Sample preparation and testing method for rsf correction sample of glow discharge mass spectrometer

Abstract

This invention relates to the field of glow discharge mass spectrometry (GFMS) analysis in chemical composition analysis, specifically to a method for preparing and testing RSF calibration samples for glow discharge mass spectrometry. The method includes: preparing and cleaning a high-purity indium sheet; cleaning and drying high-temperature alloy shavings of standard material; distributing the shavings of standard material according to a target mass ratio; placing the indium sheet in a hard alloy mold under an inert atmosphere; softening the indium sheet under vacuum conditions; sequentially laying and gradually pressing multiple portions of the shavings of standard material to form a blank; increasing the temperature and pressure; cooling and demolding to obtain a sheet-like calibration sample; and vacuum sealing after passing a stability test. The calibration samples are then used for glow discharge mass spectrometry testing, and the RSF is calculated using linear fitting. cal The calibration is completed. This invention solves the problems of mismatch between standard substances and fixtures and easy contamination. The prepared sheet samples have good size matching and uniformity, and the calibration linearity coefficient is above 0.999.

Description

Technical Field

[0001] This invention relates to the field of glow discharge mass spectrometry in chemical composition analysis, specifically to a method for sample preparation and testing using relative sensitivity factor (RSF) calibration for glow discharge mass spectrometry. Background Technology

[0002] Glow discharge mass spectrometry is a key technology for trace element analysis of solid materials. It has advantages such as direct solid sample introduction, full element detection, fast analysis speed, wide detection range, weak matrix effect and strong gas element analysis capability. It is widely used in industries such as high-purity metals, semiconductors, alloys, ceramics and coatings, and is the core means of impurity control and quality monitoring of high-purity metal and semiconductor materials.

[0003] The relative sensitivity factor (RSF) is a key parameter connecting signal intensity and elemental content in quantitative analysis by glow discharge mass spectrometry. This parameter is affected by factors such as the sample matrix, sputtering and ionization conditions, instrument status, and detection parameters; recalibration is required when any of these conditions change. Conventional calibration methods use matrix-matched standard substances with concentration gradients to plot standard calibration curves. However, achieving relative sensitivity factor calibration for glow discharge mass spectrometry has long faced the following difficulties: First, there is a shortage of standard samples. The existing metal block standard materials are not geometrically compatible with the sample clamps of glow discharge mass spectrometers and must be precision machined before they can be used. The machining process is cumbersome, time-consuming, and labor-intensive, and it is also very easy to introduce foreign contaminants, which affects the accuracy of ultra-trace element analysis results.

[0004] Second, the number of elements in the metal block standard material is too small, the identification value of some elements is too high, and the content uncertainty is large, which makes it difficult to meet the requirements of accurate quantification and quality control of ultra-trace impurity elements in glow discharge mass spectrometry.

[0005] Third, although metal shavings-shaped standard materials are superior to block-shaped standard materials in terms of the types of elements to be determined and the coverage of trace / ultra-trace content, their sample morphology is incompatible with the sample holder of glow discharge mass spectrometry and cannot be directly tested on the instrument. Summary of the Invention

[0006] To address the aforementioned problems, this invention provides a method for preparing and testing RSF-calibrated samples for glow discharge mass spectrometry.

[0007] The technical solution adopted in this invention is: A method for preparing samples for relative sensitivity factor calibration in glow discharge mass spectrometry includes the following steps: Step 1: Prepare high-purity indium sheets. The high-purity indium sheets are ultrasonically cleaned sequentially with dilute nitric acid, ultrapure water and anhydrous ethanol. After cleaning, the sheets are removed and dried. The cleaned high-purity indium sheets are then screened for impurity elements. Step 2: The high-temperature alloy shavings standard material were ultrasonically cleaned sequentially with ultrapure water and anhydrous ethanol, and then vacuum dried. Step 3: Mix the high-purity indium sheet processed in Step 1 with the high-temperature alloy chip standard material processed in Step 2 according to the target value, and divide the chip standard material into multiple equal parts. Step 4: Under an inert atmosphere, place the high-purity indium sheet in a hard alloy mold that matches the sheet fixture of the glow discharge mass spectrometer; Step 5: Under vacuum conditions, maintain the temperature at 50℃-80℃ for 10min-20min to soften the high-purity indium sheet without melting it; Step 6: Using a gradient pressurization method, multiple portions of the aforementioned shaving-like standard material are sequentially and evenly spread on the softened high-purity indium sheet and then gradually pressurized to fuse them together, forming a blank; Step 7: Heat to 100℃-120℃, further pressurize to 100MPa and hold for 10min-20min to densify the billet; Step 8: After cooling to room temperature, demold to obtain sheet-like calibration samples.

[0008] Furthermore, the high-purity indium sheet prepared in step 1 is prepared using a dedicated automated cutting and pressing device, which includes a cutting device and a pressing device.

[0009] Furthermore, the cutting device includes a cutting equipment base and a cutting base plate. The upper end of the cutting equipment base is connected to the cutting base plate, and the cutting base plate is provided with multiple cutting fixed columns. The cutting moving table is slidably fitted onto the cutting fixed columns, and the cutting top plate is fixed to the top of the cutting fixed columns. A cutting electric push cylinder passes through and is fixed to the cutting top plate, and its internal piston rod is connected to the cutting moving table. An upper pressure rod is installed at the lower end of the cutting moving table. A lower fixed mold is fixedly installed on the cutting base plate, and a tool frame is provided at the upper end of the lower fixed mold. A longitudinal cutting blade and a transverse cutting blade are installed in the tool frame, and a centering clamp is installed on the tool frame. A spring and a lower push rod are arranged sequentially from bottom to top inside the lower fixed mold, and the spring is supported inside the lower fixed mold. Between the bottom surface and the lower end of the lower push rod; the ends of the upper pressure rod and the lower push rod are grid-like columns, matching the longitudinal and transverse cutting blades; the cutting device also includes a cutting touch screen, a cutting protective cover, a cutting safety light curtain, a cutting control box, adjustable cutting feet, a cutting power switch, a cutting start button, a cutting emergency stop button, and bolts; the cutting control box is electrically connected to the cutting electric push cylinder and the cutting touch screen; the cutting power switch, the cutting start button, and the cutting emergency stop button are located on the cutting control box; the cutting protective cover and the adjustable cutting feet are located on the base of the cutting equipment; the cutting safety light curtain is installed at the cutting protective cover; and the bolts are used to fix the cutting base plate to the lower fixed mold.

[0010] Furthermore, the pressing device includes a pressing electric push cylinder, a push cylinder mounting plate, a moving stage push rod, and a pressing moving stage. The cylinder body of the pressing electric push cylinder is connected to the pressing moving stage through the push cylinder mounting plate and the moving stage push rod. The pressing moving stage is slidably sleeved on the pressing fixed column. The lower end of the pressing fixed column is fixed to the pressing base plate, and the pressing base plate is fixed to the pressing equipment base. The pressing top plate is fixed to the top of the pressing fixed column, and the upper mold base is fixed below the pressing top plate. The upper mold is fixed to the upper mold base by upper mold locking bolts. The lower mold plate is fixed to the pressing moving stage, and the lower mold is fixed to the lower mold plate by lower mold locking bolts. The sample pressing ring is placed inside the lower mold. The movable push rod is set inside the lower mold, and the fixed push rod is fixed to the pressing base plate and located below the movable push rod. The pressing electric push cylinder drives the pressing moving stage to move the lower mold. The movable push rod moves upward and cooperates with the fixed upper mold to complete the pressing; during the descent, the fixed push rod holds the movable push rod, and the pressing moving stage continues to drive the lower mold to move downward relative to the stationary movable push rod, pushing the sample out; the pressing device also includes a pressing touch screen, a pressing protective cover, a pressing safety light curtain, a pressing control box, pressing adjustable feet, a pressing power switch, a pressing start button, a pressing emergency stop button, and a pressure sensor; the pressing control box is electrically connected to the pressing electric push cylinder and the pressing touch screen, the pressure sensor is set on the push cylinder mounting plate for detecting pressure, the pressing power switch, the pressing start button, and the pressing emergency stop button are set on the pressing control box, the pressing protective cover and the pressing adjustable feet are set on the pressing equipment base, and the pressing safety light curtain is installed at the pressing protective cover.

[0011] Further, the specific operation of cleaning the high-purity indium sheet in step 1 is as follows: the high-purity indium sheet is placed in a polytetrafluoroethylene beaker, 10% dilute nitric acid is added and ultrasonically cleaned for 3 minutes, then cleaned 5 times with ultrapure water, ultrasonically cleaned with ultrapure water for 3 minutes, and then ultrasonically cleaned with anhydrous ethanol for 3 minutes. After cleaning, the sheet is taken out and dried. The high-purity indium sheet after cleaning is screened for impurity elements to detect whether the element content of As, Pb, Bi, Sn and Sb is less than 0.05 μg / g.

[0012] Furthermore, the specific operation of cleaning and drying the high-temperature alloy shavings standard material in step 2 is as follows: the weighed high-temperature alloy shavings standard material is placed in a polytetrafluoroethylene beaker, sonicated with ultrapure water for 3 minutes, then sonicated with anhydrous ethanol for 3 minutes, and then placed in a vacuum furnace for vacuum drying for 2 hours.

[0013] Furthermore, the mass ratio mentioned in step 3 is: the mass ratio of high-purity indium sheet to high-temperature alloy shavings standard material is 9:1, and the shavings standard material is divided into 3 equal parts; The vacuum level described in step 5 is <10. -3 Pa; The specific method of gradient pressurization in step 6 is as follows: the first piece of shavings of standard material is evenly spread on the softened high-purity indium sheet, pre-pressed at 10MPa-15MPa and held for 1 minute; the second piece of shavings of standard material is evenly spread, and the main pressure is 20MPa and held for 3 minutes; the third piece of shavings of standard material is evenly spread, and the pressure is 50MPa and held for 5 minutes.

[0014] Further, step 7 specifically involves: heating to 120℃, pressurizing to 100MPa and holding the pressure for 10 minutes; step 8 involves obtaining a sheet-like corrected sample with a diameter of 20mm and a thickness of 0.5mm-1.0mm after demolding.

[0015] A method for relative sensitivity factor calibration testing in glow discharge mass spectrometry, comprising the following steps: Testing a series of sheet-like calibration samples with concentration gradients prepared by the aforementioned method. Step A: Perform mass calibration and ion efficiency testing using a high-purity tantalum sample; Step B: Place the series of sheet-like calibration samples with concentration gradients into a glow discharge mass spectrometer and turn on glow discharge. After the pre-sputtering time is set, test the elements to be measured. Step C: Perform linear fitting between the test results and the standard values, and calculate the corrected relative sensitivity factor (RSF) for each element. cal , RSF cal The value is applied in the quantitative analysis of high-temperature alloy samples.

[0016] Further, in step A, when the temperature of the glow discharge mass spectrometer reaction cell base cools to -160℃, a 5N high-purity tantalum sample is placed in it; the operating parameters of the glow discharge mass spectrometer are: discharge current 1.5mA, discharge voltage 1100V, argon flow rate 0.36L / min, extraction lens voltage 4305V, vertical source voltage V1 76.5V, and horizontal source voltage H1 -53.5V; in step B, before performing the analyte test, the calibration sample is pre-sputtered for 15min, and the test method further includes: using other similar standard materials to test the RSF. cal Verify the accuracy.

[0017] The beneficial effects of this invention are as follows: 1. A dedicated cutting and pressing device is used to convert high-purity indium raw materials into high-purity indium sheets. The cutting and pressing processes are completed automatically under controlled conditions, avoiding external contamination caused by manual operation and mechanical processing. The indium sheets have uniform thickness and can be mass-produced.

[0018] 2. Utilizing the softening property of indium at temperatures below its melting point, high-purity indium sheets are softened under vacuum and at 50℃-80℃. Then, the standard material is uniformly dispersed on the indium substrate by layering shavings of standard material and applying gradient pressure. Combined with subsequent heating to 100℃-120℃ and pressurizing to 100MPa, the sheet is densified. The preparation process avoids the cracking and delamination problems caused by directly pressing high-melting-point powder.

[0019] 3. After demolding, a sheet-like calibration sample with a diameter of approximately 20 mm and a thickness of 0.5 mm to 1.0 mm is directly obtained. The size matches the sheet-like fixture of the glow discharge mass spectrometer, eliminating the need for secondary machining and solving the problem of incompatibility between the morphology of blocky standard materials and flaky standard materials.

[0020] 4. Using the above method, a series of sheet-like calibration samples with concentration gradients were tested by glow discharge mass spectrometry. The linear fitting coefficient between the test results of each analyte and the standard value can reach above 0.999. This method can complete the relative sensitivity factor calibration of trace impurity elements in high-temperature alloys. The calibrated relative sensitivity factor can also be verified by other similar standard materials. This method can be extended to glow discharge mass spectrometry calibration of other materials. Attached Figure Description

[0021] Figure 1 RSF calibration curves for each analyte were obtained by preparing shaving-like calibration samples. Figure 1 (a) is the RSF correction curve for element B. Figure 1 (b) is the RSF correction curve for Ge. Figure 1 (c) is the RSF correction curve for the As element. Figure 1 (d) is the RSF correction curve of the Sn element. Figure 1 (e) is the RSF correction curve for the Sb element. Figure 1 (f) is the RSF correction curve for Te element. Figure 1 (g) is the RSF correction curve of Bi element.

[0022] Figure 2 This is a three-dimensional view of the cutting device for a high-purity indium block in a glow discharge mass spectrometer.

[0023] Figure 3 This is a front view of the cutting device for high-purity indium blocks in a glow discharge mass spectrometer.

[0024] Figure 4 This is a top view of the cutting device for high-purity indium blocks in a glow discharge mass spectrometer.

[0025] Figure 5 This is a cross-sectional view of the cutting device for a high-purity indium block in a glow discharge mass spectrometer.

[0026] Figure 6 This is a diagram of the core component of the cutting device for high-purity indium blocks in a glow discharge mass spectrometer.

[0027] Figure 7 This is an assembly drawing of the upper pressure rod, lower push rod, and cutting blade of the cutting device for a high-purity indium block in a glow discharge mass spectrometer.

[0028] Figure 8 This is a three-dimensional view of the pressing device for high-purity indium sheets in a glow discharge mass spectrometer.

[0029] Figure 9 This is a three-dimensional view of the internal pressing system of the high-purity indium sheet pressing device for a glow discharge mass spectrometer.

[0030] Figure 10 This is a front view of the pressing device for high-purity indium sheets in a glow discharge mass spectrometer.

[0031] Figure 11 This is a top view of the pressing device for high-purity indium sheets in a glow discharge mass spectrometer.

[0032] Figure 12 This is a cross-sectional view of the pressing device for high-purity indium sheets in a glow discharge mass spectrometer.

[0033] Figure 13 This is a cross-sectional view of the upper and lower pressing molds of the pressing device for high-purity indium sheets in a glow discharge mass spectrometer.

[0034] Reference numerals: 1. Cutting touchscreen; 2. Cutting protective cover; 3. Cutting safety light curtain; 4. Cutting control box; 5. Cutting equipment base; 6. Cutting adjustable feet; 7. Cutting power switch; 8. Cutting start button; 9. Cutting emergency stop button; 10. Cutting electric push cylinder; 11. Cutting top plate; 12. Cutting moving table; 13. Cutting fixed column; 14. Longitudinal cutting blade; 15. Lower fixed mold; 16. Spring; 17. Cutting base plate; 18. Bolt; 19. Upper pressure rod; 20. High-purity indium raw material; 21. Cross-cutting blade; 22. Lower push rod; 23. Centering clamp; 24. Tool frame; 25. Pressing touchscreen; 26. Pressing protective cover. 27. Safety light curtain, 28. Control box, 29. Adjustable feet, 30. Power switch, 31. Start button, 32. Emergency stop button, 33. Electric push cylinder, 34. Push cylinder mounting plate, 35. Pressure sensor, 36. Top plate, 37. Upper mold base, 38. Upper mold, 39. Movable push rod, 40. Lower mold, 41. Moving stage, 42. Fixed push rod, 43. Base plate, 44. Equipment base, 45. Fixed column, 46. Upper mold locking bolt, 47. Moving stage push rod, 48. Lower mold locking bolt, 49. Lower mold pressure plate, 50. Sample pressure ring. Detailed Implementation

[0035] The technical solution of the present invention will be described in detail below through specific embodiments, but the scope of protection of the present invention is not limited to the embodiments described.

[0036] I. Preparation of High-Purity Indium Sheets In this embodiment, the preparation of high-purity indium sheets includes two stages: cutting high-purity indium raw materials and pressing high-purity indium sheets, which are completed using dedicated cutting and pressing devices, respectively.

[0037] Cutting of high-purity indium raw material 20: The structure of the cutting device is shown in the attached figure. Figures 2 to 7 As shown. The upper end of the cutting equipment base 5 is connected to the cutting base plate 17. The cutting base plate 17 is provided with multiple cutting fixed columns 13. The cutting moving table 12 is slidably sleeved on the cutting fixed columns 13. The cutting top plate 11 is fixed to the top of the cutting fixed columns 13. The cutting electric push cylinder 10 passes through and is fixed on the cutting top plate 11. Its internal piston rod is connected to the cutting moving table 12. The lower end of the cutting moving table 12 is equipped with an upper pressure rod 19. A lower fixed mold 15 is fixedly installed on the cutting base plate 17. The upper end is provided with a tool frame 24; the tool frame 24 is equipped with a longitudinal cutter 14 and a transverse cutter 21, and a centering clamp 23 is installed on the tool frame 24. The centering clamp 23 is used to center and fix the high-purity indium raw material 20; the lower fixed mold 15 is provided with a spring 16 and a lower push rod 22 from bottom to top inside. The spring 16 is supported between the inner bottom surface of the lower fixed mold 15 and the lower end of the lower push rod 22; the ends of the upper pressure rod 19 and the lower push rod 22 are grid columns, which match the longitudinal cutter 14 and the transverse cutter 21.

[0038] In addition, the cutting device also includes a cutting touch screen 1, a cutting protective cover 2, a cutting safety light curtain 3, a cutting control box 4, adjustable cutting feet 6, a cutting power switch 7, a cutting start button 8, a cutting emergency stop button 9, and bolts 18. The cutting control box 4 is electrically connected to the cutting electric push cylinder 10 and the cutting touch screen 1. The cutting power switch 7, the cutting start button 8, and the cutting emergency stop button 9 are all located on the cutting control box 4. The cutting protective cover 2 and the adjustable cutting feet 6 are located on the cutting equipment base 5. The cutting safety light curtain 3 is installed at the cutting protective cover 2. Bolts 18 are used to fix the cutting base plate 17 to the lower fixed mold 15.

[0039] During the cutting operation, select the cross-cutting blade 21 according to the weight of the high-purity indium raw material 20 and adjust its gap. Clean the high-purity indium raw material 20, longitudinal cutting blade 14, and cross-cutting blade 21 with alcohol and install them in the tool frame 24. Use the centering clamp 23 to place and fix the high-purity indium raw material 20 in the center. Install the upper pressure rod 19 and install the lower push rod 22 and spring 16 into the lower fixed mold 15. Turn on the cutting power switch 7 on the cutting control box 4 and program the cutting on the cutting touch screen 1. The program parameters include the pressure increase rate and lifting distance. Click the cutting start button 8, and the cutting electric push cylinder 10 starts. Its internal piston rod pushes the cutting moving table 12 downward. The upper pressure rod 19 slowly contacts the high-purity indium raw material 20 until the spring 16 is compressed to the lowest point, and the cutting begins. The high-purity indium raw material 20 first contacts the longitudinal cutter 14 to complete the longitudinal cut. Continuing its downward movement, it contacts the transverse cutter 21. The grid-like ends of the upper pressure rod 19 and the lower push rod 22 match the longitudinal cutter 14 and the transverse cutter 21, allowing for continued downward cutting until the upper pressure rod 19 and the lower push rod 22 pass through the two cutters and collide, completing the cut. Subsequently, the cutting moving table 12 rises, and the spring 16 gradually extends, pushing the cut indium block out of the longitudinal cutter 14 and the transverse cutter 21.

[0040] Pressing of high-purity indium sheets: The structure of the pressing device is shown in the attached figure. Figures 8 to 13 As shown. The cylinder body of the electric pressing cylinder 33 is connected to the pressing moving stage 41 via the pressing cylinder mounting plate 34 and the moving stage push rod 47. The pressing moving stage 41 is slidably sleeved on the pressing fixed column 45. The lower end of the pressing fixed column 45 is fixed to the pressing base plate 43, and the pressing base plate 43 is fixed to the pressing equipment base 44. The pressing top plate 36 is fixed to the top of the pressing fixed column 45, the upper mold base 37 is fixed below the pressing top plate 36, and the upper pressing mold 38 is fixed to the upper mold base 37 by the upper mold locking bolt 46. The lower mold pressing plate 49 is fixed to the pressing moving stage 41, and the lower pressing mold 40 is fixed to the lower mold pressing plate 49 by the lower mold locking bolt 48. The sample pressing ring 50 is placed inside the lower pressing mold 40. The movable push rod 39 is set inside the lower pressing mold 40, and the fixed push rod 42 is fixed on the pressing base plate 43 and located below the movable push rod 39. During pressing, the pressing electric push cylinder 33 drives the pressing moving stage 41 to move the lower pressing mold 40 and the movable push rod 39 upward, cooperating with the fixed upper pressing mold 38 to complete the pressing; during the descent, the fixed push rod 42 holds the movable push rod 39, and the pressing moving stage 41 continues to drive the lower pressing mold 40 to move downward relative to the stationary movable push rod 39, pushing the sample out.

[0041] In addition, the pressing device also includes a pressing touch screen 25, a pressing protective cover 26, a pressing safety light curtain 27, a pressing control box 28, a pressing adjustable foot 29, a pressing power switch 30, a pressing start button 31, a pressing emergency stop button 32, and a pressure sensor 35. The pressing control box 28 is electrically connected to the pressing electric push cylinder 33 and the pressing touch screen 25. The pressure sensor 35 is installed on the push cylinder mounting plate 34 for detecting pressure. The pressing power switch 30, the pressing start button 31, and the pressing emergency stop button 32 are installed on the pressing control box 28. The pressing protective cover 26 and the pressing adjustable foot 29 are installed on the pressing equipment base 44. The pressing safety light curtain 27 is installed on the pressing protective cover 26.

[0042] During the pressing operation, select an upper pressing die 38 that matches the required indium sheet thickness and diameter, install it on the upper die base 37, and secure it with the upper die locking bolt 46; fix the lower pressing die 40 on the lower die plate 49 and secure it with the lower die locking bolt 48; select a sample pressing ring 50 that matches the size of the upper pressing die 38, fix it, and wipe it clean with alcohol, then place the previously cut 1g block of high-purity indium raw material 20 inside. Turn on the pressing power switch 30 on the pressing control box 28, and program the pressing program on the pressing touch screen 25. The program parameters include pressing distance, pressure, pressurization rate, and holding time. Click the pressing start button 31, and the cylinder body of the pressing electric push cylinder 33 moves upward, driving the push cylinder mounting plate 34, the moving stage push rod 47, the pressing moving stage 41, the lower pressing die 40, and the movable push rod 39 to move upward together. The upper pressing die 38 remains stationary during the operation, while the lower pressing die 40 moves upward to complete the pressing. After pressing is completed, the pressing moving stage 41 automatically descends, moving the lower pressing die 40 and the movable ejector rod 39 downwards simultaneously. Once at a certain position, the fixed ejector rod 42 first blocks the movable ejector rod 39, preventing it from descending further. The pressing moving stage 41 continues to move the lower pressing die 40 downwards relative to the now stationary movable ejector rod 39, ejecting the pressed high-purity indium sheet along with the sample pressing ring 50 from the lower pressing die 40, resulting in a high-purity indium sheet with uniform thickness. By precisely controlling the pressing distance of the upper pressing die 38, high-purity indium sheets with a thickness controlled within the range of 1mm-2mm can be produced in batches.

[0043] II. Sample Cleaning and Pretreatment Stage Cleaning of high-purity indium sheets: The high-purity indium sheet obtained by pressing was placed in a polytetrafluoroethylene beaker and ultrasonically cleaned for 3 minutes with 10% dilute nitric acid. After acid washing, the indium sheet was rinsed five times with ultrapure water, ultrasonicated for 3 minutes with ultrapure water, and finally ultrasonicated for 3 minutes with anhydrous ethanol. It was then removed and dried. The cleaned high-purity indium sheet was screened for impurities, and the contents of As, Pb, Bi, Sn, and Sb were tested to ensure they were less than 0.05 μg / g. The results showed that the contents of As, Pb, Bi, Sn, and Sb were all less than 0.05 μg / g, the total impurity was 0.79 ppm, and the purity reached above 6N, meeting the testing requirements. The elemental contents of the prepared high-purity indium sheet are shown in Table 1.

[0044] Table 1: Element content (μg / g) in the prepared high-purity indium sheet Cleaning and drying of high-temperature alloy shavings standard materials: The weighed high-temperature alloy shavings standard material were placed in a polytetrafluoroethylene beaker, sonicated with ultrapure water for 3 minutes, then sonicated with anhydrous ethanol for 3 minutes, and then placed in a vacuum furnace for vacuum drying for 2 hours to remove the water and organic matter adsorbed on the surface.

[0045] III. Sample Preparation Stage for Relative Sensitivity Factor Correction Mass ratio: High-purity indium sheets that have been cleaned and tested to meet standards are mixed with cleaned and dried high-temperature alloy shavings of standard material at a target ratio of 9:1. The mixture is then weighed according to the target value. The weighed shavings of standard material are divided into three equal portions.

[0046] Low-temperature vacuum homogenization: In an inert atmosphere glove box environment, place weighed high-purity indium sheets and 3 parts of shavings of standard material, and store for later use. Place the high-purity indium sheets in a hard alloy mold that matches the sheet fixture of the glow discharge mass spectrometer, and place it in a temperature-controlled press. Under vacuum conditions, with a vacuum degree <10... -3 Pa is held at 50℃-80℃ for 10-20 minutes. In this embodiment, it is held at 70℃ for 15 minutes to soften the high-purity indium sheet without melting it.

[0047] The fusion process employs a gradient pressurization method: the first batch of standard material in shavings is evenly spread on the softened indium sheet, pre-pressed at 10MPa-15MPa and held for 1 minute (in this embodiment, 10MPa is used); the second batch of standard material in shavings is then evenly spread, and the main pressure is applied at 20MPa for 3 minutes; the third batch of standard material in shavings is then evenly spread, and the pressure is applied at 50MPa for 5 minutes. Through these stages of pressurization, a green body is formed.

[0048] Heating molding: The temperature is raised to 100℃-120℃, specifically to 120℃ in this embodiment, and then further pressurized to 100MPa and held for 10 minutes to densify the blank. The resulting sheet has a density of 95%.

[0049] Cooling and demolding: After slow cooling at room temperature, the sample was demolded to obtain a sheet-like calibration sample. The obtained sheet-like calibration sample had a diameter of approximately 20 mm, a thickness of 0.5 mm to 1.0 mm, a surface flatness Ra of 0.8 μm, and no cracks, voids, or leakage of flaky standard material. It also exhibited uniform conductivity.

[0050] In-situ quality control closed loop: After demolding, the sheet-like calibration sample was ultrasonically cleaned with anhydrous ethanol for 3 minutes, dried, and then subjected to multiple independent tests on the elements to be calibrated. The relative standard deviation (RSD) was calculated. In this embodiment, the elements to be calibrated were tested 5 times independently. Taking the sheet-like calibration sample numbered GBW01637 as an example, the test results and RSD values ​​of the elements to be calibrated are shown in Table 2. The RSD of each element was less than 5%, and the sample was deemed to be of acceptable stability. The sample was then placed in a sealed bag and vacuum-sealed for storage.

[0051] Table 2: RSD values ​​of each analyte in standard reference material GBW01637 IV. Relative Sensitivity Factor Correction Test Phase RSF correction tests were performed using a series of sheet-like calibration samples with concentration gradients prepared by the method described above, as follows: First, after the temperature of the glow discharge mass spectrometer's reaction cell base cooled to -160℃, a 5N high-purity tantalum sample was placed inside, and the glow discharge was initiated to perform mass calibration and ionization efficiency testing. The operating parameters of the glow discharge mass spectrometer are shown in Table 3.

[0052] Table 3: GDMS Instrument Operating Parameters Then, after pre-sputtering the series of sheet-like calibration samples with concentration gradients for 15 minutes, glow discharge was activated to test the elements to be measured.

[0053] Finally, the test results were linearly fitted to the standard values, and the calibration curves for each element are shown below. Figure 1As shown, the calibrated samples prepared using the method of this invention were verified by glow discharge mass spectrometry. The linear coefficients of all analytes reached above 0.999, and the RSD was less than 5%, which meets the RSF correction requirements for trace impurity elements in high-temperature alloys. The above method can also be extended to glow discharge mass spectrometry calibration of other material systems. The relative sensitivity factor (RSF) values ​​of each element after calibration were calculated. cal The linear coefficients of each element and the RSF values ​​before and after correction are shown in Table 4. The linear coefficients of all elements are above 0.999. The RSF values ​​are... cal The values ​​are merged and saved with the original file, and then applied to other high-temperature alloy samples to be tested, thus completing the RSF correction.

[0054] As an optional verification step, standard materials numbered GBW01638 and GBW01639 were subsequently used to verify the calibrated RSF. cal The accuracy was verified, and the results are shown in Table 5: the test results of the two standard substances for the analytes are all within their uncertainty range, indicating that the corrected RSF is within acceptable limits. cal Accurate and effective.

[0055] Table 4: Linearity coefficients and RSF values ​​before and after correction for each element Table 5: Validation Results of GBW01638 and GBW01639 Standard Reference Materials The calibrated samples prepared using the method of this invention were verified by glow discharge mass spectrometry. The linear coefficients of all analytes were above 0.999, and the RSD was less than 5%, which meets the RSF correction requirements for trace impurity elements in high-temperature alloys. Other standard materials were used to correct the RSF. cal Validation was performed, and the results proved that RSF cal The results are accurate and effective. The above method can also be extended to glow discharge mass spectrometry correction of other material systems.

Claims

1. A method for preparing samples for relative sensitivity factor calibration in glow discharge mass spectrometry, characterized in that, Includes the following steps: Step 1: Prepare high-purity indium sheets. The high-purity indium sheets are ultrasonically cleaned sequentially with dilute nitric acid, ultrapure water and anhydrous ethanol. After cleaning, the sheets are removed and dried. The cleaned high-purity indium sheets are then screened for impurity elements. Step 2: The high-temperature alloy shavings standard material were ultrasonically cleaned sequentially with ultrapure water and anhydrous ethanol, and then vacuum dried. Step 3: Mix the high-purity indium sheet processed in Step 1 with the high-temperature alloy chip standard material processed in Step 2 according to the target value, and divide the chip standard material into multiple equal parts. Step 4: Under an inert atmosphere, place the high-purity indium sheet in a hard alloy mold that matches the sheet fixture of the glow discharge mass spectrometer; Step 5: Under vacuum conditions, maintain the temperature at 50℃-80℃ for 10min-20min to soften the high-purity indium sheet without melting it; Step 6: Using a gradient pressurization method, multiple portions of the aforementioned shaving-like standard material are sequentially and evenly spread on the softened high-purity indium sheet and then gradually pressurized to fuse them together, forming a blank; Step 7: Heat to 100℃-120℃, further pressurize to 100MPa and hold for 10min-20min to densify the billet; Step 8: After cooling to room temperature, demold to obtain sheet-like calibration samples.

2. The method for preparing samples for relative sensitivity factor calibration in glow discharge mass spectrometry according to claim 1, characterized in that, The high-purity indium sheet prepared in step 1 is prepared using a dedicated automated cutting and pressing device, which includes a cutting device and a pressing device.

3. The method for preparing samples for relative sensitivity factor calibration in glow discharge mass spectrometry according to claim 2, characterized in that, The cutting device includes a cutting equipment base (5) and a cutting base plate (17). The upper end of the cutting equipment base (5) is connected to the cutting base plate (17). Multiple cutting fixed columns (13) are provided on the cutting base plate (17). The cutting moving table (12) is slidably sleeved on the cutting fixed columns (13). The cutting top plate (11) is fixed to the top of the cutting fixed columns (13). The cutting electric push cylinder (10) passes through and is fixed on the cutting top plate (11). Its internal piston rod is connected to the cutting moving table (12). 12) Connection; An upper pressure rod (19) is installed at the lower end of the cutting moving table (12); A lower fixed mold (15) is fixedly installed on the cutting base plate (17), and a tool frame (24) is provided at the upper end of the lower fixed mold (15); A longitudinal cutting blade (14) and a transverse cutting blade (21) are installed in the tool frame (24), and a centering clamp (23) is installed on the tool frame (24); A spring (16) and a lower push rod (22) are provided inside the lower fixed mold (15) from bottom to top, and the spring (16) is supported by the lower fixed mold. Between the inner bottom surface of the fixed mold (15) and the lower end of the lower ejector rod (22); the ends of the upper pressure rod (19) and the lower ejector rod (22) are grid-like columns, matching the longitudinal cutter (14) and the transverse cutter (21); the cutting device also includes a cutting touch screen (1), a cutting protective cover (2), a cutting safety light curtain (3), a cutting control box (4), a cutting adjustable foot (6), a cutting power switch (7), a cutting start button (8), a cutting emergency stop button (9), and bolts (18); the cutting control The cutting box (4) is electrically connected to the electric cutting cylinder (10) and the cutting touch screen (1). The cutting power switch (7), the cutting start button (8) and the cutting emergency stop button (9) are located on the cutting control box (4). The cutting protective cover (2) and the cutting adjustable feet (6) are located on the cutting equipment base (5). The cutting safety light grid (3) is installed at the cutting protective cover (2). The bolt (18) is used to fix the cutting base plate (17) and the lower fixed mold (15).

4. The method for preparing samples for relative sensitivity factor calibration in glow discharge mass spectrometry according to claim 2, characterized in that, The pressing device includes a pressing electric push cylinder (33), a push cylinder mounting plate (34), a moving table push rod (47), and a pressing moving table (41). The cylinder body of the pressing electric push cylinder (33) is connected to the pressing moving table (41) through the push cylinder mounting plate (34) and the moving table push rod (47). The pressing moving table (41) is slidably sleeved on the pressing fixed column (45). The lower end of the pressing fixed column (45) is fixed to the pressing base plate (43), and the pressing base plate (43) is fixed to the pressing equipment base (44). The pressing top plate (36) is fixed to the top of the pressing fixed column (45). The mold base (37) is fixed below the pressing top plate (36), and the upper mold (38) is fixed to the upper mold base (37) by the upper mold locking bolt (46); the lower mold plate (49) is fixed on the pressing moving stage (41), and the lower mold (40) is fixed on the lower mold plate (49) by the lower mold locking bolt (48); the sample pressing ring (50) is placed inside the lower mold (40); the movable push rod (39) is set inside the lower mold (40), and the fixed push rod (42) is fixed on the pressing bottom plate (43) and located below the movable push rod (39); the pressing electric push cylinder (33) drives the pressing moving stage (41) The pressing device drives the lower pressing mold (40) and the movable push rod (39) to move upward, cooperating with the fixed upper pressing mold (38) to complete the pressing; during the descent, the fixed push rod (42) holds the movable push rod (39), and the pressing moving stage (41) continues to drive the lower pressing mold (40) to move downward relative to the stationary movable push rod (39), pushing the sample out; the pressing device also includes a pressing touch screen (25), a pressing protective cover (26), a pressing safety light curtain (27), a pressing control box (28), a pressing adjustable foot (29), a pressing power switch (30), a pressing start button (31), and a pressing mechanism. Emergency stop button (32) and pressure sensor (35); the pressing control box (28) is electrically connected to the pressing electric push cylinder (33) and the pressing touch screen (25). The pressure sensor (35) is set on the push cylinder mounting plate (34) for detecting pressure. The pressing power switch (30), pressing start button (31) and pressing emergency stop button (32) are set on the pressing control box (28). The pressing protective cover (26) and pressing adjustable feet (29) are set on the pressing equipment base (44). The pressing safety light curtain (27) is installed at the pressing protective cover (26).

5. The method for preparing samples for relative sensitivity factor calibration in glow discharge mass spectrometry according to claim 1, characterized in that, The specific operation for cleaning the high-purity indium sheet in step 1 is as follows: Place the high-purity indium sheet in a polytetrafluoroethylene beaker, add 10% dilute nitric acid and ultrasonically clean for 3 minutes, clean with ultrapure water 5 times, ultrasonically clean with ultrapure water for 3 minutes, and then ultrasonically clean with anhydrous ethanol for 3 minutes. Take it out and blow it dry. Screen the high-purity indium sheet for impurity elements and detect whether the element content of As, Pb, Bi, Sn and Sb is less than 0.05 μg / g.

6. The method for preparing samples for relative sensitivity factor calibration in glow discharge mass spectrometry according to claim 1, characterized in that, The specific operation for cleaning and drying the high-temperature alloy shavings standard material in step 2 is as follows: the weighed high-temperature alloy shavings standard material is placed in a polytetrafluoroethylene beaker, sonicated with ultrapure water for 3 minutes, then sonicated with anhydrous ethanol for 3 minutes, and then placed in a vacuum furnace for vacuum drying for 2 hours.

7. The method for preparing samples for relative sensitivity factor calibration in glow discharge mass spectrometry according to claim 1, characterized in that, The mass ratio mentioned in step 3 is: the mass ratio of high-purity indium sheet to high-temperature alloy shavings standard material is 9:1, and the shavings standard material is divided into 3 equal parts; The vacuum degree of the vacuum condition described in Step 5 is <10 -3 Pa; The specific method of gradient pressurization in step 6 is as follows: the first piece of shavings of standard material is evenly spread on the softened high-purity indium sheet, pre-pressed at 10MPa-15MPa and held for 1 minute; the second piece of shavings of standard material is evenly spread, and the main pressure is 20MPa and held for 3 minutes; the third piece of shavings of standard material is evenly spread, and the pressure is 50MPa and held for 5 minutes.

8. The method for preparing samples for relative sensitivity factor calibration in glow discharge mass spectrometry according to claim 1, characterized in that, Step 7 specifically involves heating to 120℃, pressurizing to 100MPa, and holding the pressure for 10 minutes; Step 8 involves demolding to obtain sheet-like corrected samples with a diameter of 20mm and a thickness of 0.5mm-1.0mm.

9. A method for relative sensitivity factor calibration testing of a glow discharge mass spectrometer, characterized in that, The testing involves using a series of sheet-like calibration samples with concentration gradients prepared by any one of the preparation methods described in claims 1-8, including the following steps: Step A: Perform mass calibration and ion efficiency testing using a high-purity tantalum sample; Step B: Place the series of sheet-like calibration samples with concentration gradients into a glow discharge mass spectrometer and turn on glow discharge. After the pre-sputtering time is set, test the elements to be measured. Step C: Linear fit of test results to standard values to calculate the corrected relative sensitivity factor value, RSF, for each element cal The RSF cal values are applied to the quantitative analysis of the high temperature alloy sample under test.

10. The relative sensitivity factor calibration test method for glow discharge mass spectrometer according to claim 9, characterized in that, In step A, when the temperature of the glow discharge mass spectrometer reaction cell base cools to -160℃, a 5N high-purity tantalum sample is placed in the sample. The operating parameters of the glow discharge mass spectrometer are: discharge current 1.5mA, discharge voltage 1100V, argon flow rate 0.36L / min, extraction lens voltage 4305V, vertical source voltage V1 76.5V, and horizontal source voltage H1 -53.5V. In step B, before testing the analyte, the calibration sample is pre-sputtered for 15min. The testing method also includes: using other similar standard materials to test the RSF. cal Verify the accuracy.

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