CN111579570B - A method for characterizing the crystal structure of non-metallic inclusions in steel by micro-X-ray diffraction - Google Patents
A method for characterizing the crystal structure of non-metallic inclusions in steel by micro-X-ray diffraction Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000000761 in situ micro-X-ray diffraction Methods 0.000 title 1
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- 238000001514 detection method Methods 0.000 claims abstract description 25
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- 238000001228 spectrum Methods 0.000 claims description 11
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
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- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
- G01N23/2005—Preparation of powder samples therefor
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- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
本发明涉及检测分析技术领域，具体指一种利用微区X射线衍射(Micro‑XRD)表征钢中非金属夹杂物晶体结构的方法。该方法通过电解或酸溶的方式提取钢中的非金属夹杂物，对提取颗粒进行汇聚、提纯和制样，获得高质量的微区X射线衍射检测样品，通过微区X射线衍射分析，能够确定检测颗粒的晶体结构。本发明方法可以简单有效地确定钢中非金属夹杂物的晶体结构、晶格参数以及物相种类等信息，通过制备高质量的钢中非金属夹杂物粉末样品和设置合理的微区X射线衍射检测参数，来解决现有的样品制备困难、X射线衍射(XRD)检测结果不理想等技术问题。The invention relates to the technical field of detection and analysis, in particular to a method for characterizing the crystal structure of non-metallic inclusions in steel by using micro-area X-ray diffraction (Micro-XRD). The method extracts non-metallic inclusions in steel by electrolysis or acid solution, and collects, purifies and prepares the extracted particles to obtain high-quality micro-area X-ray diffraction detection samples. Determine the crystal structure of the detection particle. The method of the invention can simply and effectively determine the information such as the crystal structure, lattice parameters and phase types of the non-metallic inclusions in the steel. Detection parameters are used to solve the existing technical problems such as difficulty in sample preparation and unsatisfactory X-ray diffraction (XRD) detection results.
Description
Technical Field
The invention relates to the technical field of detection and analysis, in particular to a method for representing a crystal structure of nonmetallic inclusions in steel by utilizing Micro-area X-ray diffraction (Micro-XRD).
Background
The properties of non-metallic inclusions in steel are closely related to the properties of the steel material. In the field of ferrous metallurgy, measures such as reducing the number of inclusions in steel, modifying the types of the inclusions and the like are often adopted to reduce the harmful influence of the inclusions in the steel on materials. In the field of oxide metallurgy, fine inclusions are also used to improve the structure, promote the formation of acicular ferrite, refine crystal grains, and the like. At present, the main research modes for nonmetallic inclusions in steel are morphology observation (scanning electron microscope or optical lens), ingredient determination (EDS energy spectrum analysis or EPMA electronic probe analysis), statistical quantity (full-automatic scanning electron microscope or optical lens rating), and the like. With the progress of research, the acquisition of the crystallographic information of the nonmetallic inclusion is increasingly emphasized. Therefore, conventional crystal structure detection means such as Transmission Electron Microscopy (TEM) and X-ray diffraction (XRD) have entered the field of inclusion research.
The crystal structure of the inclusions in the steel is detected by adopting a Transmission Electron Microscope (TEM), and the problems of difficult sample preparation, single inclusion selection and the like exist. The X-ray diffraction (XRD) can be used for carrying out detection with statistical significance on the crystal structure of a large number of inclusion particles, but is limited by the quantity and purity of collected powder, the noise of a detection map is very large, and high-quality inclusion crystallography information is difficult to obtain. In the articles entitled "On Aluminum Oxy-Nitride in Aluminum Treated Steel" (Tetsu-to-Haganie, 1971,57(6), 1006-. The reason for the severe noise phenomenon is that the large slits do not produce enough diffraction for a small amount of powder, resulting in insufficient effective signal. The spectral line obtained by the method has small signal-to-noise ratio and is not beneficial to the analysis of the X-ray diffraction result. With the rapid development of the steel smelting level, the total oxygen content in special steel can be controlled below 0.001%, which is a great challenge for obtaining high-purity and sufficient amount of non-metallic inclusions in steel to carry out X-ray diffraction detection. Therefore, the preparation of high quality inclusion powder samples and the determination of preferred X-ray diffraction (XRD) detection parameters are currently key to accurately characterizing the crystal structure of non-metallic inclusions in steel.
Disclosure of Invention
The invention aims to provide a method for representing the crystal structure of nonmetallic inclusions in steel by utilizing Micro-area X-ray diffraction (Micro-XRD), which solves the technical problems of difficult preparation of the existing sample, unsatisfactory X-ray diffraction (XRD) detection effect and the like by preparing a high-quality nonmetallic inclusion powder sample in the steel and setting reasonable detection parameters.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a method for characterizing the crystal structure of nonmetallic inclusions in steel by utilizing micro-regional X-ray diffraction comprises the following steps:
1) dissolving a steel matrix by adopting an electrolysis method, collecting impurities attached to the surface of the steel matrix and in anode mud in a beaker filled with ethanol, and carrying out ultrasonic treatment;
2) immediately pouring 5-10 ml of the treated solution into a watch glass, and then adding ethanol into the watch glass, wherein the solution amount in the watch glass is not more than 2/3 of the diameter of the watch glass, and the diameter of the watch glass is 120-140 mm;
3) taking the midpoint of the bottom of the surface dish as a rotation center, enabling the surface dish to do circular motion with the rotation speed of 0.25-1 rad/s and the amplitude range of 3-7 mm, standing the surface dish on a horizontal table after 6-8 min, sucking 3-8 ml of solution in the surface dish at the edge of the surface dish by using a rubber head dropper, and supplementing equal amount of ethanol into the surface dish;
4) repeating the operation of the step 3) until the solution is clear, and adsorbing the magnetic particles in the solution by using a magnet; standing for 4-6 min, absorbing black particles at the bottom of the watch glass by using a rubber head dropper, and continuously adding 1-3 ml of deionized water into the watch glass to dissolve organic matters in the particles in the watch glass;
5) repeating the step 3) and the step 4) until the black particles at the bottom disappear, sucking 4-6 ml of solution in the watch glass at the edge by using a rubber head dropper, covering the watch glass with the same size, and standing, wherein visible aggregated particles are at the bottom of the watch glass;
6) repeating the steps 2) to 5) more than five times to obtain at least five surface dishes with particles and solution at the bottoms of the surface dishes;
7) sequentially sucking the bottom particles and the solution of the watch glass by using a clean disposable pipette, transferring the bottom particles and the solution into the watch glass with the diameter of 170-190 mm, continuously sucking the ethanol for 2-3 times by using the sucked disposable pipette, sucking 2-4 ml each time, and transferring the ethanol into the watch glass with the diameter of 170-190 mm;
8) repeating the steps 2) to 5) for several times, so that sufficient impurity particles are gathered at the bottom of the watch glass with the diameter of 170-190 mm, the impurity particles cover the bottom of the watch glass in a circular area with the diameter of 2mm, the watch glass with the same size is covered, and standing is carried out for 6-8 hours at room temperature;
9) after the ethanol in the watch glass is completely volatilized, a glass knife is used for marking an area trace with the size of 20mm multiplied by 20mm on the back surface of the watch glass, bottom particles are included in the area, a glass sheet in the area is cut off and is directly placed on a sample platform of micro-area X-ray diffraction, and a beam spot is adjusted on a particle gathering area for detection.
The method for representing the crystal structure of the nonmetallic inclusion in the steel by utilizing the micro-area X-ray diffraction comprises the following parameters in the electrolytic process: the electrolyte comprises 3-10% of triethanolamine, 3-10% of glycerol, 1-3% of tetramethylammonium chloride and the balance of methanol in percentage by volume; the current density is 40-100 mA/cm2The electrolysis time is 3-8 h, and the size of an anode sample is 60mm multiplied by 8mm multiplied by 6 mm.
The method for representing the crystal structure of the nonmetallic inclusion in the steel by utilizing the micro-area X-ray diffraction ensures that the magnet does not contact with the solution when the magnet adsorbs magnetic particles in the solution.
The method for representing the crystal structure of the nonmetallic inclusion in the steel by utilizing the micro-area X-ray diffraction ensures that other particles at the bottom are not damaged when a rubber head dropper is adopted to absorb black particles at the bottom of a surface dish.
The method for representing the crystal structure of the nonmetallic inclusion in the steel by utilizing the micro-area X-ray diffraction ensures that the particles on the glass sheet are not polluted by cutting scraps when the glass sheet in the surface dish is cut,
the method for representing the crystal structure of the nonmetallic inclusion in the steel by utilizing the micro-area X-ray diffraction comprises the following steps of: the voltage and current are 40kV/0.5mA, the 2 theta angle range is 30-90 degrees, a two-dimensional spectrum is scanned every 15 degrees from 30 degrees, 5 steps are performed in total, and the scanning time of each two-dimensional spectrum is 300 s; the diameter of the beam limiting device collimator is 0.5mm, and the two-dimensional diffraction spectrum is converted into one-dimensional diffraction spectrum line analysis by utilizing DIFFRAC.
The method for representing the crystal structure of the nonmetallic inclusion in the steel by utilizing the micro-area X-ray diffraction is widely applied to the determination of the crystal structures of the inclusions in different steel types.
The design idea of the invention is as follows:
phase analysis and crystal structure characterization in steelBoth Transmission Electron Microscopy (TEM) and X-ray methods are used. Compared with X-ray, a Transmission Electron Microscope (TEM) can observe the morphology and the crystal structure of a precipitated phase, but the preparation of an ideal transmission sample is generally difficult, the observation field is limited in a thin area, and the result has no statistical significance. X-rays can solve the above problems well. However, the incident X-ray area of the conventional X-ray diffraction is generally 10 × 15mm, the required sample amount is at least tens of milligrams, and the test sample cannot be accurately located, so the detected spectral line is generally low in quality, and the result is difficult to accurately analyze. The incident X-ray spot diffracted by the micro-regions is sufficiently small (e.g.:
) And certain intensity is ensured, the positioning function is realized, the diffraction information of a small amount of local samples can be measured, and high-quality diffraction spectral lines can be obtained. The advantages of micro-area X-ray diffraction perfectly solve the problems of phase analysis, crystal structure characterization and the like of non-metallic inclusions in steel. The invention provides a method for representing nonmetallic inclusions in steel by utilizing Micro-area X-ray diffraction (Micro-XRD), which is characterized in that the nonmetallic inclusions in the steel are extracted in an electrolytic mode, extracted particles are gathered, purified and prepared to obtain a high-quality Micro-area X-ray diffraction (Micro-XRD) detection sample, and the crystalline structure of the particles can be clearly detected to analyze the phase type through Micro-area X-ray diffraction (Micro-XRD) spectrogram analysis. Thus, information such as the crystal structure, lattice parameter, and phase type of the nonmetallic inclusions in the steel can be easily and efficiently determined.
Compared with the prior art, the technical scheme provided by the invention has the following remarkable technical effects:
1. according to the method for extracting and preparing the nonmetallic inclusion in the steel, the inclusion particles are respectively gathered at the bottoms of the plurality of surface dishes, so that the high purity of the inclusion particles is ensured. The inclusion particles are transferred by a clean pipette, the inclusion particles at the bottoms of the plurality of surface dishes are transferred into the same surface dish and are gathered in a small area at the bottom of the surface dish, the number of the collected inclusion particles is increased by times, and a high-quality detection sample can be prepared.
2. The invention adopts the Micro-area X-ray diffraction (Micro-XRD) technology to represent the crystal structure of the nonmetallic inclusion in the steel, well adapts to the characteristics of small distribution area and high aggregation degree of the particles of the inclusion in the current sample, can accurately adjust the beam spot position on the prepared powder sample, fully obtains the crystallographic information of the inclusion in the detection area, and improves the accuracy of experimental detection.
3. Compared with a Transmission Electron Microscope (TEM), the experimental method provided by the invention is simpler and more convenient, and the obtained inclusion crystal structure information has more statistical significance.
Drawings
FIGS. 1(a) - (b) show the particle morphology of non-metallic inclusions collected by Micro-area X-ray diffraction (Micro-XRD) extraction. Wherein AlN and Al are contained in the ultra-low carbon steel A shown in FIG. 1(a)2O3And MnS inclusions, rare earth inclusions in the high carbon steel B of FIG. 1 (B).
FIGS. 2(a) - (b) are plots of the Micro-zone X-ray diffraction (Micro-XRD) patterns of several samples examined by the method of the present invention. In FIG. 2(a), an ultra-low carbon steel A and a high carbon steel B are shown. In the figure, the abscissa 2 θ represents the diffraction angle (degree) and the ordinate Intensity represents the relative Intensity (a.u.).
Table 1 shows the crystal structure parameters of nonmetallic inclusions of several steel grades calculated according to the detection map.
Detailed Description
In the specific implementation process, the method extracts the nonmetallic inclusions in the steel in an electrolytic or acid-soluble mode, aggregates, purifies and samples the extracted particles to obtain a high-quality Micro-area X-ray diffraction (Micro-XRD) detection sample, and can determine the crystal structure of the detected particles through Micro-area X-ray diffraction (Micro-XRD) analysis.
In order to better understand the essence of the present invention, the following further explains the technical scheme of the present invention by specific examples.
Example 1
The method for characterizing the crystal structure of the nonmetallic inclusion in the ultra-low carbon steel A comprises the following specific steps:
step one, nondestructively extracting nonmetallic inclusions in steel
After a steel matrix is eroded by an organic electrolyte electrolysis method, anode mud (the anode mud refers to a mud-like substance attached to the surface of an anode sample and precipitated at the bottom of an electrolytic cell in the electrolysis process) and the anode sample are placed into a 50ml beaker filled with 40ml of ethanol, ultrasonic treatment is carried out for 5min to obtain a solution containing nonmetallic inclusion particles, the solution in the beaker is poured into a watch glass for 5ml, and then ethanol is added into the watch glass to ensure that the solution amount in the watch glass does not exceed 2/3 of the diameter of the watch glass, wherein the diameter of the watch glass in the first step is 130 mm.
Wherein, the electrolyte comprises 5 percent of triethanolamine, 5 percent of glycerol, 1 percent of tetramethylammonium chloride and the balance of methanol according to volume percentage; the electrolysis time is 6-8 h, and the current density is 40-60 mA/cm2Anode sample size: 60 mm. times.8 mm. times.6 mm.
Step two, particle purification
The method comprises the steps of taking the midpoint of the bottom of a surface dish as a rotation center, enabling the surface dish to do circular motion with the rotation speed of 0.75-1 rad/s, enabling the amplitude range to be 3-6 mm, standing the surface dish on a horizontal table after 6-8 min, sucking 3-8 ml of solution in the surface dish at the edge by using a rubber-headed dropper, and supplementing equal amount of ethanol into the surface dish. And repeating the steps until the solution is clear, adsorbing iron particles in the solution by using a magnet, ensuring that the magnet is not contacted with the solution, and adsorbing the iron particles to the edge of the solution in the watch glass to be contacted again. After adsorption is finished and standing for 5min, slowly absorbing black particles (the black particles are generally unremoved iron particles, iron oxide particles, impurities and the like) at the bottom of the watch glass by using a rubber-tipped dropper, and continuously adding 1-3 ml of deionized water into the watch glass to dissolve organic matters in the particles at the bottom of the watch glass; and continuously repeating the steps until the black particles at the bottom disappear, sucking 5ml of solution in the watch glass at the edge of the watch glass by using a rubber head dropper, covering the watch glass with the same size, and standing, wherein the visible aggregated particles are at the bottom of the watch glass.
Step three, particle aggregation
The operations of step one and step two were repeated six times to obtain six petri dishes with particles and solution at the bottom of the petri dish. And (3) sequentially sucking the bottom particles and the solution of the six watch glass dishes by using a clean disposable pipette, transferring the bottom particles and the solution into the watch glass with the diameter of 180mm, continuously sucking the ethanol for 3 times by using the sucked disposable pipette, sucking 3ml each time, and transferring the ethanol into the watch glass with the diameter of 180 mm. And repeating the step two (three times) to enable enough inclusion particles to be gathered at the bottom of the watch glass with the diameter of 180mm, enabling the inclusion particles to cover the bottom of the watch glass in a circular area with the diameter of 2mm, covering the watch glass with the same size, and standing for 6-8 hours at room temperature.
Step four, preparing and detecting a Micro-area X-ray diffraction (Micro-XRD) sample
After the ethanol in the watch glass is completely volatilized, a zone trace with the size of 20mm multiplied by 20mm is marked on the back surface of the watch glass by a glass cutter, bottom particles are included in the zone, a glass sheet in the zone is cut out and is directly placed on a sample platform of Micro-zone X-ray diffraction (Micro-XRD), and a beam spot is adjusted on a particle aggregation zone for detection. In the cutting process of the step, the powder on the surface of the glass sheet is ensured not to be polluted by cutting scraps. The parameters of the reference test set for Micro-area X-ray diffraction (Micro-XRD) detection are as follows: the voltage and current are 40kV/0.5mA, the 2 theta angle range is 30-90 degrees, a two-dimensional spectrum is scanned every 15 degrees from 30 degrees, 5 steps are performed in total, and the scanning time of each two-dimensional spectrum is 300 s; the diameter of the beam limiting device collimator is 0.5mm, and a two-dimensional diffraction spectrum is converted into a one-dimensional diffraction spectrum line for analysis by using DIFFAC (digital enhanced diffraction and ultraviolet) EVA software (Bruker-AXSX ray diffraction data standard processing software) of Bruker company.
Example 2
The method for characterizing the crystal structure of nonmetallic inclusions in high-carbon steel B according to the present example is the same as example 1, except that: the electrolysis time in the first step is 3-6 h. In the second step, the midpoint of the bottom of the watch glass is taken as a rotation center, so that the watch glass performs circular motion at the rotation speed of 0.25-0.75 rad/s, and the amplitude range is 4-7 mm. In step three, after the above operations are performed, the following operations are also required to be added: and horizontally inclining the watch glass for 3-7 degrees, performing circular motion at the rotating speed of 0.75-1 rad/s, wherein the amplitude range is 4-6 mm, the time is 3-5 min, and the bottom of the watch glass for uniformly spreading particles is ensured.
As shown in FIGS. 1(a) - (b), the extraction method of the present invention can ensure non-destructive extraction and obtain sufficient amount of high-purity non-metallic inclusion particles with a certain thickness in steel, and is suitable for steel grades with different carbon contents, and the sample can be directly subjected to Micro-area X-ray diffraction (Micro-XRD) detection.
As shown in FIGS. 2(a) - (b), the microstructure of the non-metallic inclusions in the steel obtained by the method of the present invention has a pattern of Micro-area X-ray diffraction (Micro-XRD). After being processed by full spectrum analysis software (TOPAS, Total Pattern Solution), the crystal structure and lattice constant of various inclusions can be calculated according to Bragg equation. The results combined with the PDF card library analysis show that the main nonmetallic inclusions in the low-carbon steel adopted in the experiment are AlN with a P63mc structure, Al with an R-3c structure and the like2O3And MnS of Fm-3m structure; the main nonmetallic inclusions in the high-carbon steel adopted in the experiment are rare earth oxysulfide with a P-3m1 structure and TiN with an Fm-3m structure. The correlation results are shown in table 1.
TABLE 1 comparison of calculated lattice constants of the results of Micro-zone X-ray diffraction (Micro-XRD) with the lattice constant of a standard PDF card
The results of the examples show that the present invention provides a method for characterizing the crystal structure of non-metallic inclusions in steel using the Micro-zone X-ray diffraction (Micro-XRD) method. The method can be used as a statistical identification means for the crystal structure of the nonmetallic inclusion in the steel, so that the information such as the phase variety, the crystal structure, the lattice constant and the like of the nonmetallic inclusion in the steel can be obtained, and powerful support in the aspect of crystallography is provided for researching the formation mechanism of the nonmetallic inclusion in the steel.
The above is some preferred embodiments of the present invention, the present invention is not limited to the functions in the above examples, and the method of the present invention can be used to extract and characterize the crystal structure of various non-metallic inclusions of steel grades with different carbon contents. It should be noted that modifications can be made by those skilled in the art without departing from the principles of the invention and these modifications should also be considered within the scope of the invention.
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