CN113607655A - Online automatic detection method for nitrogen content in steel - Google Patents
Online automatic detection method for nitrogen content in steel Download PDFInfo
- Publication number
- CN113607655A CN113607655A CN202110887833.4A CN202110887833A CN113607655A CN 113607655 A CN113607655 A CN 113607655A CN 202110887833 A CN202110887833 A CN 202110887833A CN 113607655 A CN113607655 A CN 113607655A
- Authority
- CN
- China
- Prior art keywords
- steel
- sample
- argon
- racket
- direct
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 144
- 239000010959 steel Substances 0.000 title claims abstract description 144
- 238000001514 detection method Methods 0.000 title claims abstract description 74
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 74
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 204
- 229910052786 argon Inorganic materials 0.000 claims abstract description 102
- 230000005284 excitation Effects 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000012545 processing Methods 0.000 claims abstract description 13
- 238000010183 spectrum analysis Methods 0.000 claims abstract description 10
- 238000004989 laser desorption mass spectroscopy Methods 0.000 claims abstract description 7
- 238000004886 process control Methods 0.000 claims abstract description 5
- 238000003801 milling Methods 0.000 claims description 48
- 238000012937 correction Methods 0.000 claims description 45
- 230000006837 decompression Effects 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910001369 Brass Inorganic materials 0.000 claims description 7
- 239000010951 brass Substances 0.000 claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims description 5
- 230000007246 mechanism Effects 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 238000009628 steelmaking Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000004458 analytical method Methods 0.000 description 51
- 239000007789 gas Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 22
- 230000007547 defect Effects 0.000 description 17
- 230000003595 spectral effect Effects 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 230000000007 visual effect Effects 0.000 description 12
- 238000005259 measurement Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 230000002159 abnormal effect Effects 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000005204 segregation Methods 0.000 description 6
- 239000000428 dust Substances 0.000 description 5
- 238000010301 surface-oxidation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007726 management method Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010892 electric spark Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- FXNGWBDIVIGISM-UHFFFAOYSA-N methylidynechromium Chemical compound [Cr]#[C] FXNGWBDIVIGISM-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000013523 data management Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
-
- 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
-
- 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
- G01N21/13—Moving of cuvettes or solid samples to or from the investigating station
-
- 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
- G01N2021/0106—General arrangement of respective parts
- G01N2021/0112—Apparatus in one mechanical, optical or electronic block
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
An online automatic detection method for nitrogen content in steel comprises the following steps: setting technical parameters, drawing a working curve, preparing a racket steel sample, sending the racket steel sample to a direct-reading spectrometer excitation bedplate by a spectral analysis manipulator, photographing the racket steel sample by a vision system, selecting a proper excitation point through image processing, exciting the racket steel sample, uploading detection data to an LIMS control system, and using an SPS system to complete the process control among equipment in the automatic detection process. The detection atmosphere of the direct-reading spectrometer is high-purity argon, the flow rate of the argon is 710-720L/h, the argon is subjected to secondary pressure reduction before entering the direct-reading spectrometer, and the ratio of the pressure of the argon entering the direct-reading spectrometer to the pressure of the argon in the pipeline is 0.4-0.6. The detection precision of the N element in the Q345 series steel is improved, the nitrogen content in the steel is rapidly, efficiently and accurately detected and analyzed, and reliable and timely detection data support is provided for the rapid-paced production of the steelmaking process.
Description
Technical Field
The invention belongs to the technical field of steel analysis, relates to an analysis method of steel components, and particularly relates to an on-line automatic detection method of nitrogen content (mainly aiming at steel grades with Si content of 0.15-0.45 wt%, Mn content of 1.30-1.60 wt%, and N content less than or equal to 70 ppm) in steel.
Background
The nitrogen in the steel mainly exists in the form of nitride, has harmful effects of aging, embrittlement and the like, and can generate a blue and crisp phenomenon when being heated. The nitrogen content in the steel of Q345 series and other steel grades produced by the existing company is measured by adopting an oxygen nitrogen instrument, so that the problems that the measuring process is complicated, the labor intensity is high, the detection cost is high, the existing detection period is 12min, and the requirement of 30-37 min fast-paced production in the smelting period of the steelmaking process cannot be met exist. The increase of the steel-making capacity demands puts higher requirements on timeliness and punctuality of steel-making test detection data, steel-making test detection is used as a data output unit for serving steel-making process production, and the detection capability of linking and matching with the steel-making process production rhythm is an important research subject for steel-making test detection at present. In addition, under the requirement of improving and improving the steelmaking process, the nitrogen content detection data is quickly, efficiently and accurately output, and the method is particularly important and urgent for supporting and guiding the steelmaking process improvement.
The direct-reading spectrometer analysis method can improve the speed of element content detection, can be used for detecting the nitrogen content in steel, and has higher requirements on detection precision due to lower nitrogen content in steel.
Disclosure of Invention
In view of this, an object of the embodiments of the present application is to provide an online automatic detection method for nitrogen content in steel, so as to solve the technical problem in the prior art that when a direct-reading spectrometer analysis method is adopted to measure the nitrogen content in steel, the detection accuracy does not reach the standard.
The application is realized as follows:
the application provides an online automatic detection method for nitrogen content in steel.
The method specifically comprises the following steps: setting technical parameters used by a double-station milling machine and a direct-reading spectrometer, drawing a working curve, sending a steel sample to a laboratory by a pneumatic sending system, receiving the steel sample by a pneumatic sending sample receiving manipulator, placing the steel sample at the position of a bench vice of the double-station milling machine, preparing a racket steel sample, sending the racket steel sample to an excitation bedplate of the direct-reading spectrometer by a spectral analysis manipulator, photographing the racket steel sample by a vision system, selecting a proper excitation point through image processing, exciting the racket steel sample, uploading detection data to an LIMS control system, and using an SPS system to complete process control among devices in the automatic detection process;
the detection atmosphere of the direct-reading spectrometer is high-purity argon, the flow rate of the argon is 710-720L/h, the argon is subjected to primary decompression at the outlet of a liquid argon tank, the argon is subjected to secondary decompression before entering the direct-reading spectrometer, and the ratio of the pressure of the argon entering the direct-reading spectrometer to the pressure of the argon in the pipeline is 0.4-0.6.
Si and Mn have a large influence on an N analysis result, Q345 series steel grades have the Si content of 0.15 wt% -0.45 wt%, the Mn content of 1.30 wt% -1.60 wt% and the N content of less than or equal to 70ppm, and because the Q345 series steel grades have high Si and Mn contents and low N content, the detection precision of the N element needs to be strictly controlled. Increasing the flow of argon can improve the analysis accuracy of N element, if the flow of argon is too small, other gases and compounds generated during sample excitation cannot be removed, the detection result is unstable, the repeatability is poor, but if the flow of argon is too large, the excitation spark flicker can be caused, the spark discharge instability can be caused, the analysis accuracy can also be influenced, and the flow of argon is controlled to be 710-720L/h. Except that need increase the argon gas flow, still need keep the argon gas flow stable in addition, the fluctuation of argon gas flow can cause the abnormal fluctuation of analysis result, and for the stability of guaranteeing the spectrum gas, the argon gas flow is stable when guaranteeing the analysis, reduces because of the influence that the argon gas flow is undulant to cause analysis precision, carries out once decompression to the argon gas in liquid argon tank exit, advances to directly read the appearance at the argon gas before to argon gas secondary decompression. The ratio of the pressure of the direct-reading spectrometer to the argon pressure of the pipeline is controlled to be 0.4-0.6, and the analysis result is most stable in the range. The analysis spectral line of N is in ultraviolet band wave zone, is easily absorbed by oxygen to and N content is lower in the sample, and the testing result can be influenced when argon purity is not enough especially contains nitrogen in the argon, through using high-purity argon, has effectively reduced the mild decay of spectral line and contains the unusual problem of testing result that nitrogen caused in the argon.
Optionally, the pressure of the direct-reading spectrometer is 0.40MPa to 0.45 MPa.
The detection of the OBLF direct-reading spectrometer requires that the pressure of argon is lower than 0.45MPa, the analysis precision of N elements can be improved due to the increase of the pressure of the argon, and the pressure of the OBLF direct-reading spectrometer is selected to be 0.40 MPa-0.45 MPa.
Optionally, the sample milling depth of the milling cutter in the preparation process of the steel sample of the racket is 0.6-0.8 mm, and the sample milling time of the milling cutter is 30-30.5 s.
Optionally, the vision system takes a picture and images of the racquet steel finished surface to determine the appropriate excitation point from the location of the racquet steel edge 1/4D.
Optionally, the excitation points are 4 points which are uniformly distributed, and when the difference value of the results obtained by two excitations is within the range of the repeatability allowable difference, the average value of the two points is reported.
In the Q345 series steel sample, the standard deviation of the test result can be increased due to component segregation (component nonuniformity), surface defects and the like, and the influence of the component nonuniformity, the surface defects and the like on the standard deviation of the test result can be avoided by controlling the time and the depth of a milling cutter, adopting a visual system and selecting proper excitation point positions and number. The milling cutter time is controlled to be 30-30.5 s, so that the processing quality of the sample can be ensured, and the surface defects of the sample are reduced. The molten steel of the Q345 series steel has good fluidity, the uneven surface component layer is thin, the depth of the milling cutter selected by people is 0.6-0.8 mm, the consumption of the milling cutter is high when the processing depth is too large, and the steel is easy to process to a sample central component segregation area. The visual system is adopted to photograph the processed surface of the racket steel sample, the defects such as sample surface pores and the like can be identified through the image processing software system, the center of the sample is easy to generate component segregation, a proper excitation point is determined at a position which is 1/4D away from the edge of the racket steel sample, if the apparent quality of the surface of the racket steel sample is too poor, the visual system cannot trace or has no available excitation area, and the analyzing manipulator automatically places the racket steel sample at a bad sample collecting position. However, the visual system can only identify the surface defects, the internal defects cannot be identified, but the excitation has a certain depth, and even if the visual system is adopted, the influence of the internal defects on the test result cannot be avoided. The number of excitation points is increased, 2 points with the best uniformity are selected for reporting, the influence of internal defects can be avoided, the accuracy of a test result is improved, and the detection speed is reduced due to the fact that the excitation points are more. The excitation process usually takes 4 points, at least two points are excited in the 4 points, if the uniformity of the two points meets the acceptability of GB/T4336-2016 on the measurement result and the determination requirement of the final result, the average value of the two points is reported, and if the uniformity of the two points can not meet the requirement, the average value of the three points which meets the uniformity is reported. Generally, 4 points which are uniformly distributed are taken, the representativeness of the 4 points is ensured, and the condition that the two points cannot meet the uniformity requirement of the 4 points can be avoided.
Optionally, the working curve drawing step comprises an interference correction step, interference elements are selected from Si, Mn, P, Ti and Al, the interference correction step comprises translational interference correction and rotational interference correction, the translational interference coefficient and the rotational interference correction coefficient of the Si element are-20.3 to-20.1 ppm and 11.70 to 11.75 respectively, the translational interference coefficient and the rotational interference correction coefficient of the Mn element are-5.2 to-5 ppm and 2.62 to 2.68 respectively, the translational interference coefficient and the rotational interference correction coefficient of the P element are-131.10 to-131.8 ppm and 3.61 to 3.65 respectively, the translational interference coefficient and the rotational interference correction coefficient of the Ti element are-25.4 to-25.2 ppm and 1.72 to 1.76 respectively, and the translational interference coefficient and the rotational interference correction coefficient of the Al element are 1046 to 1046.2ppm and 2.6 to 2.65 respectively.
The content of N in the Q345 series steel is less than or equal to 70ppm, the content of Si is 0.15-0.45 wt%, the content of Mn is 1.30-1.60 wt%, the content of P is less than or equal to 0.022 wt%, the content of Ti is 0.015-0.030 wt%, the content of Al is 0.015-0.040 wt%, Si, Mn, P, Ti and Al can influence the N analysis result and correct the interference of Si, Mn, P, Ti and Al elements, so that the working curve is corrected to be a straight line from a curve, the linear relation of the working curve for detecting the content of N is better, and the final detection result of the content of N is more accurate.
Optionally, the excitation platen is cooled by water and is provided with a 3-layer structure, the uppermost layer of the excitation platen with a steel sample bearing surface is made of high-carbon chromium stainless steel, the middle layer is made of brass, the lower layer is made of aluminum alloy, and the middle layer is provided with a water cooling circulation mechanism.
The N content of Q345 series steel is less than or equal to 70ppm, the N content is lower, when using the electric spark direct-reading spectrometer to detect the N content, to the result accuracy requirement higher, sample surface temperature too high can influence arouse the light intensity, and then influence the result accuracy, can be through selecting suitable arouse platen structure, improve the cooling effect, control arouse sample surface temperature rise, arouse platen structure and be 3 layers of structures, the superiors that have the bearing steel sample face are the high carbon chromium stainless steel material of high strength high rigidity, the second floor is the brass material, the third floor is the aluminum alloy, the second floor brass layer sets up water-cooling circulation mechanism, the heat conduction of copper is effectual, it is better to arouse the cooling effect of platform and sample. In addition, the good cooling effect can also reduce the fluctuation of the surface temperature of the sample during the spectral analysis and reduce the influence on the spectral line intensity.
Optionally, the temperature of the bearing steel sample surface is 20-30 ℃, and the temperature of the racket steel sample surface is 30-40 ℃ when the racket steel sample surface is excited.
Optionally, the rinsing time of the excitation process is 2.5s to 3.5s, the pre-burning time is 0.8s to 1.8s, and the exposure time is 4.5s to 6.5s
The high-purity argon is used, so that the problems of slight attenuation of spectral lines and abnormal detection results caused by nitrogen in the argon can be effectively reduced. The air in sample chamber and the pipeline can be expelled by flushing, the purity of argon gas is guaranteed when excitation, and the measurement precision is improved. The precombustion intensity reaches a stable state and then begins to expose and integrate, so that the evaporation stability of nitrogen elements can be ensured, the analysis result is stable, and the precombustion for a certain time can eliminate surface oxidation and pollution caused by sample treatment.
Optionally, the time for receiving the steel sample by the air sample receiving manipulator and placing the steel sample into the position of the bench vice of the double-station milling machine is 3 s-5.5 s, and the time for sending the racket steel sample to the excitation bedplate of the direct-reading spectrometer by the spectral analysis manipulator is 10 s-10.5 s.
The sampling time of the pneumatic conveying manipulator and the time of clamping the racket steel sample by the analysis manipulator are controlled, so that the analysis speed and the operation reliability of the manipulator can be ensured simultaneously, and the surface oxidation of the sample can be avoided.
The Q345 series steel has low nitrogen content and needs to strictly control the detection precision. According to the method, the flow of the argon is controlled to be 710-720L/h, the pressure of the argon entering the direct reading spectrometer is 0.40-0.45 MPa, the argon is subjected to primary decompression at the outlet of the liquid argon tank, the argon is subjected to secondary decompression before the argon enters the direct reading spectrometer, the ratio of the pressure of the entering direct reading spectrometer to the pressure of the argon in the pipeline is 0.4-0.6, and the detection precision of the N element is improved. By controlling the time and depth of the milling cutter, adopting a vision system and selecting proper excitation point positions and quantity, the influence of component nonuniformity, surface defects and the like on the standard deviation of a test result is avoided. The interference of Si, Mn, P, Ti and Al elements is automatically corrected, so that the accuracy of the detection result of the N content is improved. By selecting a proper water-cooling table plate structure and controlling the temperature of the surface of the steel sample during excitation, the fluctuation of spectral line intensity is reduced and the accuracy of the result is improved. By controlling the flushing time and the pre-burning time, the problems of slight attenuation of spectral lines and abnormal detection results caused by nitrogen in argon are effectively reduced, and the analysis accuracy and the result stability are improved. The sampling time of the pneumatic conveying manipulator and the time of clamping the racket steel sample by the analysis manipulator are controlled, so that the analysis speed and the operation reliability of the manipulator are ensured, and the surface oxidation of the sample is avoided. Finally, the method realizes the rapid, efficient and accurate detection and analysis of the nitrogen content in the steel, provides reliable and timely detection data support for the rapid-paced production of the steelmaking process, and meets the requirement of the rapid-paced production of the steelmaking process on the real-time monitoring of the nitrogen content process data in the steel.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is a flow chart of an on-line automatic detection method for nitrogen content in steel of the present application.
Fig. 2 is a schematic diagram of excitation point selection of a spark source OBLF direct-reading spectrometer.
Detailed Description
In order to make the objects, technical solutions and advantages of the examples of the present application clearer, the following examples are given for describing embodiments of the present application in detail, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In order to improve the detection precision when the direct-reading spectrometer is used for detecting the nitrogen content in the Q345 series steel, an online automatic detection method for the nitrogen content in the steel is provided in the example, so that the method is beneficial to the implementation of the scheme of the application by a person skilled in the art.
The automatic detection method mainly comprises the following steps:
(1) and setting the use technical parameters of the double-station milling machine and the direct-reading spectrometer. Before starting detection, firstly, the use technical parameters of the double-station milling machine during detection, including milling cutter time, milling cutter times, milling cutter depth and the like, and the use technical parameters of the direct-reading spectrometer, including flushing time, pre-burning time, exposure time and the like, need to be set.
(2) And drawing a working curve. And selecting a standard substance, and establishing a nitrogen content working curve corresponding to a nitrogen-containing detection channel of the OBLF direct-reading spectrometer.
(3) Preparing a sample, sampling from a steel ladle in a steel-making field to obtain a racket sample, conveying a steel sample to a laboratory by using an air conveying system, receiving the steel sample by using an air conveying sample receiving mechanical arm, putting the steel sample into a double-station milling machine bench clamp position, treating the surface of the sample by using an adjusted milling machine to enable the surface of the sample to be a smooth plane, and conveying the sample to a direct-reading spectrometer excitation bench plate by using a spectral analysis mechanical arm.
(4) The visual system shoots the steel sample, selects a proper excitation point through image processing, excites the steel sample by using a set spark source OBLF direct-reading spectrometer, and uploads detection data to the LIMS control system.
(5) Process control between the devices in an automatic inspection process is accomplished using an SPS (sample processing system) system.
The SPS system is used for receiving a pneumatic sample feeding and carrying out operations such as transportation, processing, analysis and filing on the sample feeding, receiving a production instruction of the upper computer by the SPS system and issuing a control instruction to the equipment. The states of all parts of the whole system are monitored, task coordination is carried out according to the states of all parts, and proper working tasks are distributed for different devices, so that the efficiency of the devices is utilized to the maximum. The main functions include: receiving a sample instruction from an upper computer, and distributing the sample instruction to a pneumatic sample sending field terminal; receiving on-site confirmation sample information; coordinating the actions of the sub SPS systems, and distributing the samples to different analysis areas; monitoring the operation state of the whole process action of the analysis system, and recording and displaying faults; setting a sample processing program, processing equipment (stations) and an analysis instrument path according to the steel grade and the sample code; setting on/off line of the instrument, and setting automatic analysis of a manual insertion sample; counting the running time and the failure rate of each process of the sample; sample information is communicated and sample sending/receiving time is counted.
It should be noted that the LIMS control system includes various data management functions, such as precision management, sample control management, display element management, and data export function, and is responsible for receiving the data result analyzed by the direct-reading spectrometer, and integrating, classifying and uploading the data for the production of the steel-making process.
Optionally, the detection atmosphere of the direct-reading spectrometer is high-purity argon, the flow rate of the argon is 710L/h-720L/h, the argon is subjected to primary decompression at the outlet of the liquid argon tank, the argon is subjected to secondary decompression before entering the direct-reading spectrometer, and the ratio of the pressure of the argon entering the direct-reading spectrometer to the pressure of the argon in the pipeline is 0.4-0.6.
Because the analysis spectral line of N is in the ultraviolet band wave zone, the analysis spectral line is easily absorbed by oxygen, the content of nitrogen in the sample is lower and is less than or equal to 70ppm, the purity of argon is insufficient, particularly the detection result is influenced when the argon contains nitrogen, and the problems of slight attenuation of the spectral line and abnormal detection result caused by nitrogen in the argon are effectively solved by using high-purity argon.
Preferably, liquid argon with the purity of more than or equal to 99.995 percent is adopted, and then the liquid argon is subjected to secondary purification by an argon purifier, so that the components such as moisture, oxygen, nitrogen, carbon dioxide and the like in the source gas are effectively removed, and the purity reaches more than 99.999 percent.
Si and Mn have a large influence on an N analysis result, Q345 series steel grades have the Si content of 0.15-0.45 wt%, the Mn content of 1.30-1.60 wt% and the N content of less than or equal to 70ppm, and because the Q345 series steel grades have the Si and Mn contents which are high and the N content is low, the detection precision of the N element needs to be strictly controlled. Increasing the flow of argon can improve the analysis accuracy of N element, if the flow of argon is too small, other gases and compounds generated during sample excitation cannot be removed, the detection result is unstable, the repeatability is poor, but if the flow of argon is too large, the excitation spark flicker can be caused, the spark discharge instability can be caused, the analysis accuracy can also be influenced, and the flow of argon is controlled to be 710-720L/h.
Preferably, the argon flow is 710L/h, 712L/h, 715L/h, 717L/h, 720L/h.
Except that need increase the argon gas flow, still need keep the argon gas flow stable in addition, the fluctuation of argon gas flow can cause the abnormal fluctuation of analysis result, and for the stability of guaranteeing the spectrum gas, the argon gas flow is stable when guaranteeing the analysis, reduces because of the influence that the argon gas flow is undulant to cause analysis precision, carries out once decompression to the argon gas in liquid argon tank exit, advances to directly read the appearance at the argon gas before to argon gas secondary decompression. The ratio of the pressure of the direct-reading spectrometer to the argon pressure of the pipeline is controlled to be 0.4-0.6, and the analysis result is most stable in the range.
Preferably, the ratio of the direct-reading spectrometer pressure to the tube argon pressure is 0.4, 0.42, 0.45, 0.47, 0.50, 0.52, 0.55 and 0.60.
Optionally, the pressure of the direct-reading spectrometer is 0.40MPa to 0.45 MPa.
The detection of the OBLF direct-reading spectrometer requires that the pressure of argon is lower than 0.45MPa, the analysis precision of N elements can be improved due to the increase of the pressure of the argon, and the pressure of the OBLF direct-reading spectrometer is selected to be 0.40 MPa-0.45 MPa.
Preferably, the pressure of the OBLF direct-reading spectrometer is 0.40MPa, 0.42MPa, 0.44MPa or 0.45 MPa.
Optionally, the milling depth of the milling cutter in the preparation process of the steel sample of the racket is 0.6-0.8 mm, and the milling time of the milling cutter is 30-30.5 s.
Alternatively, as shown in FIG. 2, the vision system takes a picture and images of the racquet steel finished surface to determine the appropriate trigger point from the location of the racquet steel edge 1/4D.
Alternatively, as shown in fig. 2, the excitation points are 4 points uniformly distributed, and when the difference between the results obtained by two excitations is within the range of the repeatability tolerance, the average value of the two points is reported.
In the Q345 series steel sample, the standard deviation of the test result can be increased due to component segregation (component nonuniformity), surface defects and the like, and the influence of the component nonuniformity, the surface defects and the like on the standard deviation of the test result can be avoided by controlling the time and the depth of a milling cutter, adopting a visual system and selecting proper excitation point positions and number. The milling cutter time is controlled to be 30-30.5 s, so that the processing quality of the sample can be ensured, and the surface defects of the sample are reduced. The molten steel of the Q345 series steel has good fluidity, the uneven surface component layer is thin, the depth of the milling cutter selected by people is 0.6-0.8 mm, the consumption of the milling cutter is high when the processing depth is too large, and the steel is easy to process to a sample central component segregation area. The visual system is adopted to photograph the processed surface of the racket steel sample, the defects such as sample surface pores and the like can be identified through the image processing software system, the center of the sample is easy to generate component segregation, a proper excitation point is determined at a position which is 1/4D away from the edge of the racket steel sample, if the apparent quality of the surface of the racket steel sample is too poor, the visual system cannot trace or has no available excitation area, and the analyzing manipulator automatically places the racket steel sample at a bad sample collecting position. However, the visual system can only identify the surface defects, the internal defects cannot be identified, but the excitation has a certain depth, and even if the visual system is adopted, the influence of the internal defects on the test result cannot be avoided. The number of excitation points is increased, 2 points with the best uniformity are selected for reporting, the influence of internal defects can be avoided, the accuracy of a test result is improved, and the detection speed is reduced due to the fact that the excitation points are more. The excitation process usually takes 4 points, at least two points are excited in the 4 points, if the uniformity of the two points meets the acceptability of GB/T4336-2016 on the measurement result and the determination requirement of the final result, the average value of the two points is reported, and if the uniformity of the two points can not meet the requirement, the average value of the three points which meets the uniformity is reported. Generally, 4 points which are uniformly distributed are taken, the representativeness of the 4 points is ensured, and the condition that the two points cannot meet the uniformity requirement of the 4 points can be avoided.
Preferably, the milling cutter depth is 0.6mm, 0.65mm, 0.7mm, 0.75mm, 0.8mm, and the milling cutter time is 30s, 30.2s, 30.4s, 30.5 s.
Optionally, the working curve drawing comprises an interference correction step, interference elements are selected from Si, Mn, P, Ti and Al, the interference correction step comprises translational interference correction and rotational interference correction, the translational interference coefficient and the rotational interference correction coefficient of the Si element are-20.3 to-20.1 ppm and 11.7 to 11.75 respectively, the translational interference coefficient and the rotational interference correction coefficient of the Mn element are-5.2 to-5 ppm and 2.62 to 2.68 respectively, the translational interference coefficient and the rotational interference correction coefficient of the P element are-131.10 to-131.8 ppm and 3.61 to 3.65 respectively, the translational interference coefficient and the rotational interference correction coefficient of the Ti element are-25.4 to-25.2 ppm and 1.72 to 1.76 respectively, and the translational interference coefficient and the rotational interference correction coefficient of the Al element are 1046 to 1046.2ppm and 2.6 to 2.65 respectively. .
Before drawing a working curve, firstly selecting a characteristic spectral line of N with less interference and high sensitivity, selecting 149.262nm, then selecting standard substances which are similar to components of Q345 series steel and have similar smelting process, drawing the working curve, wherein the N content of the Q345 series steel is less than or equal to 70ppm, the Si content is 0.15-0.45 wt%, the Mn content is 1.30-1.60 wt%, the P content is less than or equal to 0.022 wt%, the Ti content is 0.015-0.030 wt%, the Al content is 0.015-0.040 wt%, the obtained working curve is a nonlinear curve due to the influence of Si, Mn, P, Ti and Al on the N analysis result, and the interference generated by the interference elements needs to be corrected, the interference correction comprises translational interference correction and rotational interference correction, the translational interference is an absolute concentration value which is fixed by plus or minus, the rotational interference is a slope of the curve multiplied by a coefficient, and the translational deflection coefficient and the rotational interference correction coefficient of the Si element are respectively-20.3 to-20.1 ppm and 11.75-11.7 ppm, the translational interference coefficient and the rotational interference correction coefficient of the Mn element are-5.2 to-5 ppm and 2.62 to 2.68 respectively, the translational interference coefficient and the rotational interference correction coefficient of the P element are-131.10 to-131.8 ppm and 3.61 to 3.65 respectively, the translational interference coefficient and the rotational interference correction coefficient of the Ti element are-25.4 to-25.2 ppm and 1.72 to 1.76 respectively, and the translational interference coefficient and the rotational interference correction coefficient of the Al element are 1046 to 1046.2ppm and 2.6 to 2.65 respectively.
Preferably, in the test process, the spectral line can also shift due to factors such as temperature, humidity and vibration, or the working curve shifts due to light intensity changes, and standard substances are adopted to carry out standardized correction on the shift of the working curve, so that the corrected element intensity is restored to the intensity when the working curve is initially established.
Preferably, the working curve is validated with at least one standard substance prior to analysis of the test sample.
Optionally, the excitation platen is cooled by water and is provided with a 3-layer structure, the uppermost layer of the excitation platen with a steel sample bearing surface is made of high-carbon chromium stainless steel, the middle layer is made of brass, the lower layer is made of aluminum alloy, and the middle layer is provided with a water cooling circulation mechanism.
The N content of Q345 series steel is less than or equal to 70ppm, the N content is lower, when using the electric spark direct-reading spectrometer to detect the N content, to the result accuracy requirement higher, sample surface temperature too high can influence arouse the light intensity, and then influence the result accuracy, can be through selecting suitable arouse platen structure, improve the cooling effect, control arouse sample surface temperature rise, arouse platen structure and be 3 layers of structures, the superiors that have the bearing steel sample face are the high carbon chromium stainless steel material of high strength high rigidity, the second floor is the brass material, the third floor is the aluminum alloy, the second floor brass layer sets up water-cooling circulation mechanism, the heat conduction of copper is effectual, it is better to arouse the cooling effect of platform and sample. In addition, the good cooling effect can also reduce the fluctuation of the surface temperature of the sample during the spectral analysis and reduce the influence on the spectral line intensity.
Optionally, the temperature of the bearing steel sample surface is 20-30 ℃, and the temperature of the racket steel sample surface is 30-40 ℃ when the racket steel sample surface is excited.
Preferably, the temperature of the bearing steel sample surface is 20 ℃, 22 ℃, 24 ℃, 27 ℃ and 30 ℃, and the temperature of the racket steel sample surface when excited is 30 ℃, 33 ℃, 36 ℃, 38 ℃ and 40 ℃.
Optionally, the rinsing time in the excitation process is 2.5s to 3.5s, the pre-burning time is 0.8s to 1.8s, and the exposure time is 4.5s to 6.5 s.
The high-purity argon is used, so that the problems of slight attenuation of spectral lines and abnormal detection results caused by nitrogen in the argon can be effectively reduced. The air in sample chamber and the pipeline can be expelled by flushing, the purity of argon gas is guaranteed when excitation, and the measurement precision is improved. The precombustion intensity reaches a stable state and then begins to expose and integrate, so that the evaporation stability of nitrogen elements can be ensured, the analysis result is stable, and the precombustion for a certain time can eliminate surface oxidation and pollution caused by sample treatment.
Optionally, the time for receiving the steel sample by the air sample receiving manipulator and placing the steel sample into the position of the bench vice of the double-station milling machine is 3 s-5.5 s, and the time for sending the racket steel sample to the excitation bedplate of the direct-reading spectrometer by the spectral analysis manipulator is 10 s-10.5 s.
The sampling time of the pneumatic conveying manipulator and the time of clamping the racket steel sample by the analysis manipulator are controlled, so that the analysis speed and the operation reliability of the manipulator can be ensured simultaneously, and the surface oxidation of the sample can be avoided.
Preferably, the time for placing the steel sample into the position of the bench clamp of the double-station milling machine is 3s, 3.5s, 4s, 4.5s and 5.5s, and the time for sending the racket steel sample to the direct-reading spectrometer to excite the bench plate is 10s, 10.3s and 10.5 s.
Optionally, the spark excitation device adopts a spark excitation device with an automatic electrode brush, metal dust is generated on the surface of the sample due to discharge ignition in the excitation process, part of the metal dust enters the waste gas pipe along with the flushing of argon gas to be discharged, part of the metal dust accumulates in the excitation table, and a small part of the metal dust adheres to the surface of the tip of the electrode. If the dust adheres to the surface of the tip of the electrode too much, the discharge state is affected, and the analysis result is affected. In the analysis process of common steel grades, the electrode cannot be cleaned in a short time, so that the analysis result is not greatly influenced, but under the condition of analyzing nitrogen and steel grades with lower element content, if the electrode is not cleaned in time, the electrode has a great influence on the nitrogen and the elements with lower content. When measuring the N content of Q345 series steel grade, can realize automatic clearance electrode according to external control command, after receiving clearance electrode command, automatic electrode brush can follow the cylinder downstream, after descending spacing sensor down, the brush head of automatic electrode brush can contact the tip portion of electrode, and direct current motor drive brush head is rotatory to play the effect of clearance electrode.
Optionally, the automatic detection method uses a TIS system, and the TIS is responsible for communicating with the SPS and the spectrometer, including receiving and displaying sample information, steel type information, required call analysis curve information and the like sent by the SPS to the analysis instrument; collecting and uploading analysis data of the fast-splitting automatic line spectrometer to an LIMS system; converting the communication formats of various analytical instruments into a unified communication format; automatic sample number input, message monitoring system, repeated transmission and data editing functions and the like.
Optionally, samples were taken from steel making site ladles and were racquet samples having a size specification of 35mm x h12 mm.
The size specification is mainly easy for on-site sampling and automatic processing, enough analysis surface area can be used for multipoint analysis, and the sample has enough thickness, so that the temperature rise of the sample in the analysis process can be effectively reduced, and the detection result is influenced.
Example 1
The method for automatically detecting the nitrogen content in the steel on line comprises the following steps: (1) and setting the technical parameters for use. The time for receiving the steel sample and placing the steel sample into a bench vice position of a double-station milling machine by a pneumatic sample receiving mechanical hand is 4.5s, the milling time of a milling cutter of the double-station milling machine is 30.2s, the milling times of the milling cutter are 2 times, the milling depth of the milling cutter is 0.7mm, the time for sending the racket steel sample to the direct-reading spectrometer to excite a bedplate is 10s, the use technical parameters of the direct-reading spectrometer comprise flushing time 3s, pre-burning time 1s, exposure time 5s and the like, the flow of argon is 710L/h, the pressure of argon in a pipeline is 0.8MPa, 0.84MPa, 0.88MPa and 0.90MPa, and the racket steel sample is secondarily decompressed to 0.40MPa, 0.42MPa, 0.44MPa and 0.45MPa before being conveyed to the spectrometer.
(2) And drawing a working curve. And (3) selecting national standard substances and industrial standard substances as standard substances, and establishing a nitrogen content working curve corresponding to a nitrogen-containing detection channel of the OBLF direct-reading spectrometer. During testing, 15 medium and low alloy steel standard samples with different nitrogen contents and a certain gradient are selected as control standard samples, and the nitrogen content interval of the standard samples is 0.00024% -0.184%. Specifically, as shown in table 1:
TABLE 1 calibration standards for nitrogen analysis lines
And (2) carrying out interference correction on Si, Mn, P, Ti and Al elements, wherein the interference correction comprises translational interference correction and rotational interference correction, the translational interference coefficient and the rotational interference correction coefficient of the Si element are respectively-20.2 ppm and 11.73, the translational interference coefficient and the rotational interference correction coefficient of the Mn element are respectively-5.1 ppm and 2.66, the translational interference coefficient and the rotational interference correction coefficient of the P element are respectively-131.9 ppm and 3.64, the translational interference coefficient and the rotational interference correction coefficient of the Ti element are respectively-25.3 ppm and 1.75, and the translational interference coefficient and the rotational interference correction coefficient of the Al element are respectively 1046.1ppm and 2.63.
(3) Preparing a sample, sampling from a steel ladle on a steel-making site, taking the sample as a racket sample with the size specification of phi 35mm x h12mm, sending the steel sample to a laboratory by using an air supply system, receiving the steel sample by using an air supply sample receiving mechanical arm, putting the steel sample into a position of a bench vice of a double-station milling machine, treating the surface of the sample by using an adjusted milling machine to enable the surface of the sample to be a smooth plane, and sending the sample to an excitation bedplate of a direct-reading spectrometer by using a spectral analysis mechanical arm.
(4) The visual system shoots the steel sample, selects a proper excitation point through image processing, excites the steel sample by using a set spark source OBLF direct-reading spectrometer, controls the temperature of the surface of the bearing steel sample to be 25 ℃ by using a water-cooling excitation bedplate, controls the temperature of the surface of the racket steel sample to be 35 ℃ during excitation, and uploads detection data to the LIMS control system.
(5) The SPS system is used to perform process control between devices in the automatic detection process.
Example 2
According to the method for automatically detecting the nitrogen content in the embodiment 1, the pressure of the argon gas in the pipeline is 0.55, 0.58, 0.60, 0.62, 0.65, 0.68, 0.69, 0.71 and 0.74Mpa, and the argon gas is secondarily decompressed to 0.36, 0.38, 0.39, 0.40, 0.42, 0.44, 0.45, 0.46 and 0.48Mpa before being conveyed to a spectrometer.
The argon pressure in the pipeline is 0.72, 0.76, 0.78, 0.92 and 0.96Mpa, and the argon pressure is secondarily reduced to 0.36, 0.38, 0.39, 0.46 and 0.48Mpa before being transmitted to the spectrometer.
The nitrogen content test was carried out by the method of example 1 and example 2 on the Q345 steel production sample, and the specific results are shown in Table 2.
TABLE 2 determination of Q345 steel nitrogen content values for different values of argon pressure of direct reading spectrometer and ratio of pressure of direct reading spectrometer to argon pressure of pipeline
The above table shows that the measurement result of the nitrogen content of the Q345 steel is stable and the repeatability is best when the argon pressure is 0.40-0.45 Mpa and the pressure ratio is 0.4-0.6.
Example 3
According to the nitrogen content automatic detection method of example 1, the nitrogen content of the standard samples YSBS11188a-2016 and IMZ110A was measured, the pressure of the direct-reading spectrometer was 0.42MPa, and the ratio of the pressure of the direct-reading spectrometer to the pressure of the argon gas in the pipeline was selected to be 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65 and 0.70, and the specific results are shown in Table 3 and Table 4.
TABLE 3 ratio of different direct-reading spectrometer pressure to pipeline argon pressure YSBS11188a-2016 standard sample nitrogen content value
TABLE 4 determination of nitrogen content values for IMZ110A standard samples by ratio of different in-line direct-reading spectrometer pressure to tube argon pressure
From tables 3 and 4, the ratio of the pressure of the direct-reading spectrometer to the pressure of the argon in the pipeline is 0.4-0.6, and the measured nitrogen content value of the standard sample has better accuracy.
Example 4
The nitrogen content of the standard sample YSBS11188a-2016 was measured according to the method for automatically detecting nitrogen content of example 1, and no secondary decompression was performed before the measurement was sent to the spectrometer, and the specific results are shown in Table 5.
TABLE 5 Standard sample YSBS11188a-2016 Nitrogen content value without secondary depressurization
From table 5, secondary decompression is not performed before the sample is conveyed to the spectrometer, the measured nitrogen content result of the standard sample is extremely poor, and the measurement accuracy is poor.
Example 5
According to the method for automatically detecting nitrogen content in example 1, the light intensity values of the standard sample YSBS11188a-2016 were measured, and under the conditions that the ratio of the direct-reading spectrometer pressure to the pipeline argon pressure was 0.50 and the direct-reading spectrometer pressure was 0.42MPa, the flushing time was selected to be 2.0, 2.5, 3.0, 3.5 and 4.0s, and the specific results are shown in Table 6.
TABLE 6 determination of light intensity values of YSBS11188a-2016 standard sample at different washing times
From table 6, the washing time is selected to be 2.5s to 3.5s, the measured light intensity value of the nitrogen content of the standard sample is relatively stable, and the detection time is shortest and the consumption is minimum.
Example 6
According to the method for automatically detecting the nitrogen content in example 1, the light intensity values of the standard sample YSBS11188a-2016 were measured, and the pre-combustion time was selected to be 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, and 2.0s under the conditions that the ratio of the direct-reading spectrometer pressure to the pipeline argon pressure was 0.50, and the direct-reading spectrometer pressure was 0.42MPa, and the specific results are shown in Table 7.
TABLE 7 measurement of light intensity of YSBS11188a-2016 standard sample at different pre-burning times
From table 7, it can be seen that: the pre-burning time is selected to be 0.8 s-1.8 s, the measured light intensity value of the nitrogen content of the standard sample is relatively stable, and the detection time is shortest and the consumption is minimum.
Example 7
According to the method for automatically detecting nitrogen content in example 1, the light intensity values of the standard sample YSBS11188a-2016 were measured, and the exposure time was selected to be 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, and 7.0s under the conditions that the ratio of the direct-reading spectrometer pressure to the pipeline argon pressure was 0.50, and the direct-reading spectrometer pressure was 0.42MPa, and the specific results are shown in Table 8.
TABLE 8 measurement of light intensity values of YSBS11188a-2016 standard sample at different exposure times
From table 8, it can be seen that: the exposure time is selected to be 4.5 s-6.5 s, the measured light intensity value of the nitrogen content of the standard sample is relatively stable, and the detection time is shortest and the consumption is minimum.
Test example
According to the method for automatically detecting nitrogen content in example 1, a precision test was performed, and 6 detections were performed on the prepared nitrogen-containing working curve using the standard sample YSBS11188a-2016, the standard sample GCR152, and the standard sample 1766, 3 different nitrogen-containing standard samples, respectively, as shown in table 9.
TABLE 9 precision results
From the table, it can be known that the detection results obtained by the automatic nitrogen content detection method according to the embodiment 1 have better consistency, and the laboratory coefficient of variation CV of the method meets the requirements of table f.2 in GB/T27404-2008[3 ].
Standard sample validation of the accuracy test was performed according to the method for automatically detecting nitrogen content of example 1.6 standard substances with different nitrogen contents, such as GCR15, 185A, YSBS11188a-2016 and the like, are selected, and the mean value and the standard value of the standard substances are respectively and continuously detected for 6 times for verification and comparison, and the specific table 10 shows.
Table 10 accuracy standards verification results
From the above table, it can be seen that the deviation of the detection result from the nominal value is small and the accuracy is high by adopting the method for detecting the nitrogen content in the steel of example 1.
A continuous 10-furnace Q345 steel production sample is selected, the nitrogen content automatic detection method and the ONH836 oxygen-nitrogen-hydrogen analyzer of the embodiment 1 are used for detection, and the comparison test determination results are shown in Table 11.
TABLE 11 verification results of different methods of accuracy
It can be seen from tables 10 and 11 that the deviation of the mean values measured for the standard substances from the standard values and the deviation of the mean values measured for the direct-reading spectroscopic measurement and the oxygen-nitrogen-hydrogen analyzer meet the requirements of appendix F.3 of GB/T27404-2008.
Claims (10)
1. An online automatic detection method for nitrogen content in steel is characterized by comprising the following steps: setting technical parameters used by a double-station milling machine and a direct-reading spectrometer, drawing a working curve, sending a steel sample to a laboratory by a pneumatic sending system, receiving the steel sample by a pneumatic sending sample receiving manipulator, placing the steel sample at the position of a bench vice of the double-station milling machine, preparing a racket steel sample, sending the racket steel sample to an excitation bedplate of the direct-reading spectrometer by a spectral analysis manipulator, photographing the racket steel sample by a vision system, selecting a proper excitation point through image processing, exciting the racket steel sample, uploading detection data to an LIMS control system, and using an SPS system to complete process control among devices in the automatic detection process;
the detection atmosphere of the direct-reading spectrometer is high-purity argon, the flow rate of the argon is 710-720L/h, the argon is subjected to primary decompression at the outlet of a liquid argon tank, the argon is subjected to secondary decompression before entering the direct-reading spectrometer, and the ratio of the pressure of the argon entering the direct-reading spectrometer to the pressure of the argon in the pipeline is 0.4-0.6.
2. The on-line automatic detection method for nitrogen content in steel according to claim 1, wherein the pressure of the direct reading spectrometer is 0.40 MPa-0.45 MPa.
3. The method for automatically detecting the nitrogen content in the steel on line according to claim 1, wherein the milling depth of a milling cutter in the preparation process of the racket steel sample is 0.6-0.8 mm, and the milling time of the milling cutter is 30-30.5 s.
4. The method for on-line automatic detection of nitrogen content in steel according to claim 3, wherein the vision system takes a picture and images of the processed surface of the steel sample of the racket to determine a suitable excitation point from the position of the edge 1/4D of the steel sample of the racket.
5. The method for automatically detecting the content of nitrogen in steel according to claim 4, wherein 4 excitation points are uniformly distributed, and when the difference value of the results obtained by two excitations is within the range of the repeatability tolerance, the average value of the two points is reported.
6. The method for the on-line automatic detection of the nitrogen content in the steel according to claim 1, wherein the drawing of the working curve comprises an interference correction step, wherein interference elements are selected from Si and Mn, p, Ti and Al, the interference correction comprises translational interference correction and rotational interference correction, the translational interference coefficient and the rotational interference correction coefficient of Si element are-20.3 to-20.1 ppm and 11.70 to 11.75 respectively, the translational interference coefficient and the rotational interference correction coefficient of Mn element are-5.2 to-5 ppm and 2.62 to 2.68 respectively, the translational interference coefficient and the rotational interference correction coefficient of P element are-131.10 to-131.8 ppm and 3.61 to 3.65 respectively, the translational interference coefficient and the rotational interference correction coefficient of Ti element are-25.4 to-25.2 ppm and 1.72 to 1.76 respectively, and the translational interference coefficient and the rotational interference correction coefficient of Al element are 1046 to 1046.2ppm and 2.6 to 2.65 respectively.
7. The method for automatically detecting the nitrogen content in the steel on line as claimed in claim 1, wherein the excitation bedplate is a water-cooled excitation bedplate, the excitation bedplate has a 3-layer structure, the uppermost layer of the steel sample bearing surface is made of high-carbon chromium stainless steel, the middle layer is made of brass, the lower layer is made of aluminum alloy, and the middle layer is provided with a water-cooled circulation mechanism.
8. The method for automatically detecting the nitrogen content in the steel on line according to claim 7, wherein the temperature of the bearing steel sample surface is 20-30 ℃, and the temperature of the racket steel sample surface is 30-40 ℃ when the racket steel sample surface is excited.
9. The method for automatically detecting the nitrogen content in the steel in an online manner according to claim 1, wherein the flushing time in the excitation process is 2.5 s-3.5 s, the pre-combustion time is 0.8 s-1.8 s, and the exposure time is 4.5 s-6.5 s.
10. The method for automatically detecting the nitrogen content in the steel on line according to claim 1, wherein the time for the air sample sending and receiving manipulator to receive the steel sample and place the steel sample in the position of the bench vice of the double-station milling machine is 3 s-5.5 s, and the time for the spectral analysis manipulator to send the racket steel sample to the excitation bench of the direct-reading spectrometer is 10 s-10.5 s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110887833.4A CN113607655A (en) | 2021-08-03 | 2021-08-03 | Online automatic detection method for nitrogen content in steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110887833.4A CN113607655A (en) | 2021-08-03 | 2021-08-03 | Online automatic detection method for nitrogen content in steel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113607655A true CN113607655A (en) | 2021-11-05 |
Family
ID=78306622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110887833.4A Pending CN113607655A (en) | 2021-08-03 | 2021-08-03 | Online automatic detection method for nitrogen content in steel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113607655A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102890080A (en) * | 2012-09-05 | 2013-01-23 | 江苏永钢集团有限公司 | Method of direct-reading spectrometer for rapidly analyzing nitrogen element in steel |
| CN112858190A (en) * | 2021-03-31 | 2021-05-28 | 天津电力机车有限公司 | Device for assisting direct-reading spectrometer in component detection |
| CN112857871A (en) * | 2021-01-13 | 2021-05-28 | 广东韶钢松山股份有限公司 | Positioning and sampling device and method for manipulator |
-
2021
- 2021-08-03 CN CN202110887833.4A patent/CN113607655A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102890080A (en) * | 2012-09-05 | 2013-01-23 | 江苏永钢集团有限公司 | Method of direct-reading spectrometer for rapidly analyzing nitrogen element in steel |
| CN112857871A (en) * | 2021-01-13 | 2021-05-28 | 广东韶钢松山股份有限公司 | Positioning and sampling device and method for manipulator |
| CN112858190A (en) * | 2021-03-31 | 2021-05-28 | 天津电力机车有限公司 | Device for assisting direct-reading spectrometer in component detection |
Non-Patent Citations (1)
| Title |
|---|
| 邓朝刚 等: "直读光谱仪在线自动快速测定HRB400E钢中氮含量的方法研究", 南方金属, no. 239, pages 1441 - 24 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1380833B8 (en) | Apparatus for spectrometrically measuring an isotopic gas | |
| CN113607655A (en) | Online automatic detection method for nitrogen content in steel | |
| KR100717486B1 (en) | Hydrogen sulfide monitoring system | |
| CN107179312A (en) | The method for determining sour molten Boron contents in steel | |
| EP0890839B1 (en) | Method for analytically determining oxygen for each form of oxide | |
| CN115032162A (en) | Method for analyzing oxygen content of 300-series stainless steel sample | |
| SE444819B (en) | PROCEDURE FOR REGULATION OF A MANUFACTURING PROCESS | |
| JP2856006B2 (en) | Trace oxygen analysis method for steel | |
| JP3439974B2 (en) | Method and apparatus for analyzing oxygen or oxide by type of oxide in analysis sample | |
| JPS61283866A (en) | Method and apparatus for analyzing trace of carbon contained in steel material | |
| JP2789432B2 (en) | Method and apparatus for collecting gas for analysis | |
| JP4022347B2 (en) | Analytical oxygen analysis method | |
| JP2014066652A (en) | Method for quantitatively analyzing alumina in steel | |
| JPS6247418A (en) | Method for estimating oxygen concentration in molten steel | |
| JP3328448B2 (en) | Metal sample decomposition device | |
| KR970002502B1 (en) | Carbon concentration measuring method in low carbon steel | |
| JP3850237B2 (en) | Device for measuring minute changes in solution | |
| CN117191720A (en) | Method for rapidly analyzing chemical components of steel grade by using direct-reading spectrometer | |
| JPH08327625A (en) | Method and equipment for analyzing carbon, sulfur and phosphorus in metal sample | |
| CN113588584A (en) | Method for measuring oxygen content in lanthanum, cerium metal or lanthanum-cerium alloy | |
| JPH0862139A (en) | Emission spectral analysis | |
| JP2000019118A (en) | Method for quantitatively determining element concentration in metallic material | |
| JPH07253407A (en) | Analyzing method for component contained in metal sample | |
| Lange et al. | Preparation and analysis of a reference material for the measurement of oxygen in copper | |
| GB1183252A (en) | Improvements in or relating to a Method and Apparatus for Rapidly Determining the Gas Content of a Metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |