Alloy material microcell element content surface distribution quantitative analysis method

Abstract

The invention relates to the technical field of alloy element content micro-area analysis, and discloses an alloy material micro-area element content surface distribution quantitative analysis method, which comprises: carrying out micro-area distribution continuous analysis of less than 100 [mu] m on a target element in an alloy material based on laser ablation-inductively coupled plasma mass spectrometry detection; performing correction analysis on laser ablation-inductively coupled plasma mass spectrometry detection data by adopting an inductively coupled plasma mass spectrometry detection result to obtain a more accurate quantitative analysis result of a micro-area target element below 100 microns in an alloy material target area; the problems that in the prior art, it is difficult to achieve large-area continuous multi-size analysis on microcell distribution with the element content being 100 [mu] g / g or below, microcell traceability fixed value analysis cannot be achieved, and rapid and accurate quantitative traceability analysis cannot be provided for segregation analysis of target elements in alloy are solved.

Description

Technical Field

[0001] The invention belongs to the technical field of alloy element content micro-area analysis, and in particular relates to a quantitative analysis method for surface distribution of element content in a micro-area of ​​an alloy material. Background Art

[0002] The powder metallurgy process eliminates macroscopic segregation, improves the structure of the alloy, and improves the performance of the disk. Due to its unique process steps, it also brings some inevitable defects. The main defects in powder high-temperature alloys are original grain boundaries and inclusions. The original grain boundaries such as γ' phase, carbides and oxides, as well as inclusions such as oxides, nitrides and sulfides have a significant effect on the mechanical properties of powder high-temperature alloys. They are very easy to become crack sources in the alloy, resulting in a significant reduction in the fatigue life of the powder turbine disk. Therefore, the micro-area distribution of target elements in powder high-temperature alloys and the micro-area analysis size requirements for the content of trace elements are getting higher and higher. With the help of a single micro-area analysis technology, it is impossible to achieve large-area micro-area distribution analysis of alloy materials, especially micro-area traceability and fixed value analysis. The current micro-area analysis component analysis technology mainly has the following problems: With the help of a single micro-area analysis technology, it is impossible to achieve large-area micro-area distribution analysis of alloy materials, especially micro-area traceability and fixed value analysis of element contents below 100μg / g, and it is impossible to provide a fast and accurate quantitative traceability analysis method for the segregation analysis of target elements in alloys: Therefore, there is an urgent need to develop a micro-area traceability analysis technology for the element content of alloy materials, which can realize large-area continuous multi-size micro-area segregation evaluation technology in any area of ​​interest of the alloy and provide basic data for material evaluation. Summary of the invention

[0003] In view of the above analysis, the present invention provides a method for quantitative analysis of the surface distribution of element content in micro-areas of alloy materials, in order to solve at least one of the problems in the prior art that it is difficult to realize large-area continuous multi-size analysis of the micro-area distribution below 100 μm with an element content below 100 μg / g, the micro-area traceability and fixed value analysis cannot be realized, and the segregation analysis of target elements in alloys cannot provide fast and accurate quantitative traceability analysis.

[0004] The purpose of the present invention is mainly achieved through the following technical solutions: A quantitative analysis method for the surface distribution of element content in a micro-area of ​​an alloy material, comprising: Based on laser ablation-inductively coupled plasma mass spectrometry detection, the target elements in the alloy material are continuously analyzed in the micro-area below 100 μm; The detection results of inductively coupled plasma mass spectrometry were used to correct and analyze the laser ablation-inductively coupled plasma mass spectrometry detection data, and more accurate quantitative analysis results of target elements in the micro-area below 100 μm in the target area of ​​the alloy material were obtained.

[0005] Preferably, the quantitative analysis method for the surface distribution of the elemental content in the alloy material microregion includes: Performing continuous analysis of the microregion distribution on the target area with a step size of less than 100 μm by using laser ablation-inductively coupled plasma mass spectrometry detection; Detecting the alloy material samples of some microregions within the target area by using inductively coupled plasma mass spectrometry; Calibrating the laser ablation-inductively coupled plasma mass spectrometry detection data of the same microregion by using the detection results of inductively coupled plasma mass spectrometry to obtain a more accurate quantitative analysis result of the target elements in the alloy material microregion with a size of less than 100 μm in the target area.

[0006] Preferably, the quantitative analysis method for the surface distribution of the elemental content in the alloy material microregion includes: S1: Preparing an alloy sample for solid mass spectrometry detection, where the concentration of the target element in the alloy sample is within the detection range of the mass spectrometry; S2: Obtaining continuous analysis data of the microregion distribution of the target elements in the target area based on laser ablation-inductively coupled plasma mass spectrometry detection of the target area; S3: Selecting alloy material samples from some microregions within the target area, and detecting the alloy material samples by using inductively coupled plasma mass spectrometry; S4: Calibrating the laser ablation-inductively coupled plasma mass spectrometry detection data of the same microregion by using the detection results of inductively coupled plasma mass spectrometry of the alloy material samples to obtain the quantitative analysis results of each microregion of the target elements after calibration.

[0007] Preferably, the mass concentration of the target element in the alloy sample in step S1 satisfies: 10 -1 μg / g~10 5 μg / g.

[0008] Preferably, the laser spot diameter (i.e., the scanning step size) of the laser ablation-inductively coupled plasma mass spectrometry in step S2 is 40 μm to 100 μm.

[0009] Preferably, step S3 includes: Uniformly taking multiple points in the target area by using a micro-drilling method.

[0010] Preferably, the number of points taken in the target area is 15 to 30; the ratio of the micro-drilling sampling area in the target area to the target area is: 0.1 to 0.2.

[0011] Preferably, step S4 includes: S401: Calibrating the surface scan results of the laser ablation-inductively coupled plasma mass spectrometry at the same coordinate points by using the spatial coordinates of the micro-drilling sampling positions calibrated by using an optical microscope and the quantitative analysis results of the target elements obtained by using inductively coupled plasma mass spectrometry in step S3; S402: Calibrate the surface scanning results of each micro-region corresponding to the spatial coordinates of the micro-drilling sampling position by laser ablation-inductively coupled plasma mass spectrometry to obtain the quantitative analysis results of each micro-region of the target element after calibration.

[0012] A method for calibrating the surface distribution of micro-region element content in an alloy material, including the above-mentioned method for quantitative analysis of the surface distribution of micro-region element content in an alloy material, and a step S102 is provided between step S1 and step S2: Use glow discharge mass spectrometry to measure the target element in the alloy sample in the target area.

[0013] Preferably, the method for calibrating the surface distribution of micro-region element content in the alloy material further includes step S5: Compare and verify the average value μ of the quantitative analysis results of each micro-region of the target element obtained in step S4 with the glow mass spectrometry analysis result μ0 of the target element in the target area; If |μ - μ0| / μ0 ≤ threshold η, the average value μ of the quantitative analysis results of each micro-region and the accuracy of the micro-region element content analysis of the alloy material meet the requirements; If |μ - μ0| / μ0 > threshold η, adjust the number of micro-drilling sampling points in the target area to |μ - μ0| / μ0 ≤ η or the change rate of the average value μ of the quantitative analysis results of each micro-region of the target element before and after adjusting the number of micro-drilling sampling points in the target area ≤ 1%.

[0014] Compared with the prior art, the present invention can at least achieve one of the following beneficial effects: (1) By using the inductively coupled plasma mass spectrometry detection results to correct and analyze the laser ablation-inductively coupled plasma mass spectrometry detection data, the present invention realizes accurate continuous quantitative analysis of target elements in micro-regions below 100 μm in the target area of alloy materials, overcoming the defect in the prior art that it is difficult to achieve large-area continuous multi-size analysis of the distribution of micro-regions below 100 μm with element content below 100 μg / g.

[0015] (2) By selecting a scanning step size below 100 μm through laser ablation-inductively coupled plasma mass spectrometry detection, micro-regions below 100 μm are obtained, providing a continuous change trend for the metallographic changes and element segregation of alloy materials; at the same time, with the help of the inductively coupled plasma mass spectrometry detection results, the segregation area can be accurately determined, providing accurate quantitative data for the segregation analysis of target elements; overcoming the defect in the prior art that micro-region traceability value analysis cannot be realized and rapid and accurate quantitative traceability analysis cannot be provided for the segregation analysis of target elements in alloys.

[0016] (3) When the deviation between the detection results of laser ablation-inductively coupled plasma mass spectrometry and glow discharge mass spectrometry in the present invention is relatively large, the number of micro-drilling points in the target area smaller than μ micrometer is increased, so that μ after adjustment increases, |μ - μ0| decreases, and |μ - μ0| / μ0 moves towards the ≤η interval. Increasing the number of micro-drilling points in the micro-areas in the target area where the detected value is less than μ and correcting as many micro-areas less than μ in the target area as possible helps to improve the accuracy of the quantitative analysis results of each micro-area. At the same time, adding new micro-drilling points near the micro-areas where the detected value is less than μ in the area where micro-drilling points have been made helps to reduce the number of times of adjusting the number of micro-drilling points in the target area, making |μ - μ0| / μ0 converge faster.

[0017] In the present invention, the above technical solutions can also be combined with each other to achieve more preferred combination solutions. Other features and advantages of the present invention will be described in the subsequent description. Moreover, some advantages can be made obvious from the description or understood by implementing the present invention. The objectives and other advantages of the present invention can be achieved and obtained through the content specifically pointed out in the description. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The drawings are only for the purpose of showing specific embodiments and are not considered as a limitation to the present invention. Among them: Figure 1 is the quantitative analysis test flow chart of the surface distribution of micro-area element content of alloy materials; Figure 2 is the schematic diagram of surface scan analysis by laser ablation-inductively coupled plasma mass spectrometry; Figure 3 is the surface scan data and distribution diagram of boron element content by laser ablation-inductively coupled plasma mass spectrometry; Figure 4 is the spatial coordinate distribution diagram of micro-drilling sampling positions under an optical microscope; Figure 5 is the schematic diagram of interval analysis by glow discharge mass spectrometry in Comparative Example 1. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0019] The following will specifically describe the preferred embodiments of the present invention with reference to the drawings. Among them, the drawings form a part of the present invention and are used together with the embodiments of the present invention to explain the principle of the present invention, and are not used to limit the scope of the present invention.

[0020] The applicant's research found that: for elemental analysis of alloys, there are energy spectrum analysis, probe analysis technology, mass spectrometry analysis technology and spark source atomic emission spectrometry.

[0021] In the prior art, energy spectrum analysis technology (EDS) and X-ray photoelectron spectroscopy (XPS) belong to energy spectrum analysis. The composition analysis results can only be qualitative and semi-quantitative, and the detection ability cannot measure the element content below 100 μg / g.

[0022] When using a single electron / atom probe analysis technique (EPMA / APT) to analyze target elements, for large-area measurements, especially when scanning areas above 100 μm, it takes an extremely long time and is only theoretically possible. It is impossible to evaluate the segregation analysis of alloy components in areas larger than 100 μm.

[0023] Spark source atomic emission spectrometry in-situ statistics can complete the continuous distribution analysis of the composition state of bulk metals in a large size range, but due to disadvantages such as relatively low spatial resolution and element detection limit, it cannot achieve micro-area analysis below 100 μm.

[0024] Secondary ion mass spectrometry (SIMS) uses map analysis, but it cannot achieve traceability analysis and cannot achieve large-area and large-size rapid analysis.

[0025] Among other mass spectrometry analysis techniques: 1. The combined method of laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) can achieve rapid scanning of the content at the micro-area level of 10 μm to 1 mm, but the disadvantage is that the analysis fluctuation is relatively large. 2. The combined technology of micro-drilling-inductively coupled plasma mass spectrometry can achieve large-area multi-scale discontinuous traceability analysis, but it cannot achieve large-area and multi-size continuous micro-area segregation analysis; it can obtain discontinuous content distribution data in areas above 500 μm, and the disadvantage is that it cannot give a continuous surface distribution. 3. Glow Discharge Mass Spectrometry (GDMS) can use a glow discharge source as an ion source to be connected to a mass spectrometer for mass spectrometry determination. Although the analysis speed is fast, the measurement area is about Φ 8mm, and it cannot achieve micro-area analysis.

[0026] As can be seen from the above, existing mass spectrometry analysis techniques are also difficult to achieve large-area continuous multi-size analysis of the micro-area distribution of elements with a content below 100 μg / g at the micro-area level below 100 μm, cannot achieve micro-area traceability and quantification analysis, and cannot provide rapid and accurate quantitative traceability analysis for the segregation analysis of target elements in alloys.

[0027] In view of the above defects of the existing technology: The present invention proposes a method for quantitative analysis of the surface distribution of micro-area element content in alloy materials, including: Based on laser ablation-inductively coupled plasma mass spectrometry detection, continuously analyze the micro-area distribution below 100 μm of target elements in alloy materials; Use the detection results of inductively coupled plasma mass spectrometry to correct and analyze the detection data of laser ablation-inductively coupled plasma mass spectrometry to obtain a more accurate quantitative analysis result of the target elements in the micro-areas below 100 μm in the target area of the alloy material.

[0028] During implementation, laser ablation-inductively coupled plasma mass spectrometry detection is used to perform continuous micro-area distribution analysis on the target area with a step size of less than 100 μm; The alloy material samples in some micro-areas within the target area are detected by inductively coupled plasma mass spectrometry; The laser ablation-inductively coupled plasma mass spectrometry detection data of the same micro-area is corrected by using the detection results of inductively coupled plasma mass spectrometry to obtain a more accurate quantitative analysis result of the target elements in the micro-areas below 100 μm in the alloy material target area.

[0029] It should be noted that the existing mass spectrometry analysis technologies are divided into two categories: discontinuous analysis and continuous analysis. Discontinuous analysis can accurately analyze the tiny local parts of alloy materials. However, due to the discontinuous data sampling, it is inevitable to miss some areas and it is difficult to accurately reflect the element change trend of alloy materials. For example, the micro-drilling-inductively coupled plasma mass spectrometry combined technology in the existing technology; while continuous analysis can give the element change trend of alloy materials from the detection results, but limited by the analysis principle and hardware limitations, there are often the following defects: 1. The measurement area is too large, about Φ8mm, such as glow discharge mass spectrometry, which cannot give accurate detection results for the element change trend of alloy materials in the area below 1mm and 100 μm, and the area below 100 μm is an important size interval for the metallographic change and element segregation of alloy materials; 2. The measurement fluctuation is large and the accuracy is poor, such as laser ablation-inductively coupled plasma mass spectrometry, which is also difficult to give accurate detection results for the element change trend of alloy materials in the area below 100 μm.

[0030] Compared with the existing technology, the present invention realizes accurate continuous quantitative analysis of the target elements in the micro-areas below 100 μm in the alloy material target area by using the detection results of inductively coupled plasma mass spectrometry to correct and analyze the laser ablation-inductively coupled plasma mass spectrometry detection data, overcoming the defect in the existing technology that it is difficult to realize large-area continuous multi-size analysis of the micro-area distribution of elements below 100 μg / g and below 100 μm.

[0031] Compared with the existing technology, the present invention selects a scanning step size of less than 100 μm through laser ablation-inductively coupled plasma mass spectrometry detection, and then obtains micro-areas below 100 μm, providing a continuous change trend for the metallographic change and element segregation of alloy materials; at the same time, with the help of the detection results of inductively coupled plasma mass spectrometry, the segregation area can be accurately determined, providing accurate quantitative data for the segregation analysis of target elements; overcoming the defect in the existing technology that micro-area traceability value analysis cannot be realized and rapid and accurate quantitative traceability analysis cannot be provided for the segregation analysis of target elements in alloys.

[0032] It should be noted that the laser ablation-inductively coupled plasma mass spectrometry method can achieve rapid scanning of the content in the micro-region from 10 microns to millimeters; the combined technology of micro-drilling sampling + inductively coupled plasma mass spectrometry can obtain the discontinuous content distribution data in the area above 500 μm, with stable data and traceability analysis can be realized.

[0033] Specifically, the method for quantitative analysis of the surface distribution of micro-region element content in alloy materials includes: S1: Prepare an alloy sample for solid mass spectrometry detection, and the target element concentration of the alloy sample is within the detection range of the mass spectrometry method; S2: Based on laser ablation-inductively coupled plasma mass spectrometry, continuously analyze the micro-region distribution data of the target element in the target region by detecting the target region; S3: Select a part of the micro-regions from the target region to obtain an alloy material sample, and detect the alloy material sample by inductively coupled plasma mass spectrometry; S4: Use the detection results of inductively coupled plasma mass spectrometry of the alloy material sample to correct the laser ablation-inductively coupled plasma mass spectrometry detection data of the same micro-region, and obtain the quantitative analysis results of each micro-region of the target element after correction.

[0034] Specifically, the mass concentration of the target element in the alloy sample in step S1 satisfies: 10 -1 μg / g ~ 10 5 μg / g.

[0035] Preferably, in step S2, the laser spot diameter (i.e., the scanning step size) of the laser ablation-inductively coupled plasma mass spectrometry is 40 μm to 100 μm, and it can be 40 μm, 42 μm, 46 μm, 48 μm, 50 μm, 52 μm, 56 μm, 58 μm, 60 μm, 65 μm, 64 μm, 66 μm, 70 μm, 75 μm, 77 μm, 80 μm, 84 μm, 86 μm, 88 μm, 90 μm, 92 μm, 96 μm or 100 μm.

[0036] Further preferably, in step S2, the laser spot diameter (scanning step size) of the laser ablation-inductively coupled plasma mass spectrometry is 50 μm.

[0037] Specifically, step S3 includes: uniformly taking multiple points in the target region by means of micro-drilling.

[0038] Preferably, the number of sampling points in the target area is 15 to 30, which can be 15, 16, 17, 19, 20, 22, 24, 26, 28, 29 or 35; the ratio of the micro-drilling sampling area to the target area in the target area is: 0.1 to 0.2, which can be 0.1, 0.115, 0.12, 0.125, 0.13, 0.135, 0.140, 0.145, 0.15, 0.155, 0.1, 0.16, 0.165, 0.17, 0.175, 0.18, 0.185, 0.19 or 0.2; the sampling point diameter ≤ the laser spot diameter (scanning step size) in step S2.

[0039] It should be noted that if the number of micro-drilling sampling points and the micro-drilling sampling area in the target area are too small, the correction effect of the inductively coupled plasma mass spectrometry detection result on the laser ablation-inductively coupled plasma mass spectrometry detection data of the same micro-region will decrease; if the number of micro-drilling sampling points and the micro-drilling sampling area in the target area are too large, the correction effect of the inductively coupled plasma mass spectrometry detection result on the laser ablation-inductively coupled plasma mass spectrometry detection data of the same micro-region will not be significantly improved.

[0040] More preferably, the number of micro-drilling sampling points in the target area is 20 to 30, and the ratio of the micro-drilling sampling area to the target area in the target area is: 0.1 to 0.15.

[0041] More preferably, the ratio of the micro-drilling sampling area to the target area in the target area is: 0.1 to 0.13.

[0042] As an example, step S3 can be to use a micro-drilling method to take multiple points of Φ 50μm in a Φ 8mm area, and use inductively coupled plasma mass spectrometry to determine the content of target elements at each sampling point.

[0043] Specifically, step S4 includes: S401: Use an optical microscope to calibrate the spatial coordinates of the micro-drilling sampling position, and correct the laser ablation-inductively coupled plasma mass spectrometry surface scan results at the same coordinate points using the inductively coupled plasma mass spectrometry target element quantitative analysis results obtained in step S3; S402: Correct the laser ablation-inductively coupled plasma mass spectrometry surface scan results of each micro-region corresponding to the spatial coordinates of the micro-drilling sampling position to obtain the corrected quantitative analysis results of the target element in each micro-region.

[0044] During implementation, correcting the laser ablation-inductively coupled plasma mass spectrometry surface scan results at the same coordinate points using the inductively coupled plasma mass spectrometry target element quantitative analysis results obtained in step S3 includes: replacing the laser ablation-inductively coupled plasma mass spectrometry surface scan data at the same coordinate points with the inductively coupled plasma mass spectrometry data of micro-drilling sampling.

[0045] It should be noted that the micro-region data without micro-drilling sampling does not need to be corrected.

[0046] On the other hand, the present invention proposes a method for correcting the surface distribution of micro-region element contents of an alloy material, including a quantitative analysis method for the surface distribution of micro-region element contents of the alloy material, and further including a step S102 provided between step S1 and step S2: Using glow discharge mass spectrometry to measure the target elements in the alloy sample in the target region.

[0047] Specifically, in step S102, the detection region of glow discharge mass spectrometry ≤ the target region, so that the detection region of glow discharge mass spectrometry is all detected by laser ablation-inductively coupled plasma mass spectrometry.

[0048] Preferably, the detection data of laser ablation-inductively coupled plasma mass spectrometry in step S1 and the detection data of glow discharge mass spectrometry in S102 are corrected by an alloy reference material, and the detection parameters of laser ablation-inductively coupled plasma mass spectrometry and glow discharge mass spectrometry are adjusted so that the difference between the detection data of laser ablation-inductively coupled plasma mass spectrometry and glow discharge mass spectrometry and the labeled value of the target element in the alloy reference material ≤ 1%.

[0049] Further preferably, the alloy reference materials used for the correction of laser ablation-inductively coupled plasma mass spectrometry detection and glow discharge mass spectrometry detection in S102 are the same to ensure the consistency of the standards.

[0050] Specifically, the measurement region of glow discharge mass spectrometry can be the smallest detection region in the prior art glow discharge mass spectrometry, which is a circular region of about Φ 8 mm.

[0051] Specifically, the method for correcting the surface distribution of micro-region element contents of the alloy material further includes step S5: comparing and verifying the average value μ of the quantitative analysis results of each micro-region of the target element obtained in step S4 with the glow mass spectrometry analysis result μ0 of the target element in the target region; If |μ - μ0| / μ0 ≤ η, then the average value μ of the quantitative analysis results of each micro-region and the accuracy of the analysis of the micro-region element contents of the alloy material meet the requirements; If |μ - μ0| / μ0 > η, then adjust the number of micro-drilling sampling points in the target region until |μ - μ0| / μ0 ≤ η or the change rate of the average value μ of the quantitative analysis results of each micro-region of the target element before and after adjusting the number of micro-drilling sampling points in the target region ≤ 1%.

[0052] Specifically, η can be taken as 2%.

[0053] It should be noted that the applicant found that in actual measurement, μ - μ0 satisfies ≤ 0. When |μ - μ0| / μ0 > η, it is necessary to increase the number of micro-drilling sampling points in the target region.

[0054] Preferably, it is necessary to increase the number of micro-drilling points in the target area that are smaller than the μ micro-region, so that μ increases after adjustment, |μ - μ0| decreases, and |μ - μ0| / μ0 moves towards the ≤η interval.

[0055] It should be noted that when |μ - μ0| / μ0 > η, the main influencing factor is that the correction of the laser ablation-inductively coupled plasma mass spectrometry detection data by inductively coupled plasma mass spectrometry is incomplete. In particular, the data of the detection values in the target area that are smaller than the μ micro-region are not fully corrected, resulting in a low μ value and |μ - μ0| / μ0 > η. Therefore, increasing the number of micro-drilling points in the target area where the detection values are smaller than the μ micro-region and correcting as many micro-regions smaller than μ as possible in the target area helps to improve the accuracy of the quantitative analysis results of each micro-region.

[0056] More preferably, new micro-drilling points are added near the micro-regions in the area where micro-drilling points have been made and the detection values are smaller than μ.

[0057] It should be noted that the changes of the target elements in the alloy mostly show continuous and gradual changes, and there is a higher probability that the detection values of the micro-regions near the micro-regions in the target area with detection values smaller than μ are also smaller than μ. The above settings help to reduce the number of times of adjusting the number of micro-drilling points in the target area, making |μ - μ0| / μ0 converge faster.

[0058] It should be noted that the number of micro-drilling points in the target area should always satisfy ≤30.

[0059] Example 1: To further illustrate the present invention, the present invention is described using the FGH96 powder superalloy. The mass percentages of the respective constituent elements in the powder superalloy raw material are approximately: carbon 0.045 - 0.060 wt%, chromium 15.50 - 16.50 wt%, cobalt 12.50 - 13.50 wt%, aluminum 3.80 - 4.20 wt%, niobium 0.60 - 0.80 wt%, tungsten 3.80 - 4.20 wt%, molybdenum 3.80 - 4.20 wt%, titanium 3.55 - 3.90 wt%, zirconium 0.03 - 0.06 wt%, and the balance is nickel, with the impurity element boron being around 150 μg / g.

[0060] This embodiment discloses a method for quantitative analysis of the surface distribution of micro-region element contents of an alloy material as Figures 1-4 shown, including: Step 1: Prepare an FGH96 powder superalloy sample for solid mass spectrometry detection, meeting the requirements of solid mass spectrometry detection, taking the target element boron as an example; Step 2: Use laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) for area scanning analysis of the target element content. Select a laser beam spot size of Φ 50 μm and use a micro-area homogeneous alloy reference material to calibrate the precision. Adjust the LA-ICP-MS detection parameters so that the difference between the LA-ICP-MS detection data and the labeled value of the target element in the alloy reference material is ≤ 1%. Figure 3 The left table in Figure 3 is a typical micro-area scanned by LA-ICP-MS, and the data in the gray area is used to illustrate the data processing process as an example. Figure 3 The square area is the target area scanned by LA-ICP-MS; Step 3: Adopt the micro-drilling method to take multiple points of Φ 50 μm × 50 μm within a Φ 8 mm area, and use inductively coupled plasma mass spectrometry to determine the content of the target element at each sampling point; use inductively coupled plasma mass spectrometry to determine the content of the target element. Use an optical microscope to calibrate the spatial coordinates of the micro-drilling sampling positions, and use the quantitative analysis results of the target element by inductively coupled plasma mass spectrometry to correct the area scanning results of LA-ICP-MS at the same coordinate points.

[0061] In Step 3, adopt the micro-drilling method to take 20 points of Φ 50 μm × 50 μm within a Φ 8 mm area, and use inductively coupled plasma mass spectrometry to determine the content of the target element. The data is shown in Table 1.

[0062] Table 1 Measurement data for 20 points taken at Φ 50 μm × 50 μm

[0063] Use an optical microscope to calibrate the spatial coordinates of the micro-drilling sampling positions, and use the quantitative analysis results of the target element by inductively coupled plasma mass spectrometry to correct the area scanning results of LA-ICP-MS at the same coordinate points. The marked positions of the optical microscope are shown in Figure 4 the position of the needle eye in Figure 4 .

[0064] Step 4: Correct the overall area scanning results of LA-ICP-MS based on the correction results of Step 4; the correction results show that the boron element content fluctuates within the range of 134 μg / g to 154 μg / g.

[0065] Correct the overall area scanning results of LA-ICP-MS based on the local multi-point correction results; taking Figure 2 the data in the gray area in Figure 2 as an example, the corrected data after laser ablation is shown in Table 2.

[0066] Table 2 Results after calibration of LA-ICP-MS

[0067] This embodiment also discloses a method for correcting the surface distribution of micro-region element contents of an alloy material, including the above quantitative analysis method. There is a step 102 between step 1 and step 2: Using glow discharge mass spectrometry, after calibrating with a micro-region homogeneous alloy reference material, determine the target elements in the alloy sample to be measured, and mark the measurement area. As Figure 2 shown, this area is approximately Φ 8 mm; adjust the detection parameters of glow discharge mass spectrometry so that the difference between the detection data of glow discharge mass spectrometry and the labeled values of the target elements in the alloy reference material is ≤ 1%.

[0068] In step 2, laser ablation-inductively coupled plasma mass spectrometry is used within the glow sputtering area. Figure 3 The circular dark area in Figure 2 corresponds to the

[0069] corresponding glow sputtering area.

[0070] Example 2: This embodiment discloses a method for quantitatively analyzing the surface distribution of micro-region element contents of an alloy material. Using the same FGH96 powder superalloy sample as in Example 1, the process parameters in step 14 are the same as those in Example 1, except that: In step 3, a micro-drilling method is used to take 15 points of Φ 50 μm × 50 μm within a Φ 8 mm area, and inductively coupled plasma mass spectrometry is used to determine the content of the target elements. The quantitative analysis results of the target elements by inductively coupled plasma mass spectrometry are used to correct the surface scan results of laser ablation-inductively coupled plasma mass spectrometry at the same coordinate points. The micro-drilling sampling method uses sampling points with exactly the same spacing and evenly distributed in the target area; it can perform quantitative analysis of the surface distribution of micro-region element contents for any specified area of the alloy.

[0071] This embodiment also discloses a method for correcting the surface distribution of micro-region element contents of an alloy material, including the above method for quantitatively analyzing the surface distribution of micro-region element contents of an alloy material. There is a step 102 between step 1 and step 2: Using glow discharge mass spectrometry, after calibrating with a micro-region homogeneous alloy reference material, determine the target elements in the alloy sample to be measured, and mark the measurement area. As Figure 2As shown, the area is approximately Φ 8 mm; adjust the laser ablation-inductively coupled plasma mass spectrometry detection parameters so that the difference between the laser ablation-inductively coupled plasma mass spectrometry detection and the labeled value of the target element in the alloy reference material is ≤ 1%.

[0072] The method for correcting the surface distribution of the micro-area element content of the alloy material further includes step 5: comparing and verifying the average value μ of the quantitative analysis results of each micro-area of the target element with the glow mass spectrometry analysis result μ0 of the target element in the target area; Compare and verify the average value of the laser ablation Φ 8 mm area of the correction result with the glow mass spectrometry analysis result obtained in step 2. The detected value of boron after correction is: 138.9 μg / g. The detected value of boron by glow mass spectrometry is the same as that in Example 1: 143.5 μg / g, and the change rate relative to the detected value of boron by glow mass spectrometry is greater than 2%. Adjust the number of micro-drilling sampling points in the micro-areas smaller than μ in the target area according to the following steps, and then adjust μ: Select 5 micro-areas with the smallest detected values by laser ablation-inductively coupled plasma mass spectrometry, add a micro-drilling sampling area in each adjacent area, obtain the inductively coupled plasma mass spectrometry detection values of the newly added micro-drilling sampling areas, and correct the inductively coupled plasma mass spectrometry detection values of the micro-drilling sampling areas again with the inductively coupled plasma mass spectrometry detection values of the amplified micro-drilling sampling areas. The detected value of boron after correction is: 141.9 μg / g, which is less than 2% and meets the requirements. Repeating this process can evaluate the multi-scale uniformity traceability quantitative analysis results of the target element in any designated area of the alloy.

[0073] Comparative Example 1 This comparative example also discloses a method for GDMS analysis of the element content of an alloy material: Step 1: The mass percentages of the constituent elements in the FGH96 powder superalloy are as follows: carbon is 0.045 - 0.060 wt%, chromium is 15.50 - 16.50 wt%, cobalt is 12.50 - 13.50 wt%, aluminum is 3.80 - 4.20 wt%, niobium is 0.60 - 0.80 wt%, tungsten is 3.80 - 4.20 wt%, molybdenum is 3.80 - 4.20 wt%, titanium is 3.55 - 3.90 wt%, zirconium is 0.03 - 0.06 wt%, and the balance is nickel. Determine that the element to be measured by GDMS is boron: the content is approximately 150 μg / g; Step 2: Using glow discharge mass spectrometry, after calibration with a micro-region homogeneous alloy reference material, determine the key elements in the alloy sample to be measured, mark the measurement area, which is approximately Φ 8 mm. The glow mass spectrometry analysis result for boron is 143.5 μg / g; Using glow discharge mass spectrometry, after calibration with a micro-region homogeneous alloy reference material, determine the key elements in the alloy sample to be measured. The mass percentage of element boron determined by GDMS in the micro-region homogeneous standard material of trace elements in powder superalloy is: boron is 143.5 μg / g; Step 3: Repeat this process to evaluate the traceability and quantitative analysis results of the multi-scale uniformity of key elements in any designated area of the alloy. On the surface of the FGH96 powder superalloy, excite at an interval of Φ 8 mm step length. The data is shown in Table 3. The interval analysis by glow discharge mass spectrometry within the 8 mm area is shown in Figure 5 the middle annular area.

[0074] Table 3 GDMS measurement results

[0075] Compared with Example 1, it can achieve the micro-region distribution analysis ability of Φ 50 μm×50 μm step length within the Φ 8 mm area of the large area of the alloy material. This Comparative Example 1 can only achieve the discontinuous quantitative analysis result of Φ 8 mm.

[0076] Comparative Example 2 This comparative example also discloses a method for correcting the surface distribution of micro-region element content in an alloy material. Using the same FGH96 powder superalloy sample as in Example 1, the difference from Example 1 is that: In Step 4, a micro-drilling method is used to take 35 points of Φ 50 μm×50 μm within the Φ 8 mm area, and an inductively coupled plasma mass spectrometry is used to determine the content of the target element. The quantitative analysis result of the target element by inductively coupled plasma mass spectrometry is used to correct the surface scan result of laser ablation-inductively coupled plasma mass spectrometry at the same coordinate points. The micro-drilling sampling method uses sampling points with exactly the same spacing and is uniformly distributed in the target area.

[0077] The average value of the detected value of boron after Step 6 correction is: 141.9 μg / g, which is almost unchanged from Example 1. It can be seen from this that when the number of micro-drilling samples > 30 and the ratio of the micro-drilling sampling area to the target area in the target area > 0.2, it cannot bring an improvement in the accuracy of the quantitative analysis of the surface distribution of micro-region element content in the alloy material.

[0078] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. A method for quantitative analysis of the surface distribution of elemental contents in micro-regions of an alloy material, characterized in that, Including: Performing continuous analysis of the micro-area distribution of target elements in alloy materials below 100 μm based on laser ablation-inductively coupled plasma mass spectrometry detection; Using the detection results of inductively coupled plasma mass spectrometry to correct and analyze the laser ablation-inductively coupled plasma mass spectrometry detection data, and obtaining more accurate quantitative analysis results of target elements in the micro-areas below 100 μm in the target area of alloy materials.

2. The quantitative analysis method for the surface distribution of micro-region element contents of the alloy material according to claim 1, characterized in that, The method for quantitative analysis of the surface distribution of micro-area element contents in the alloy material includes: Performing continuous analysis of the micro-area distribution with a step size below 100 μm on the target area by using laser ablation-inductively coupled plasma mass spectrometry detection; Detecting alloy material samples of some micro-areas within the target area by using inductively coupled plasma mass spectrometry; Using the detection results of inductively coupled plasma mass spectrometry to correct the laser ablation-inductively coupled plasma mass spectrometry detection data of the same micro-area, and obtaining more accurate quantitative analysis results of target elements in the micro-areas below 100 μm in the target area of alloy materials.

3. The quantitative analysis method for the surface distribution of micro-region element contents of the alloy material according to claim 2, characterized in that, The method for quantitative analysis of the surface distribution of micro-area element contents in the alloy material includes: S1: Preparing an alloy sample for solid mass spectrometry detection, where the concentration of the target element in the alloy sample is within the detection range of mass spectrometry; S2: Obtaining continuous analysis data of the micro-area distribution of target elements within the target area based on laser ablation-inductively coupled plasma mass spectrometry detection of the target area; S3: Selecting alloy material samples from some micro-areas within the target area, and detecting the alloy material samples by using inductively coupled plasma mass spectrometry; S4: Using the detection results of inductively coupled plasma mass spectrometry of the alloy material samples to correct the laser ablation-inductively coupled plasma mass spectrometry detection data of the same micro-area, and obtaining the quantitative analysis results of each micro-area of the corrected target element.

4. The method for quantitatively analyzing the surface distribution of micro-region element contents of the alloy material according to claim 3, wherein In step S1, the mass concentration of the target element in the alloy sample satisfies: 10 -1 μg / g ~ 10 5 μg / g.

5. The quantitative analysis method for the surface distribution of micro-region element contents of the alloy material according to claim 4, characterized in that, In step S2, the laser spot diameter of the laser ablation-inductively coupled plasma mass spectrometry is 40 μm to 100 μm.

6. The method for quantitatively analyzing the surface distribution of micro-region element contents of the alloy material according to claim 5, characterized in that, Step S3 includes: Uniformly taking multiple points in the target area by using a micro-drilling method.

7. The quantitative analysis method for the surface distribution of micro-region element contents of the alloy material according to claim 6, characterized in that, The number of points taken in the target area is 15 to 30; the ratio of the micro-drilling sampling area in the target area to the target area is: 0.1 to 0.

2.

8. The method for quantitatively analyzing the surface distribution of micro-region element contents of the alloy material according to claim 7, characterized in that, Step S4 includes: S401: Calibrating the spatial coordinates of the micro-drilling sampling position by using an optical microscope, and correcting the surface scan results of the laser ablation-inductively coupled plasma mass spectrometry at the same coordinate points by using the quantitative analysis results of the target element obtained by inductively coupled plasma mass spectrometry in step S3; S402: Correcting the surface scan results of the laser ablation-inductively coupled plasma mass spectrometry of each micro-area corresponding to the spatial coordinates of the micro-drilling sampling position, and obtaining the quantitative analysis results of each micro-area of the corrected target element.

9. A method for correcting the surface distribution of micro-region element contents of an alloy material, characterized in that: Including the method for quantitative analysis of the surface distribution of micro-area element contents in the alloy material according to any one of claims 1-8, and there is a step S102 between step S1 and step S2: Measuring the target element in the alloy sample in the target area by using glow discharge mass spectrometry.

10. The method for correcting the surface distribution of micro-region element contents of the alloy material according to claim 9, characterized in that, The method for correcting the surface distribution of micro-area element contents in the alloy material further includes step S5: Comparing and verifying the average value μ of the quantitative analysis results of each micro-area of the target element obtained in step S4 with the glow mass spectrometry analysis result μ0 of the target element in the target area. If |μ - μ0| / μ0 ≤ threshold η, the average value μ of the quantitative analysis results of each micro-region and the analysis accuracy of the micro-region element content of the alloy material meet the requirements; If |μ - μ0| / μ0 > threshold η, adjust the number of micro-drilling points in the target area to |μ - μ0| / μ0 ≤ η or the change rate of the average value μ of the quantitative analysis results of each micro-region of the target element before and after adjusting the number of micro-drilling points in the target area ≤ 1%.

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