeline; 741. Pressure reducing valve; 742. Pressure reducing valve;

[0033] 80. Ultrasonic vibrator;

[0034] 90. Powder filter. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the accompanying drawings in the embodiments of the present invention.

[0036] The present invention provides a standard sample preparation and calibration device for laser induced breakdown spectroscopy analysis, the first embodiment of which is as follows: Figures 1 to 3As shown, it includes an in-situ calibrator 10, a three-dimensional adjustment platform 20, a heating furnace 30, a laser generating mechanism 40, a spectral analysis mechanism 50, an air pressure regulating mechanism 60 and a sample preparation mechanism 70; the in-situ calibrator 10 is arranged on the three-dimensional adjustment platform 20; the three-dimensional adjustment platform 20 is used to adjust the movement and alignment of the in-situ calibrator 10; the heating furnace 30 is surrounded by the in-situ calibrator 10, and the heating furnace 30 is used to heat the in-situ calibrator 10; the laser generating mechanism 40 is used to generate laser to irradiate the in-situ calibrator 10; the spectral analysis mechanism 50 is used to collect light from the in-situ calibrator 10 The spectrum is analyzed; the air pressure regulating mechanism 60 is connected to the inside of the in-situ calibrator 10, and the air pressure regulating mechanism 60 is used to adjust the air pressure in the in-situ calibrator 10; the sample preparation mechanism 70 includes a metering bottle 71 that can be controlled to open and close, a preparation barometer 72 that can be controlled to open and close at the monitoring end, a plurality of gas storage bottles 73 that can be controlled to open and close, and a plurality of air inlet pipelines 74 that can be controlled to open and close; the air pressure regulating mechanism 60, the metering bottle 71, the preparation barometer 72 and the plurality of gas storage bottles 73 are connected in parallel to the inside of the in-situ calibrator 10; the plurality of air inlet pipelines 74 are respectively connected to the plurality of gas storage bottles 73.

[0037] Regarding the above-mentioned in-situ calibrator 10, Figures 1 to 3 As shown, the in-situ calibrator 10 includes a receiving tube 11 and a flip cover 12; the receiving tube 11 is placed in the space surrounded by the heating furnace 30, and the end opening of the receiving tube 11 is rotatably connected to the flip cover 12 in a flip-closed manner, and the side of the receiving tube 11 is provided with a side flange 13, and the side flange 13 connects the interior of the receiving tube 11 and the air pressure regulating mechanism 60; a quartz glass window 14 is provided at the through-hole of the flip cover 12, and the quartz glass window 14 is used to cover the end opening of the receiving tube 11.

[0038] When using, it is only necessary to open the flip cover 12 to place the sample material in the receiving tube 11, and then close the flip cover 12 to carry out subsequent operations; wherein, a locking bolt 15 is rotatably connected to the periphery of the receiving tube 11, the locking bolt 15 can be flipped on a vertical plane, and a locking nut 16 is threadedly connected to the locking bolt 15; and grooves are provided at the corresponding positions of the flip cover 12 and the locking bolt 15, so when the locking bolt 15 is flipped up and embedded in the groove of the flip cover 12, it is only necessary to tighten the locking nut 16 to achieve a tight closure of the flip cover 12 and, of course, it is only necessary to loosen the locking nut 16 to naturally achieve the opening of the flip cover 12.

[0039] Regarding the above-mentioned three-dimensional adjustment platform 20, as Figure 1 As shown, the in-situ calibrator 10 only needs to be installed on the three-dimensional adjustment platform 20, so that the in-situ calibrator 10 can be moved forward, backward, left, right, and vertically, thereby meeting the displacement adjustment requirements of the in-situ calibrator 10.

[0040] Among them, there are various ways to implement the three-dimensional adjustment platform 20, for example, it can be a robotic arm that can move freely in multiple directions, or it can be equipped with guide rails and sliders in the three directions of the coordinate axis; and in order to meet the needs of fine and precise distance adjustment, it can also be preferably implemented by using a screw rod to accurately drive the slider to move, and technical personnel in this field can choose according to actual usage requirements.

[0041] In addition, if Figure 1 and Figure 3 As shown, in this embodiment, a mounting plate 17 is also provided at the periphery of the in-situ calibrator 10 to facilitate detachable mounting connection between the three-dimensional adjustment platform 20 and the mounting plate 17 .

[0042] Regarding the above-mentioned heating furnace 30, as Figure 1 As shown, the heating furnace 30 surrounds the in-situ calibrator 10, and the heating furnace 30 and the in-situ calibrator 10 are separated from each other, thereby leaving space for the in-situ calibrator 10 to be movable and adjustable; specifically, this embodiment preferably sets the rated power of the heating furnace 30 to 8kW, the maximum temperature can reach 1200°C, and the maximum heating rate is 10°C / min; and ensure that the in-situ calibrator 10 is placed in the heating furnace 30 from top to bottom, so that the in-situ calibrator 10 is spatially located in the center of the heating furnace 30 to ensure the uniformity and stability of the reaction temperature field; in addition, the heating furnace 30 can be connected to an external negative feedback temperature control system, which can provide real-time feedback to adjust the temperature and achieve the purpose of stable temperature control.

[0043] Regarding the above-mentioned laser generating mechanism 40, Figure 1 and Figure 3 As shown, the laser generating mechanism 40 includes a laser 41, a laser reflector 42 and a focusing mirror 43. The reflecting surface of the laser reflector 42 is arranged opposite to the emitting end of the laser 41 and the focusing mirror 43. The focusing mirror 43 is arranged between the laser reflector 42 and the quartz glass window 14.

[0044] When in use, the strong pulse laser generated by the laser 41 will irradiate the reflecting surface of the laser reflector 42, and the laser reflector 42 can reflect the strong pulse laser to the focusing mirror 43, so that the focusing mirror 43 can focus the strong pulse laser to the quartz glass window 14. After the strong pulse laser passes through the quartz glass window 14 and bombards the sample, the sample will generate plasma.

[0045] The laser 41 of this embodiment can be set as a Nimma-1500 ND:YAG pulse laser with a wavelength of 1064nm and a pulse width of 9ns. The pulse laser can be triggered and controlled by an external DG645 delay controller.

[0046] Regarding the above-mentioned spectral analysis mechanism 50, Figure 1 and Figure 3As shown, the spectrum analysis mechanism 50 includes a spectrum analyzer 51 and an analysis reflector 52 , and the reflection surface of the analysis reflector 52 is arranged opposite to the receiving end of the spectrum analyzer 51 and the quartz glass window 14 .

[0047] When used, the spectrum of atomic excitation and deexcitation emission in the laser plasma can pass through the quartz glass window 14 and be reflected by the analysis mirror 52, so as to be received and analyzed by the spectrum analyzer 51.

[0048] The spectrum analyzer 51 of this embodiment can be set as a Princeton Instruments SP2756A spectrometer, equipped with a PIXIS charge coupler, with a detection wavelength range of 200-1050nm and a resolution of up to 0.06nm. The spectrometer can be triggered and controlled by an external DG645 delay controller.

[0049] Regarding the above-mentioned air pressure regulating mechanism 60, as Figure 1 As shown, the air pressure regulating mechanism 60 includes a molecular pump 61 whose opening and closing can be controlled at the exhaust end, a mechanical pump 62 whose opening and closing can be controlled at the exhaust end, a pressure regulating barometer 63 whose opening and closing can be controlled at the monitoring end, and a vacuum gauge 64 whose opening and closing can be controlled at the monitoring end; the exhaust end of the molecular pump 61 is connected to the exhaust end of the mechanical pump 62 in a controllable manner, and the exhaust end of the molecular pump 61, the exhaust end of the mechanical pump 62, the pressure regulating barometer 63 and the vacuum gauge 64 are connected in parallel with the inside of the in-situ calibrator 10.

[0050] Specifically, in order to realize various opening and closing controls, this embodiment has a needle valve 631 connected to the monitoring end of the pressure regulating barometer 63, a needle valve 641 connected to the monitoring end of the vacuum gauge 64, a needle valve 611 connected to the exhaust end of the molecular pump 61, a control valve 621 connected to the exhaust end of the mechanical pump 62, a control valve 65 connected between the exhaust end of the molecular pump 61 and the exhaust end of the mechanical pump 62, and a needle valve 66 connected in parallel to the needle valve 641, the needle valve 611 and the control valve 621, and a needle valve 67 connected in parallel to the needle valve 66 and the needle valve 611, and the needle valve 67 is connected to the interior of the in-situ calibrator 10.

[0051] In order to improve the accuracy of air pressure regulation, this embodiment also preferably provides a vacuum bellows 68 between the in-situ calibrator 10 and the air pressure regulating mechanism 60, that is, at this time, one end of the vacuum bellows 68 is connected to the inside of the in-situ calibrator 10, and the other end is connected to the needle valve 67.

[0052] Regarding the above-mentioned sample preparation mechanism 70, Figure 1As shown, in order to realize various opening and closing controls, this embodiment is connected with a needle valve 731 on the first gas storage cylinder 73, a needle valve 732 on the second gas storage cylinder 73, a needle valve on the metering bottle 71, a pressure reducing valve 741 on the first air intake pipeline 74, a pressure reducing valve 742 on the second air intake pipeline 74, a needle valve 721 on the monitoring end of the preparation pressure gauge 72, and a needle valve 711 on the metering bottle 71.

[0053] Assume that the device is used to prepare titanium hydrogen deuteride (TiH 0.5 D 0.5 ) standard samples and perform in-situ LIBS calibration, the following steps can be roughly included:

[0054] STEP 1. Place a 10 mm × 10 mm, 0.25 mm thick, 99.99% pure titanium foil flatly into the in-situ calibrator 10, close the flip cover 12, connect all the pipes of the standard sample preparation device for in-situ calibration of laser induced breakdown spectroscopy, then open all needle valves and control valves, start the mechanical pump 62, and after the vacuum gauge 64 reads below 1 Pa, start the molecular pump 61 to reduce the vacuum degree to 10 -3 Below Pa;

[0055] STEP 2, prepare quantitative H2 and D2, first prepare quantitative high-purity H2, close the pressure reducing valve 742, needle valve 732, needle valve 711, needle valve 631, needle valve 67, needle valve 66, needle valve 641, needle valve 611, control valve 621, open the pressure reducing valve 741, needle valve 731 and needle valve 721, and fill the high-purity hydrogen (purity 99.9999%) into the gas storage bottle 73 to determine the air pressure value, which is read by the preparation barometer 72, then close the pressure reducing valve 741 and needle valve 731, open the needle valve 66 and control valve 621, and use the mechanical Pump 62 discharges excess hydrogen, and then closes needle valve 66; then prepare quantitative high-purity D2, open pressure reducing valve 742 and needle valve 732, and fill high-purity deuterium gas (purity 99.9999%) into gas storage bottle 73 until the air pressure value is determined, and the air pressure value is read by the preparation barometer 72, then close pressure reducing valve 742 and needle valve 732, and then open needle valve 66, use mechanical pump 62 to remove excess deuterium gas, then open needle valve 641 and needle valve 611, close needle valve 721 and control valve 621, and use molecular pump 61 to continuously evacuate and maintain until the vacuum gauge 64 shows 10- 6 Pa or better;

[0056] STEP3, prepare hydrogen-deuterium mixed gas at a ratio of 1:1, close needle valve 66, open needle valve 731, needle valve 732, needle valve 711, and needle valve 631, so that H2 and D2 in the two gas storage bottles 73 are fully mixed through random molecular motion and charged into the measuring bottle 71, and the pressure value of the mixed gas is measured by the pressure regulating barometer 63, and then close needle valve 731, needle valve 732, needle valve 711, and needle valve 611, open needle valve 66 and control valve 621, and use mechanical pump 62 to pump away excess hydrogen-deuterium mixed gas, so that the readings of the pressure regulating barometer 63 and vacuum gauge 64 are below 1Pa;

[0057] STEP4, high temperature annealing and activation of solid titanium foil sample, close control valve 621, open needle valve 67, wait for the pressure gauge 63 and vacuum gauge 64 to drop to 10 -3 Pa, open the heating furnace 30, heat the titanium foil sample in the in-situ calibrator 10, discharge the residual gas impurities adsorbed on its surface and inside, and raise the temperature to the annealing temperature of 800°C at a heating rate of 10°C / min, keeping the vacuum gauge 64 reading less than 10 -3 Pa, and then continue to maintain 800℃ for more than 10 minutes after the pressure stabilizes;

[0058] STEP5, control the heating furnace 30 to reduce its heating temperature to 500°C, the reaction temperature of hydrogen and deuterium adsorption of the titanium foil sample, close the needle valve 67 and the needle valve 66, set the calculated inflation volume to 28.74 kPa, open the needle valve 711 and the needle valve 67, record the reading of the pressure regulating barometer 63 through the automatic recorder, control the closing time of the needle valve 67 according to the pressure change, and quantitatively fill the gas. To ensure that the injected gas is evenly distributed in the sample material, after closing the needle valve 67, continue to maintain the reaction temperature of 500°C for at least 10 minutes, then close the heating furnace 30, and cool it naturally to room temperature to obtain TiH 0.5 D 0.5 Standard samples;

[0059] STEP6, control and adjust the position of the in-situ calibrator 10 through the three-dimensional adjustment platform 20, and determine whether the laser beam spot can hit the specified position of the standard sample in combination with the auxiliary light source, then turn on the laser 41 and the spectrometer to perform data acquisition and in-situ calibration testing of the laser-induced breakdown spectroscopy.

[0060] The second embodiment of the present invention is Figure 4 As shown, it is basically the same as the first embodiment, except that the sample preparation mechanism 70 includes an ultrasonic vibrator 80, and the ultrasonic vibrator 80 is detachably mounted on the bottom of the in-situ calibrator 10.

[0061] Regarding the ultrasonic vibrator 80, this embodiment preferably sets the vibration frequency of the ultrasonic vibrator 80 between 10kHz and 60kHz, and the amplitude between 1μm and 100μm. When mixing powder samples (such as used for vibrating and mixing five solid powder samples of Ni, Co, Cr, Al, and Y), the ultrasonic vibrator 80 is fixed to the in-situ calibrator 10, and the two are fixed and released after uniform mixing is completed.

[0062] In order to prevent dust from entering other pipelines and avoid damaging other equipment, this embodiment also preferably provides a powder filter 90 between the in-situ calibrator 10 and the air pressure regulating mechanism 60; specifically, the material of this powder filter 90 is 304 stainless steel, and a filter containing a small-sized filter mesh is prepared by laser cutting. The filter mesh has 5 layers, a filtration accuracy of 2μm, an operating temperature of less than 400°C, and a working pressure difference of less than 1MPa.

[0063] Assuming that the device is used to prepare a solid powder NiCoCrAlY (39.5:32:20:8:0.5wt%) standard sample and perform in-situ LIBS calibration, the following steps can be roughly included:

[0064] STEP1. Use a precision analytical balance (accuracy 0.1 mg) to weigh nickel powder (maximum particle size 150 μm, purity 99.99%), cobalt powder (maximum particle size 150 μm, minimum particle size 50 μm, purity 99.9%), chromium powder (maximum particle size 150 μm, minimum particle size 45 μm, purity 99.0%), aluminum powder (maximum particle size 60 μm, purity 99.99%), and yttrium powder (maximum particle size 500 μm, purity 99.99%) according to the mass percentage Ni:Co:Cr:Al:Y=39.5:32:20:8:0.5, and then mix and put into the in-situ calibrator. 10, close the flip cover 12, fix the standard in-situ calibrator 10 and the ultrasonic vibrator 80, turn on the power to make the ultrasonic vibrator 80 vibrate at a frequency of 30 Hz for 10 minutes to mix the powder sample evenly, turn off the power, then loosen the in-situ calibrator 10 and the ultrasonic vibrator 80, fix the standard in-situ calibrator 10 and the three-dimensional adjustment table 20, then connect all the pipelines of the standard sample preparation device for in-situ calibration of laser induced breakdown spectroscopy, then open all the needle valves and control valves, turn on the mechanical pump 62, and after the vacuum gauge 64 shows a value below 1 Pa, turn on the molecular pump 61 to reduce the vacuum degree to 10 -6 Pa or better;

[0065] STEP2, high temperature degassing of NiCoCrAlY solid powder mixed sample, close control valve 621, wait for the pressure gauge 63 and vacuum gauge 64 to drop to 10 -6Pa, open the heating furnace 30, heat the solid powder mixed sample in the in-situ calibrator 10, so that the residual gas impurities adsorbed on the surface and inside are discharged, and raise the temperature to the degassing temperature of 400°C at a heating rate of 10°C / min, observe the change of the vacuum gauge 64 reading, and wait until the pressure is stable and less than 10 -6 Pa, and then continue to maintain 400°C for more than 10 minutes, then turn off the heating furnace 30, and naturally cool to room temperature to obtain a NiCoCrAlY (39.5:32:20:8:0.5wt%) standard sample;

[0066] STEP3, control and adjust the position of the in-situ calibrator 10 through the three-dimensional adjustment table 20, and combine with the auxiliary light source to determine whether the laser beam spot can bombard the specified position of the NiCoCrAlY (39.5:32:20:8:0.5wt%) standard sample, then turn on the laser and spectrometer to perform laser induced breakdown spectroscopy data acquisition and in-situ calibration test.

[0067] In addition to solid mixing, the embodiment can also achieve liquid metal mixing. For example, the device can be used to prepare mixed liquid metal (Pb 50 Bi 50 ) standard samples and perform in-situ LIBS calibration, the following steps can be roughly included:

[0068] STEP 1. Use a precision analytical balance (accuracy 0.1 mg) to weigh lead powder (maximum particle size 150 μm, purity 99.5%) and bismuth powder (maximum particle size 150 μm, purity 99.999%) in a mass percentage of 1:1, mix and put into the in-situ calibrator 10, close the flip cover 12, fix the in-situ calibrator 10 and the ultrasonic vibrator 80, turn on the power to make the ultrasonic vibrator 80 vibrate at a frequency of 30 Hz for 10 minutes to mix the powder samples evenly, turn off the power, then loosen the in-situ calibrator 10 and the ultrasonic vibrator 80, fix the in-situ calibrator 10 and the three-dimensional adjustment table 20, and then connect all the pipelines of the standard sample preparation device for in-situ calibration of laser induced breakdown spectroscopy, then open all needle valves and control valves, turn on the mechanical pump 62, and after the vacuum gauge 64 reading reaches below 1 Pa, turn on the molecular pump 61 to reduce the vacuum degree to 10 -6 Pa or better;

[0069] STEP2, high temperature degassing of lead-bismuth metal powder mixed sample, close control valve 621, wait for the pressure gauge 63 and vacuum gauge 64 to drop to 10 -6Pa, open the heating furnace 30, heat the lead-bismuth metal powder mixed sample in the in-situ calibrator 10, discharge the residual gas impurities adsorbed on its surface and inside, and raise the temperature to about 280°C at a heating rate of 10°C / min. At this time, the metal bismuth first reaches the melting point and becomes liquid metal. Continue to heat it to about 330°C, at which time the metal lead reaches the melting point and becomes liquid metal. Continue to raise the temperature to the degassing temperature of 600°C, observe the change in the reading of the vacuum gauge 64, and wait until the pressure stabilizes and is less than 10 -6 Pa, and then continue to maintain 600℃ for more than 10 minutes, then control the heating furnace 30 to cool down to 550℃ and maintain it stably, then liquid metal Pb 50 Bi 50 Standard samples;

[0070] STEP3, control the position of the in-situ calibrator 10 through the three-dimensional adjustment platform 20, and determine whether the laser beam spot can bombard the liquid metal Pb by combining with the auxiliary light source. 50 Bi 50 The standard sample is placed at a designated position, and then the laser 41 and the spectrometer are turned on to perform data acquisition and in-situ calibration testing of the laser induced breakdown spectroscopy.

[0071] The third embodiment of the present invention is Figure 5 As shown, it is basically the same as the first embodiment, the difference is that the sample preparation mechanism 70 also includes an ultrasonic vibrator 80, and the ultrasonic vibrator 80 is detachably mounted on the bottom of the in-situ calibrator 10, that is, this embodiment is a combination of the first embodiment and the second embodiment, and can realize various operations such as solid-gas mixing, solid-state mixing, solid-liquid mixing, and liquid-liquid mixing, so as to meet the usage requirements in different situations.

[0072] The above is a preferred embodiment of the present invention. It should be pointed out that a person skilled in the art can make several improvements and modifications without departing from the principle of the present invention. These improvements and modifications are also considered to be within the scope of protection of the present invention.

Claims

1. A standard sample preparation and calibration device for laser induced breakdown spectroscopy analysis, characterized in that: It includes an in-situ calibrator, a three-dimensional adjustment table, a heating furnace, a laser generating mechanism, a spectrum analysis mechanism, a gas pressure regulating mechanism and a sample preparation mechanism; The in-situ calibrator is arranged on the three-dimensional adjustment platform; The three-dimensional adjustment platform is used to adjust the movement and alignment of the in-situ calibrator; The heating furnace is surrounded by the in-situ calibrator, and the heating furnace is used to heat the in-situ calibrator; The laser generating mechanism is used to generate laser light to irradiate into the in-situ calibrator; The spectrum analysis mechanism is used to collect spectrum from the in-situ calibrator for analysis; The air pressure regulating mechanism is connected to the inside of the in-situ calibrator, and the air pressure regulating mechanism is used to regulate the air pressure in the in-situ calibrator; The sample preparation mechanism is used to prepare samples in the in-situ calibrator; The sample preparation mechanism further comprises an ultrasonic vibrator, which is detachably mounted on the bottom of the in-situ calibrator; The sample preparation mechanism includes a metering bottle that can be controlled to open and close, a preparation barometer that can be controlled to open and close at the monitoring end, a plurality of gas storage bottles that can be controlled to open and close, and a plurality of air intake pipelines that can be controlled to open and close; The air pressure regulating mechanism, the measuring bottle, the prepared barometer and the plurality of gas storage bottles are connected in parallel to the interior of the in-situ calibrator; The plurality of air intake pipelines are respectively connected to the plurality of gas storage bottles; The air pressure regulating mechanism includes a molecular pump that can be controlled to open and close at the air extraction end, a mechanical pump that can be controlled to open and close at the air extraction end, a pressure regulating barometer that can be controlled to open and close at the monitoring end, and a vacuum gauge that can be controlled to open and close at the monitoring end; The outlet end of the molecular pump is connected to the suction end of the mechanical pump in a controllable manner. The suction end of the molecular pump, the suction end of the mechanical pump, the pressure regulating barometer and the vacuum gauge are connected in parallel to the inside of the in-situ calibrator.

2. The standard sample preparation and calibration device according to claim 1, characterized in that: A powder filter is connected between the in-situ calibrator and the air pressure regulating mechanism.

3. The standard sample preparation and calibration device according to claim 1, characterized in that: A vacuum bellows is connected between the in-situ calibrator and the air pressure regulating mechanism.

4. The standard sample preparation and calibration device according to claim 1, characterized in that: The in-situ calibrator comprises a receiving tube and a flip cover; The receiving tube is placed in the space surrounded by the heating furnace, the opening at the end of the receiving tube is rotatably connected to the flip cover in a foldable manner, and the side of the receiving tube is provided with a side flange, and the side flange is connected to the inside of the receiving tube and the air pressure regulating mechanism; A quartz glass window is provided at the through position of the flip cover, and the quartz glass window is used to cover the end opening of the receiving tube.

5. The standard sample preparation and calibration device according to claim 4, characterized in that: The laser generating mechanism comprises a laser, a laser reflector and a focusing mirror. The reflecting surface of the laser reflector is arranged opposite to the emitting end of the laser and the focusing mirror. The focusing mirror is arranged between the laser reflector and the quartz glass window.

6. The standard sample preparation and calibration device according to claim 4, characterized in that: The spectrum analysis mechanism comprises a spectrum analyzer and an analysis reflector, wherein the reflection surface of the analysis reflector is arranged opposite to the receiving end of the spectrum analyzer and the quartz glass window.

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