A quantitative analysis method for the surface distribution of element content in micro-areas of alloy materials

Abstract

The present invention relates to the technical field of micro-area analysis of alloy element content, and discloses a method for quantitative analysis of the surface distribution of element content in micro-areas of alloy materials. The analysis method comprises: performing continuous analysis of the distribution of target elements in micro-areas below 100 μm in the alloy material based on laser ablation-inductively coupled plasma mass spectrometry detection; correcting and analyzing laser ablation-inductively coupled plasma mass spectrometry detection data using inductively coupled plasma mass spectrometry detection results to obtain more accurate quantitative analysis results of target elements in micro-areas below 100 μm in the target area of ​​the alloy material. The method solves the problems in the prior art of difficulty in performing large-area continuous multi-size analysis of the distribution of micro-areas below 100 μm with an element content below 100 μg / g, inability to perform micro-area traceability and fixed value analysis, and inability to provide rapid and accurate quantitative traceability analysis for segregation analysis of target elements in alloys.

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 the surface distribution of element content in a micro-area of ​​an alloy material. Background Art

[0002] The powder metallurgy process eliminates macrosegregation, improves the alloy structure, and enhances disk performance. Due to its unique process steps, it also brings some inevitable defects. The main defects in powder high-temperature alloys are primary grain boundaries and inclusions. Primary grain boundaries such as γ' phase, carbides and oxides, as well as inclusions such as oxides, nitrides and sulfides, have a significant impact on the mechanical properties of powder high-temperature alloys. They can easily become crack sources in the alloy, resulting in a significant reduction in the fatigue life of the powder turbine disk. Therefore, the micro-area analysis size requirements for the micro-area distribution of target elements and the content of trace elements in powder high-temperature alloys are becoming increasingly 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 it is impossible to achieve micro-area traceability and fixed value analysis. The current micro-area analysis and component analysis technology has the following main 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 it is impossible to achieve 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:

[0003] 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

[0004] 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 of being 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, being unable to realize micro-area traceability and fixed value analysis, and being unable to provide fast and accurate quantitative traceability analysis for the segregation analysis of target elements in alloys.

[0005] The purpose of the present invention is mainly achieved through the following technical solutions:

[0006] A quantitative analysis method for the surface distribution of element content in a micro-area of ​​an alloy material, comprising:

[0007] Based on laser ablation-inductively coupled plasma mass spectrometry, the target elements in the alloy material are continuously analyzed in the micro-area below 100 μm.

[0008] The 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.

[0009] Preferably, the method for quantitative analysis of the surface distribution of element content in micro-areas of the alloy material comprises:

[0010] Laser ablation-inductively coupled plasma mass spectrometry was used to continuously analyze the micro-area distribution of the target area with a step size of less than 100 μm.

[0011] Conduct inductively coupled plasma mass spectrometry testing on alloy material samples in some micro-areas within the target area;

[0012] The results of inductively coupled plasma mass spectrometry were used to correct the laser ablation-inductively coupled plasma mass spectrometry data of the same micro-area, and more accurate quantitative analysis results of target elements in the target area of ​​the alloy material below 100 μm were obtained.

[0013] Preferably, the method for quantitative analysis of the surface distribution of element content in micro-areas of alloy materials comprises:

[0014] S1: Prepare alloy samples for solid mass spectrometry detection, and the concentration of target elements in the alloy samples is within the detection range of mass spectrometry;

[0015] S2: Detect the target area based on laser ablation-inductively coupled plasma mass spectrometry to obtain continuous analysis data of the micro-area distribution of the target element in the target area;

[0016] S3: Selecting a micro area in the target area to obtain an alloy material sample, and subjecting the alloy material sample to inductively coupled plasma mass spectrometry testing;

[0017] S4: Using the inductively coupled plasma mass spectrometry test results of the alloy material sample, the laser ablation-inductively coupled plasma mass spectrometry test data of the same micro-area are corrected to obtain the corrected quantitative analysis results of each micro-area of ​​the target element.

[0018] Preferably, the target element mass concentration of the alloy sample in step S1 satisfies: 10 -1 μg / g~10 5 μg / g.

[0019] Preferably, the laser spot diameter (ie, scanning step length) of the laser ablation-inductively coupled plasma mass spectrometry in step S2 is 40 μm to 100 μm.

[0020] Preferably, step S3 includes: uniformly selecting multiple points in the target area using a micro-drilling method.

[0021] Preferably, the number of sampling points in the target area is 15-30; the ratio of the micro-drill sampling area to the target area is 0.1-0.2.

[0022] Preferably, step S4 includes:

[0023] S401: Using an optical microscope to calibrate the spatial coordinates of the micro-drill sampling position, and using the quantitative analysis results of the target elements by inductively coupled plasma mass spectrometry obtained in step S3 to correct the laser ablation-inductively coupled plasma mass spectrometry surface scan results at the same coordinate point;

[0024] S402: Correcting the laser ablation-inductively coupled plasma mass spectrometry surface scan results of each micro-area corresponding to the spatial coordinates of the micro-drill sampling position to obtain corrected quantitative analysis results of each micro-area of ​​the target element.

[0025] A method for correcting the surface distribution of element content in a micro-area of ​​an alloy material includes the above-mentioned method for quantitatively analyzing the surface distribution of element content in a micro-area of ​​an alloy material, and further includes step S102 between step S1 and step S2:

[0026] Glow discharge mass spectrometry is used to measure the target elements in the alloy sample in the target area.

[0027] Preferably, the alloy material micro-area element content surface distribution correction method further includes step S5:

[0028] Compare and verify 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;

[0029] If |μ-μ0| / μ0≤threshold η, the average value μ of the quantitative analysis results of each micro-area and the accuracy of the element content analysis of the alloy material micro-area meet the requirements;

[0030] If |μ-μ0| / μ0>threshold η, the number of micro-drilling points in the target area is adjusted to |μ-μ0| / μ0≤η, or the change rate of the average value μ of the quantitative analysis results of each micro-area of ​​the target element before and after adjusting the number of micro-drilling points in the target area is ≤1%.

[0031] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0032] (1) The present invention uses the detection results of inductively coupled plasma mass spectrometry to correct and analyze the laser ablation-inductively coupled plasma mass spectrometry detection data, thereby achieving accurate continuous quantitative analysis of target elements in micro-areas below 100 μm in the target area of ​​the alloy material, overcoming the defect in the prior art that it is difficult to achieve large-area continuous multi-size analysis of the distribution of micro-areas below 100 μm with element contents below 100 μg / g.

[0033] (2) The present invention selects a scanning step size of less than 100 μm through laser ablation-inductively coupled plasma mass spectrometry detection, thereby obtaining a micro-area of ​​less than 100 μm, providing a continuous change trend for the metallographic changes and element segregation of the alloy material; 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 the target element; it overcomes the defects of the prior art that the micro-area traceability fixed value analysis cannot be realized, and the rapid and accurate quantitative traceability analysis cannot be provided for the segregation analysis of the target element in the alloy.

[0034] (3) When the deviation between the laser ablation-inductively coupled plasma mass spectrometry detection result and the glow discharge mass spectrometry detection result is large, the present invention increases the number of micro-drilling points smaller than μ in the target area, so that the adjusted μ increases, |μ-μ0| decreases, and |μ-μ0| / μ0 moves to the interval ≤η, and increases the number of micro-drilling points in the target area with a detection value smaller than μ. Correcting as many micro-areas smaller than μ as possible in the target area 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-area with a detection value smaller than μ in the area where micro-drilling points have been performed helps to reduce the number of times the number of micro-drilling points in the target area is adjusted, so that |μ-μ0| / μ0 converges faster.

[0035] In the present invention, the above-mentioned technical solutions can be combined with each other to achieve more preferred combinations. Other features and advantages of the present invention will be described in the following description, and some advantages will become apparent from the description or be learned through practice of the present invention. The objectives and other advantages of the present invention can be achieved and obtained through the contents particularly pointed out in the description. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The accompanying drawings are only used to illustrate specific embodiments and are not to be considered as limiting the present invention.

[0037] Figure 1 This is a flow chart for quantitative analysis of element content distribution in micro-areas of alloy materials;

[0038] Figure 2 Schematic diagram of laser ablation-inductively coupled plasma mass spectrometry surface scanning analysis;

[0039] Figure 3 This is the surface scanning data and distribution diagram of boron content by laser ablation-inductively coupled plasma mass spectrometry;

[0040] Figure 4 This is the optical microscope spatial coordinate distribution diagram of the micro-drill sampling position;

[0041] Figure 5 Schematic diagram of interval analysis by glow discharge mass spectrometry in comparative example 1. DETAILED DESCRIPTION

[0042] The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings, wherein the accompanying drawings constitute a part of the present invention and are used together with the embodiments of the present invention to illustrate the principles of the present invention, but are not used to limit the scope of the present invention.

[0043] The applicant has found that the elemental analysis of alloys includes energy spectrum analysis, probe analysis technology, mass spectrometry analysis technology and spark source atomic emission spectroscopy.

[0044] In existing technologies, energy dispersive spectroscopy (EDS) and photoelectron spectroscopy (XPS) belong to energy dispersive spectroscopy. The composition analysis results can only be qualitative and semi-quantitative, and the detection capability cannot determine the element content below 100 μg / g.

[0045] When analyzing target elements using single electron / atom probe analysis technology (EPMA / APT), large-area measurements, especially those over 100 μm, take a very long time, making this only theoretically possible and unable to assess component segregation analysis over large areas of alloys larger than 100 μm.

[0046] In-situ statistics of spark source atomic emission spectroscopy can complete the continuous distribution analysis of the composition state of bulk metals in a large size range, but it has disadvantages such as relatively low spatial resolution and element detection limit, and cannot achieve micro-area analysis below 100 μm.

[0047] Secondary ion mass spectrometry (SIMS) uses map analysis, but it cannot achieve traceability analysis or rapid analysis of large areas and sizes.

[0048] Among other mass spectrometry techniques: 1. Laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) allows for rapid content scanning in micro-areas ranging from 10 μm to 1 mm, but suffers from large analytical fluctuations. 2. Micro-drilling-inductively coupled plasma mass spectrometry, while capable of large-scale, multi-scale discontinuous source analysis, cannot achieve large-scale, multi-scale, continuous micro-area segregation analysis. While it can provide discontinuous content distribution data for areas larger than 500 μm, it lacks a continuous surface distribution. 3. Glow discharge mass spectrometry (GDMS), which utilizes a glow discharge source as an ion source and connects to a mass spectrometer for mass spectrometry, offers rapid analysis speeds, but its measurement area is limited to approximately 8 mm, making it incapable of performing micro-area analysis.

[0049] From the above, it can be seen that the existing mass spectrometry analysis technology is also difficult to achieve large-area continuous multi-size analysis of the micro-area distribution below 100 μm with element content below 100 μg / g, cannot realize micro-area traceability and fixed value analysis, and cannot provide fast and accurate quantitative traceability analysis for the segregation analysis of target elements in alloys.

[0050] In view of the above defects of the prior art, the present invention proposes a method for quantitative analysis of the surface distribution of element content in a micro-area of ​​an alloy material, comprising:

[0051] Based on laser ablation-inductively coupled plasma mass spectrometry, the target elements in the alloy material are continuously analyzed in the micro-area below 100 μm.

[0052] The 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.

[0053] During implementation, laser ablation-inductively coupled plasma mass spectrometry was used to continuously analyze the micro-area distribution of the target area with a step size of less than 100 μm.

[0054] Conduct inductively coupled plasma mass spectrometry testing on alloy material samples in some micro-areas within the target area;

[0055] The results of inductively coupled plasma mass spectrometry were used to correct the laser ablation-inductively coupled plasma mass spectrometry data of the same micro-area, and more accurate quantitative analysis results of target elements in the target area of ​​the alloy material below 100 μm were obtained.

[0056] It should be noted that existing mass spectrometry analysis technologies are divided into two categories: intermittent analysis and continuous analysis. Intermittent analysis can accurately analyze tiny parts of alloy materials, but due to discontinuous data sampling, some areas will inevitably be missed, and it is difficult to accurately reflect the element change trend of alloy materials, such as the micro-drilling-inductively coupled plasma mass spectrometry combined technology in the existing technology; and although continuous analysis can give the element change trend of alloy materials from the test results, it is limited by the analysis principle and hardware limitations, and often has 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 100μm, and the area below 100μm is the important size range for metallographic changes and element segregation of alloy materials; 2. The measurement fluctuation is large and the accuracy is poor. For example, laser ablation-inductively coupled plasma mass spectrometry is also difficult to give accurate detection results for the element change trend of alloy materials in the area below 100μm.

[0057] Compared with the existing technology, the present invention uses the detection results of inductively coupled plasma mass spectrometry to correct and analyze the laser ablation-inductively coupled plasma mass spectrometry detection data, thereby achieving accurate continuous quantitative analysis of target elements in micro-areas below 100 μm in the target area of ​​the alloy material, overcoming the defect of the existing technology that it is difficult to achieve large-area continuous multi-size analysis of the distribution of micro-areas below 100 μm with element contents below 100 μg / g.

[0058] 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, thereby obtaining a micro-area of ​​less than 100 μm, providing a continuous change trend for the metallographic changes and element segregation of the alloy material; 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 the target element; it overcomes the defects of the existing technology that cannot realize micro-area traceability and fixed value analysis, and cannot provide fast and accurate quantitative traceability analysis for the segregation analysis of the target element in the alloy.

[0059] It should be noted that the laser ablation-inductively coupled plasma mass spectrometry method can achieve rapid scanning of content in micro-areas from 10 microns to millimeters; the micro-drilling sampling + inductively coupled plasma mass spectrometry technology can achieve discontinuous content distribution data in areas above 500μm, the data is stable, and traceability analysis can be achieved.

[0060] Specifically, the quantitative analysis method of the surface distribution of element content in micro-areas of alloy materials includes:

[0061] S1: Prepare alloy samples for solid mass spectrometry detection, and the concentration of target elements in the alloy samples is within the detection range of mass spectrometry;

[0062] S2: Detect the target area based on laser ablation-inductively coupled plasma mass spectrometry to obtain continuous analysis data of the micro-area distribution of the target element in the target area;

[0063] S3: Selecting a micro area in the target area to obtain an alloy material sample, and subjecting the alloy material sample to inductively coupled plasma mass spectrometry testing;

[0064] S4: Using the inductively coupled plasma mass spectrometry test results of the alloy material sample, the laser ablation-inductively coupled plasma mass spectrometry test data of the same micro-area are corrected to obtain the corrected quantitative analysis results of each micro-area of ​​the target element.

[0065] Specifically, the target element mass concentration of the alloy sample in step S1 satisfies: 10 -1 μg / g ~10 5 μg / g.

[0066] Preferably, the laser spot diameter (i.e., scanning step length) of the laser ablation-inductively coupled plasma mass spectrometry in step S2 is 40μm to 100μm, which can be 40μm, 42μm, 46μm, 48μm, 50μm, 52μm, 56μm, 58μm, 60μm, 65μm, 64μm, 66μm, 70μm, 75μm, 77μm, 80μm, 84μm, 86μm, 88μm, 90μm, 92μm, 96μm or 100μm.

[0067] Further preferably, the laser spot diameter (scanning step length) of the laser ablation-inductively coupled plasma mass spectrometry in step S2 is 50 μm.

[0068] Specifically, step S3 includes: using a micro-drilling method to evenly select multiple points in the target area.

[0069] Preferably, the number of points in the target area is 15-30, which can be 15, 16, 17, 19, 20, 22, 24, 26, 28, 29 or 35; the ratio of the micro-drill sampling area to the target area in the target area is: 0.1-0.2, 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 point diameter is ≤ the laser spot diameter (scanning step length) in step S2.

[0070] It should be noted that the number of micro-drilling points and the micro-drilling sampling area in the target area are too small, resulting in a decrease in the correction effect of the inductively coupled plasma mass spectrometry test results on the laser ablation-inductively coupled plasma mass spectrometry test data of the same micro area; the number of micro-drilling points and the micro-drilling sampling area in the target area are too large, resulting in no significant improvement in the correction effect of the inductively coupled plasma mass spectrometry test results on the laser ablation-inductively coupled plasma mass spectrometry test data of the same micro area.

[0071] Further preferably, the number of micro-drilling points in the target area is 20-30, and the ratio of the micro-drilling sampling area to the target area is 0.1-0.15.

[0072] Further preferably, the ratio of the micro-drill sampling area to the target area in the target area is 0.1-0.13.

[0073] As an example, step S3 may be to use a micro-drilling method to sample multiple points of Φ 50 μm in a Φ 8 mm area, and use inductively coupled plasma mass spectrometry to determine the target element content at each sampling point.

[0074] Specifically, step S4 includes:

[0075] S401: Using an optical microscope to calibrate the spatial coordinates of the micro-drill sampling position, and using the quantitative analysis results of the target elements by inductively coupled plasma mass spectrometry obtained in step S3 to correct the laser ablation-inductively coupled plasma mass spectrometry surface scan results at the same coordinate point;

[0076] S402: Correcting the laser ablation-inductively coupled plasma mass spectrometry surface scan results of each micro-area corresponding to the spatial coordinates of the micro-drill sampling position to obtain corrected quantitative analysis results of each micro-area of ​​the target element.

[0077] During implementation, the quantitative analysis results of the target elements by inductively coupled plasma mass spectrometry obtained in step S3 are used to correct the surface scan results of laser ablation-inductively coupled plasma mass spectrometry at the same coordinate point, including: using micro-drill sampling inductively coupled plasma mass spectrometry data to replace the surface scan data of laser ablation-inductively coupled plasma mass spectrometry at the same coordinate point.

[0078] It should be noted that the data of micro-areas without micro-drill sampling do not need to be corrected.

[0079] On the other hand, the present invention provides a method for correcting the surface distribution of element content in a micro area of ​​an alloy material, including a method for quantitatively analyzing the surface distribution of element content in a micro area of ​​an alloy material, and further including a step S102 between step S1 and step S2:

[0080] Glow discharge mass spectrometry is used to measure the target elements in the alloy sample in the target area.

[0081] Specifically, in step S102 , the glow discharge mass spectrometry detection area is less than or equal to the target area, so that the glow discharge mass spectrometry detection area is all subjected to laser ablation-inductively coupled plasma mass spectrometry detection.

[0082] Preferably, the laser ablation-inductively coupled plasma mass spectrometry detection data in step S1 and the glow discharge mass spectrometry detection data in S102 are calibrated with an alloy standard substance, and the laser ablation-inductively coupled plasma mass spectrometry detection and glow discharge mass spectrometry detection parameters are adjusted so that the difference between the laser ablation-inductively coupled plasma mass spectrometry detection and glow discharge mass spectrometry detection data and the target element marked value in the alloy standard substance is ≤1%.

[0083] Further preferably, the alloy standard material used for the laser ablation-inductively coupled plasma mass spectrometry detection and the glow discharge mass spectrometry detection and calibration in S102 is the same, so as to ensure the consistency of the standards.

[0084] Specifically, the glow discharge mass spectrometry measurement area may be the smallest detection area in the prior art glow discharge mass spectrometry, which is a circular area of ​​about Φ 8 mm.

[0085] Specifically, the alloy material micro-area element content surface distribution correction method 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;

[0086] If |μ-μ0| / μ0≤η, the average value μ of the quantitative analysis results of each micro-area and the accuracy of the element content analysis of the alloy material micro-area meet the requirements;

[0087] If |μ-μ0| / μ0>η, the number of micro-drilling points in the target area is adjusted to |μ-μ0| / μ0≤η, or the change rate of the average value μ of the quantitative analysis results of each micro-area of ​​the target element before and after adjusting the number of micro-drilling points in the target area is ≤1%.

[0088] Specifically, η can be taken as 2%.

[0089] It should be noted that the applicant found that μ-μ0 satisfies ≤0 during actual measurement. When |μ-μ0| / μ0>η, it is necessary to increase the number of micro-drilling points in the target area.

[0090] Preferably, the number of micro-drilling points smaller than the μ micro-area in the target area needs to be increased so that the adjusted μ increases, |μ-μ0| decreases, and |μ-μ0| / μ0 moves toward the interval ≤η.

[0091] It should be noted that when |μ-μ0| / μ0>η, the main influencing factor is that the incomplete correction of the laser ablation-inductively coupled plasma mass spectrometry detection data by inductively coupled plasma mass spectrometry detection, especially the data of the micro-area with detection values ​​less than μ in the target area is not fully corrected, which leads to low μ and causes |μ-μ0| / μ0>η; therefore, increasing the number of micro-drilling points with detection values ​​less than μ in the target area and correcting as many micro-areas smaller than μ as possible in the target area will help improve the accuracy of the quantitative analysis results of each micro-area.

[0092] Further preferably, a new micro-drilling point is added near a micro-region where the detection value is less than μ in an area where micro-drilling points have been performed.

[0093] It should be noted that changes in target elements in alloys often occur continuously and gradually. Detection values ​​within the target region are more likely to be less than μ in the vicinity of the μ region. The above settings help reduce the number of microdrilling points adjusted within the target region, leading to faster convergence of |μ-μ0| / μ0.

[0094] It should be noted that the number of micro-drilling points in the target area should always be ≤30.

[0095] Example 1:

[0096] To further illustrate the present invention, the present invention uses FGH96 powder high-temperature alloy for illustration. The mass percentages of the constituent elements in the powder high-temperature alloy raw material are approximately 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. The impurity element boron is contained at approximately 150 μg / g.

[0097] This embodiment discloses a method for quantitatively analyzing the surface distribution of element content in a micro area of ​​an alloy material. Figure 1-4 Shown, including:

[0098] Step 1: Prepare FGH96 powder high-temperature alloy samples for solid mass spectrometry detection, which meet the requirements of solid mass spectrometry detection, taking boron as an example;

[0099] Step 2: Use laser ablation-inductively coupled plasma mass spectrometry to perform a surface scan analysis of the target element content. The laser beam spot size is selected to be Φ 50 μm, and the precision is calibrated using a micro-area uniform alloy standard material. The laser ablation-inductively coupled plasma mass spectrometry detection parameters are adjusted so that the difference between the laser ablation-inductively coupled plasma mass spectrometry detection data and the target element labeled value in the alloy standard material is ≤1%. Figure 3 The table on the left is a typical micro-area scanned by laser ablation-inductively coupled plasma mass spectrometry, in which the gray area data is used as an example to illustrate the data processing process. Figure 3 The square area is the target area of ​​laser ablation-inductively coupled plasma mass spectrometry scanning;

[0100] Step 3: Using a micro-drill, sample multiple points of 50 μm × 50 μm in an area of ​​8 mm in diameter, and determine the target element content at each sampling point using inductively coupled plasma mass spectrometry.

[0101] An optical microscope was used to calibrate the spatial coordinates of the micro-drill sampling position, and the target element quantitative analysis results of inductively coupled plasma mass spectrometry were used to correct the laser ablation-inductively coupled plasma mass spectrometry surface scanning results at the same coordinate point.

[0102] In step 3, micro-drilling was used to sample 20 points of 50 μm × 50 μm within an 8 mm area. The target element content was determined using inductively coupled plasma mass spectrometry. The data are shown in Table 1.

[0103] Table 1 Measurement data of 20 points in a Φ 50 μm × 50 μm area

[0104]

[0105] The spatial coordinates of the micro-drill sampling position were calibrated using an optical microscope, and the target element quantitative analysis results of inductively coupled plasma mass spectrometry were used to correct the laser ablation-inductively coupled plasma mass spectrometry surface scan results at the same coordinate point. Figure 4 The position of the needle eye.

[0106] Step 4: The overall surface scan results of the laser ablation-inductively coupled plasma mass spectrometry were corrected using the correction results of step 4. The correction results showed that the boron content fluctuated within the range of 134 μg / g to 154 μg / g.

[0107] The overall surface scan results of laser ablation-inductively coupled plasma mass spectrometry were corrected by using the local multi-point correction results. Figure 2 The data in the middle gray area are used as an example, and the data after laser ablation correction are shown in Table 2.

[0108] Table 2 Results of laser ablation-inductively coupled plasma mass spectrometry after calibration

[0109]

[0110] This embodiment also discloses a method for calibrating the surface distribution of element content in a micro-area of ​​an alloy material, including the above-mentioned quantitative analysis method, wherein step 102 is provided between step 1 and step 2: using glow discharge mass spectrometry, after calibration with a micro-area uniform alloy standard substance, the target element in the alloy sample to be measured is measured, and the measurement area is marked, such as Figure 2 As shown, the area is approximately Φ 8 mm; the detection parameters of the glow discharge mass spectrometry are adjusted so that the difference between the detection data of the glow discharge mass spectrometry and the marked value of the target element in the alloy standard material is ≤1%.

[0111] Step 2 uses laser ablation-inductively coupled plasma mass spectrometry in the glow sputtering area. Figure 3 The dark area in the middle circle corresponds to Figure 2 The glow sputtering area.

[0112] The distribution correction method also includes step 5 after step 4: the average value of the corrected laser ablation Φ8 mm area is compared with the glow mass spectrometry analysis results obtained in step 2. The average boron detection value after correction is 141.8 μg / g. The boron detection value obtained by glow mass spectrometry is 143.5 μg / g, which is within 2% of the boron detection value obtained by glow mass spectrometry, and is within the allowable difference. This process can be repeated to evaluate the traceable quantitative analysis results of the multi-scale uniformity of the target element in any specified area of ​​the alloy.

[0113] Example 2:

[0114] This embodiment discloses a method for quantitatively analyzing the surface distribution of element content in a micro-area of ​​an alloy material. The same FGH96 powder superalloy sample as in Example 1 is used, and the process parameters of step 14 are the same as in Example 1, except that:

[0115] In step 3, microdrilling was used to sample 15 points measuring 50 μm x 50 μm within an 8 mm area. The target element content was determined using inductively coupled plasma mass spectrometry (ICP-MS). The quantitative analysis of target elements using ICP-MS was used to calibrate the surface scan results of laser ablation-ICP-MS at the same coordinates. Microdrilling sampling ensures uniform sampling across the target area with identical spacing between sampling points. This allows for quantitative surface analysis of element content in any specific area of ​​the alloy.

[0116] This embodiment also discloses a method for calibrating the surface distribution of element content in a micro-area of ​​an alloy material, including the above-mentioned method for quantitatively analyzing the surface distribution of element content in a micro-area of ​​an alloy material, wherein step 102 is provided between step 1 and step 2: using glow discharge mass spectrometry, after calibration with a micro-area uniform alloy standard substance, the target element in the alloy sample to be measured is measured, and the measurement area is marked, such as Figure 2 As shown in FIG, the area is approximately Φ 8 mm; the laser ablation-inductively coupled plasma mass spectrometry detection parameters are adjusted so that the difference between the laser ablation-inductively coupled plasma mass spectrometry detection value and the target element labeled value in the alloy standard material is ≤1%.

[0117] The alloy material micro-area element content surface distribution correction method 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;

[0118] The average value of the corrected laser ablation Φ8 mm area was compared with the glow mass spectrometry analysis results obtained in step 2 for verification. The corrected boron detection value was: 138.9 μg / g. The detection value of boron by glow mass spectrometry analysis was the same as in Example 1: 143.5 μg / g, with a change rate of greater than 2% relative to the detection value of boron by glow mass spectrometry analysis. The number of micro-drilling points smaller than the μ micro-area in the target area was adjusted according to the following steps, thereby adjusting μ:

[0119] Five micro-regions with the lowest laser ablation-inductively coupled plasma-mass spectrometry (LAA-ICP-MS) values ​​were selected, and micro-drill sampling areas were added to adjacent regions. The ICP-MS values ​​of the newly added micro-drill sampling areas were then used to calibrate the ICP-MS values ​​of the micro-drill sampling areas. The corrected boron value was 141.9 μg / g, less than 2%, meeting the requirement. This process can be repeated to evaluate the multi-scale traceability quantitative analysis results for target elements in any specified area of ​​the alloy.

[0120] Comparative Example 1

[0121] This comparative example also discloses a GDMS analysis method for element content in alloy materials:

[0122] Step 1: The mass percentages of the constituent elements in the FGH96 powder superalloy are as follows: 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 nickel (the remainder). GDMS analysis confirmed boron, with a content of approximately 150 μg / g.

[0123] Step 2: Using glow discharge mass spectrometry, after calibration with a micro-area uniform alloy standard substance, determine the key elements in the alloy sample to be tested. Mark the measurement area, which is approximately Φ 8 mm. The glow mass spectrometry analysis result shows boron: 143.5 μg / g. Using glow discharge mass spectrometry, after calibration with a micro-area uniform alloy standard substance, determine the key elements in the alloy sample to be tested. GDMS determines the element boron, and the mass percentage of the powder high-temperature alloy trace element micro-area uniform standard substance is: boron is 143.5 μg / g.

[0124] Step 3: Repeat this process to evaluate the quantitative analysis results of the multi-scale uniformity of key elements in any specified area of ​​the alloy. On the surface of FGH96 powder superalloy, the excitation was performed with a step length of Φ 8 mm. The data are shown in Table 3. The interval analysis of the glow discharge mass spectrometry in the 8 mm area is shown in Table 3. Figure 5 Middle ring area.

[0125] Table 3 GDMS measurement results

[0126]

[0127] Compared with Example 1, which can achieve micro-area distribution analysis capability within a large area of ​​Φ 8 mm and a step size of Φ 50 μm×50 μm in the alloy material, this comparative example 1 can only achieve intermittent quantitative analysis results within Φ 8 mm.

[0128] Comparative Example 2

[0129] This comparative example also discloses a method for correcting the surface distribution of element content in a micro-area of ​​an alloy material, using the same FGH96 powder high-temperature alloy sample as in Example 1. The method differs from Example 1 in that:

[0130] In step 4, microdrilling was used to sample 35 points measuring 50 μm x 50 μm within an 8 mm area. The target element content was determined using inductively coupled plasma mass spectrometry (ICP-MS). The quantitative analysis of target elements by ICP-MS was used to calibrate the laser ablation-ICP-MS surface scan results at the same coordinates. Microdrilling sampling ensures that the sampling points are evenly spaced and evenly distributed across the target area.

[0131] The average value of the boron detection value after correction in step 6 is 141.9 μg / g, which is almost unchanged from Example 1. Therefore, it can be seen that the number of micro-drill sampling is greater than 30, and the ratio of the micro-drill sampling area to the target area in the target area is greater than 0.2, which cannot bring about an improvement in the accuracy of the quantitative analysis of the surface distribution of element content in the micro area of ​​the alloy material.

[0132] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with this technical field within the technical scope disclosed by the present invention should be covered by the scope of protection of the present invention.

Claims

1. A method for quantitative analysis of element content distribution in micro-areas of alloy materials, characterized in that: include: Based on laser ablation-inductively coupled plasma mass spectrometry, the target elements in the alloy material are continuously analyzed in the micro-area below 100 μm. The results of inductively coupled plasma mass spectrometry (ICP-MS) were used to calibrate and analyze the data from laser ablation-ICP-MS, obtaining more accurate quantitative analysis results for target elements in the target area of ​​the alloy material, with the diameter below 100 μm. The segregation area is accurately determined by using the inductively coupled plasma mass spectrometry test results; S1: Prepare alloy samples for solid mass spectrometry detection, and the concentration of target elements in the alloy samples is within the detection range of mass spectrometry; S2: Based on laser ablation-inductively coupled plasma mass spectrometry, the target area is detected with a step size of less than 100 μm to obtain continuous analysis data of the micro-area distribution of the target element in the target area; S3: Selecting a micro area in the target area to obtain an alloy material sample, and subjecting the alloy material sample to inductively coupled plasma mass spectrometry testing; S4: Using the inductively coupled plasma mass spectrometry test results of the alloy material sample, the laser ablation-inductively coupled plasma mass spectrometry test data of the same micro-area are corrected to obtain the corrected quantitative analysis results of each micro-area of ​​the target element.

2. The method for quantitative analysis of element content surface distribution in micro-areas of alloy materials according to claim 1, characterized in that: The target element mass concentration of the alloy sample in step S1 satisfies: 10 -1 μg / g ~10 5 μg / g.

3. The method for quantitative analysis of element content surface distribution in micro-areas of alloy materials according to claim 2, characterized in that: The laser spot diameter of the laser ablation-inductively coupled plasma mass spectrometry in step S2 is 40 μm to 100 μm.

4. The method for quantitative analysis of element content surface distribution in micro-areas of alloy materials according to claim 3, characterized in that: Step S3 includes: uniformly selecting multiple points in the target area using a micro-drilling method.

5. The method for quantitative analysis of element content distribution in micro-areas of alloy materials according to claim 4, characterized in that: The number of sampling points in the target area is 15~30; the ratio of the micro-drill sampling area to the target area is 0.1~0.

2.

6. The method for quantitative analysis of element content surface distribution in micro-areas of alloy materials according to claim 5, characterized in that: Step S4 includes: S401: Using an optical microscope to calibrate the spatial coordinates of the micro-drill sampling position, and using the quantitative analysis results of the target elements by inductively coupled plasma mass spectrometry obtained in step S3 to correct the laser ablation-inductively coupled plasma mass spectrometry surface scan results at the same coordinate point; S402: Correcting the laser ablation-inductively coupled plasma mass spectrometry surface scan results of each micro-area corresponding to the spatial coordinates of the micro-drill sampling position to obtain corrected quantitative analysis results of each micro-area of ​​the target element.

7. A method for correcting the surface distribution of element content in a micro-area of ​​an alloy material, characterized by: The method includes the method for quantitative analysis of the surface distribution of element content in a micro area of ​​an alloy material according to any one of claims 1 to 6, and a step S102 is provided between step S1 and step S2: Glow discharge mass spectrometry is used to measure the target elements in the alloy sample in the target area.

8. The method for correcting the surface distribution of element content in a micro-area of ​​an alloy material according to claim 7, characterized in that: The alloy material micro-area element content surface distribution correction method further includes step S5: Compare and verify 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-area and the accuracy of the element content analysis of the alloy material micro-area meet the requirements; If |μ-μ0| / μ0>threshold η, the number of micro-drilling points in the target area is adjusted to |μ-μ0| / μ0≤η, or the change rate of the average value μ of the quantitative analysis results of each micro-area of ​​the target element before and after adjusting the number of micro-drilling points in the target area is ≤1%.

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