Method for detecting alsi cu alloy by glow discharge mass spectrometer

Abstract

The present application relates to a kind of methods for detecting AlSiCu alloy by glow discharge mass spectrometer, the method comprises the following steps: S1, according to the volume ratio of nitric acid, hydrofluoric acid and water is 1:1:(4-6), mixed acid solution is prepared;S2, according to the volume ratio of water, nitric acid and mixed acid solution is 1:1:(0.5-2), first pickling solution is prepared;S3, according to the volume ratio of water, nitric acid and mixed acid solution is 1:1:(1-4), second pickling solution is prepared;S4, the sample to be measured AlSiCu alloy is immersed in first pickling solution and is carried out first ultrasonic cleaning, then first flushing is carried out, then immersed in second pickling solution and is carried out second ultrasonic cleaning, then second flushing is carried out, then baking is carried out, and pretreated sample is obtained;S5, the pretreated sample is detected by glow discharge mass spectrometer.The method provided by the present application can effectively reduce the introduction and residue of chlorine element on alloy surface, reduce total impurity content, so as to shorten sputtering time in GDMS detection process.

Description

Technical Field

[0001] This invention relates to the field of elemental analysis technology, specifically to a method for detecting AlSiCu alloys using a glow discharge mass spectrometer. Background Technology

[0002] Aluminum (Al) is an important metallic element. In its elemental form, it is a silvery-white, lightweight metal with malleability, and is commonly produced in rods, sheets, foils, powders, strips, and wires. In moist air, it forms an oxide film that prevents corrosion. Aluminum powder burns violently in air with a dazzling white flame and is readily soluble in dilute sulfuric acid, nitric acid, hydrochloric acid, sodium hydroxide, and potassium hydroxide solutions, but sparingly soluble in water. Aluminum is the third most abundant metallic element in the Earth's crust, after oxygen and silicon.

[0003] Elemental silicon (Si) exists in both crystalline and amorphous forms. Crystalline silicon is bluish-gray and has a relative density of 2.32-2.34 g / cm³. 3 Silicon has a melting point of 1414℃ and a boiling point of 2355℃. Amorphous silicon is a grayish-black powder, insoluble in water and hydrogen fluoride solution, but soluble in alkalis and a mixture of hydrogen fluoride and nitric acid. Crystalline silicon has significant electrical conductivity, lower than that of metals, and increases with increasing temperature. High-purity silicon doped with trace amounts of phosphorus can be used to prepare n-type semiconductors, and doped with trace amounts of boron can be used to prepare p-type semiconductors.

[0004] Copper (Cu) is a transition metal element. Pure copper is reddish-purple in color and has good ductility, thermal conductivity, and electrical conductivity. Therefore, it is widely used in cables and electrical and electronic components, building materials, and alloys.

[0005] As modern industry develops towards lightweight, high-performance, and high-reliability, single metal materials can no longer meet the requirements. Aluminum, silicon, and copper have significant complementary properties. Aluminum can provide lightweight and machinability, silicon can provide hardness and wear resistance, and copper can improve strength and conductivity. Therefore, AlSiCu alloys have broad application prospects due to the synergistic effect of each element.

[0006] The purity of AlSiCu alloys has a significant impact on the material's properties. Glow discharge mass spectrometry (GDMS) is a solid-state analysis technique with advantages such as high sensitivity, high resolution, minimal matrix effects, and full elemental analysis, making it the optimal method for detecting high-purity metallic solid samples. Typically, AlSiCu alloy samples need to be cleaned before GDMS analysis. However, existing cleaning processes suffer from excessively high chlorine (Cl) content after cleaning, requiring sputtering for more than 2 hours to complete the test, and even extending the sputtering time cannot reduce the Cl content.

[0007] Therefore, there is a need to provide a cleaning method for AlSiCu alloys to reduce Cl residue and shorten the sample testing time. Summary of the Invention

[0008] To address the above problems, the present invention aims to provide a method for detecting AlSiCu alloys using a glow discharge mass spectrometer.

[0009] To achieve this objective, the present invention adopts the following technical solution: This invention provides a method for detecting AlSiCu alloys using glow discharge mass spectrometry, the method comprising the following steps: S1. Prepare a mixed acid solution with a volume ratio of nitric acid, hydrofluoric acid and water of 1:1:(4-6); S2, prepare the first pickling solution according to the volume ratio of water, nitric acid and mixed acid solution of 1:1:(0.5-2); S3. Prepare the second pickling solution according to the volume ratio of water, nitric acid and mixed acid solution of 1:1:(1-4); S4. The AlSiCu alloy sample to be tested is immersed in the first pickling solution for the first ultrasonic cleaning, then rinsed first, then immersed in the second pickling solution for the second ultrasonic cleaning, then rinsed second, and then baked to obtain the pretreated sample. S5, the pretreated sample is detected by glow discharge mass spectrometry.

[0010] In this invention, by combining the first ultrasonic cleaning, the first rinsing, the second ultrasonic cleaning, the second rinsing, and the baking, and by controlling the composition of the first pickling solution and the second acid solution, the reaction rate on the surface of the AlSiCu alloy sample to be tested can be slowed down, the amount of hydrofluoric acid added can be reduced, the introduction and residue of chlorine on the alloy surface can be effectively reduced, the total impurity content can be reduced, thereby shortening the sputtering time in the GDMS detection process and reducing the detection limit of the elements.

[0011] In this invention, the volume ratio of nitric acid, hydrofluoric acid, and water is 1:1:(4-6), for example, it can be 1:1:4, 1:1:4.2, 1:1:4.4, 1:1:4.6, 1:1:4.8, 1:1:5, 1:1:5.2, 1:1:5.4, 1:1:5.6, 1:1:5.8, or 1:1:6, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0012] In this invention, the volume ratio of water, nitric acid, and mixed acid solution is 1:1:(0.5-2), for example, it can be 1:1:0.5, 1:1:0.6, 1:1:0.8, 1:1:1, 1:1:1.2, 1:1:1.4, 1:1:1.6, 1:1:1.8, or 1:1:2, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0013] In this invention, the volume ratio of water, nitric acid, and mixed acid solution is 1:1:(1-4), for example, it can be 1:1:1, 1:1:1.2, 1:1:1.4, 1:1:1.6, 1:1:1.8, 1:1:2, 1:1:2.2, 1:1:2.4, 1:1:2.6, 1:1:2.8, 1:1:3, 1:1:3.2, 1:1:3.4, 1:1:3.6, 1:1:3.8, or 1:1:4, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0014] Preferably, the mass concentration of the nitric acid is 12.5-16.7%, for example, it can be 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5% or 16.7%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0015] Preferably, the mass concentration of the hydrofluoric acid is 12.5-16.7%, for example, it can be 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5% or 16.7%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0016] In this invention, to avoid introducing pollution, all water used is deionized water, and the preparation process is carried out in a fume hood.

[0017] Preferably, the AlSiCu alloy sample to be tested is in block form.

[0018] Preferably, the length of the AlSiCu alloy sample to be tested is ≤20cm, for example, it can be 20cm, 15cm, 10cm, 5cm or 1cm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0019] Preferably, the width of the AlSiCu alloy sample to be tested is ≤20cm, for example, it can be 20cm, 15cm, 10cm, 5cm or 1cm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0020] Preferably, the thickness of the AlSiCu alloy sample to be tested is ≤10cm, for example, it can be 10cm, 5cm or 1cm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0021] In this invention, the AlSiCu alloy sample to be tested is pre-processed into a block shape, for example, a block sample of 20mm×20mm×10mm.

[0022] Preferably, the power of the first ultrasonic cleaning is 120-180W, for example, it can be 120W, 130W, 140W, 150W, 160W, 170W or 180W, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0023] Preferably, the first ultrasonic cleaning time is 2-3 minutes, for example, it can be 2 minutes, 2.2 minutes, 2.4 minutes, 2.6 minutes, 2.8 minutes or 3 minutes, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0024] In this invention, the AlSiCu alloy sample to be tested is placed in a polytetrafluoroethylene cup, a first pickling solution is added to cover the sample surface, and then placed in an ultrasonic cleaner for cleaning. By controlling the composition of the first pickling solution and the time of the first ultrasonic cleaning, the impurities remaining on the sample surface can be effectively removed, thereby reducing the subsequent sputtering time.

[0025] Preferably, the washing solution for the first rinse includes water.

[0026] Preferably, the first rinsing is performed 5-6 times.

[0027] Preferably, the power of the second ultrasonic cleaning is 120-180W, for example, it can be 120W, 130W, 140W, 150W, 160W, 170W or 180W, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0028] Preferably, the second ultrasonic cleaning time is 0.5-1 min, for example, it can be 0.5 min, 0.6 min, 0.7 min, 0.8 min, 0.9 min or 1 min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0029] In this invention, the AlSiCu alloy sample to be tested is placed in a polytetrafluoroethylene cup, a second pickling solution is added to cover the sample surface, and then placed in an ultrasonic cleaner for cleaning. By controlling the composition of the second pickling solution and the time of the second ultrasonic cleaning, the impurities remaining on the sample surface can be effectively removed, thereby reducing the subsequent sputtering time.

[0030] Preferably, the second rinsing includes a water rinse and an ethanol rinse performed sequentially.

[0031] Preferably, the number of water washes is 5-6.

[0032] Preferably, the ethanol washing is performed 1-2 times.

[0033] Preferably, the baking temperature is 80-100℃, for example, it can be 80℃, 82℃, 84℃, 86℃, 88℃, 90℃, 92℃, 94℃, 96℃, 98℃ or 100℃, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0034] Preferably, the baking time is 15-20 minutes, for example, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes or 20 minutes, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0035] Preferably, the glow discharge mass spectrometer detection includes sequentially performing vacuuming, cooling, pre-sputtering, and sputtering.

[0036] Preferably, the final vacuum level of the vacuuming process is 10. -7 Up to 10 -6 Pa, for example, could be 1×10 -7 Pa, 2×10 - 7 Pa, 4×10 -7 Pa, 6×10 -7 Pa, 8×10 -7 Pa or 1×10 -6 Pa, but not limited to the listed values, applies to other unlisted values ​​within the range as well.

[0037] Preferably, the refrigeration temperature is -180 to -175°C, for example, it can be -180°C, -178°C, -176°C or -175°C, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0038] Preferably, the cooling time is 10-30 min, for example, it can be 10 min, 12 min, 14 min, 16 min, 18 min, 20 min, 22 min, 24 min, 26 min, 28 min or 30 min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0039] Preferably, the pre-sputtering time is 10-20 min, for example, it can be 10 min, 12 min, 14 min, 16 min, 18 min or 20 min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0040] Preferably, the sputtering time is 30-60 minutes, for example, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes or 60 minutes, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0041] Compared with existing cleaning methods, the method provided by this invention can control the pre-sputtering and sputtering time to within 80 minutes, and the obtained test results show low impurity content, especially significantly reducing chlorine content. Existing cleaning methods require extending the sputtering time to reduce interference from impurity elements, and even if the sputtering time is extended to more than 2 hours, the chlorine content cannot be reduced.

[0042] Preferably, the voltage used for detection by the glow discharge mass spectrometer is 1-1.1kV, for example, it can be 1kV, 1.05kV or 1.1kV, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0043] Preferably, the current used for detection by the glow discharge mass spectrometer is 1-3mA, for example, it can be 1mA, 1.2mA, 1.4mA, 1.6mA, 1.8mA, 2mA, 2.2mA, 2.4mA, 2.6mA, 2.8mA or 3mA, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0044] Preferably, the resolution of the glow discharge mass spectrometer is 4000-5000, for example, it can be 4000, 4200, 4400, 4600, 4800 or 5000, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0045] As a preferred embodiment of the present invention, the method includes the following steps: S1. Prepare a mixed acid solution with a volume ratio of nitric acid, hydrofluoric acid and water of 1:1:(4-6); S2, prepare the first pickling solution according to the volume ratio of water, nitric acid and mixed acid solution of 1:1:(0.5-2); S3. Prepare the second pickling solution according to the volume ratio of water, nitric acid and mixed acid solution of 1:1:(1-4); S4. Immerse the AlSiCu alloy sample to be tested in the first pickling solution and perform the first ultrasonic cleaning at 120-180W for 2-3 minutes. Then rinse it with water 5-6 times. After that, immerse it in the second pickling solution and perform the second ultrasonic cleaning at 120-180W for 0.5-1 minutes. Then perform the second rinsing, i.e., first wash with water 5-6 times, then wash with ethanol 1-2 times. After that, bake it at 80-100℃ for 15-20 minutes to obtain the pretreated sample. S5. The pretreated sample is analyzed by glow discharge mass spectrometry, and the vacuum is first evacuated to a final vacuum level of 10. -7 Up to 10 -6 Pa, then cooled at -180 to -175℃ for 10-30 min, followed by pre-sputtering for 10-20 min, then sputtering for 30-60 min, and then detected by glow discharge mass spectrometry under the conditions of voltage 1-1.1 kV, current 1-3 mA, and resolution 4000-5000.

[0046] Compared with the prior art, the present invention has the following beneficial effects: (1) The method provided by the present invention can slow down the reaction rate on the surface of the AlSiCu alloy sample to be tested, reduce the amount of hydrofluoric acid added, effectively reduce the introduction and residue of chlorine on the alloy surface, and reduce the total impurity content.

[0047] (2) The method provided by the present invention can control the pre-sputtering and sputtering time to within 80 minutes, which shortens the detection time and improves the detection efficiency. Detailed Implementation

[0048] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0049] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0050] Example 1 This embodiment provides a method for detecting AlSiCu alloys using a glow discharge mass spectrometer, the method comprising the following steps: S1. A mixed acid solution is prepared according to the volume ratio of nitric acid, hydrofluoric acid, and water of 1:1:5; the mass concentration of nitric acid and hydrofluoric acid used in this embodiment is 12.5%; S2. Prepare the first pickling solution by mixing water, nitric acid and mixed acid solution in a volume ratio of 1:1:1. S3. Prepare the second pickling solution according to the volume ratio of water, nitric acid and mixed acid solution of 1:1:3. S4. The AlSiCu alloy sample to be tested with an initial purity of 5N (size 20mm×20mm×10mm) was immersed in the first pickling solution and subjected to the first ultrasonic cleaning at 150W for 2.5min. Then, it was rinsed with water 5 times. After that, it was immersed in the second pickling solution and subjected to the second ultrasonic cleaning at 150W for 0.8min. Then, it was rinsed with water 5 times and then with ethanol once. Finally, it was baked at 90℃ for 18min to obtain the pretreated sample. S5. The pretreated sample is analyzed by glow discharge mass spectrometry, and the vacuum is first evacuated to a final vacuum level of 10. - 7 Pa, then cooled at -170℃ for 20 min, followed by pre-sputtering for 15 min, then sputtering for 40 min, and then detected by glow discharge mass spectrometry under the conditions of voltage 1 kV, current 2 mA, and resolution 4500.

[0051] Example 2 This embodiment provides a method for detecting AlSiCu alloys using a glow discharge mass spectrometer, the method comprising the following steps: S1. A mixed acid solution is prepared according to the volume ratio of nitric acid, hydrofluoric acid, and water of 1:1:4. In this embodiment, the mass concentration of nitric acid and hydrofluoric acid is 16.7%. S2. Prepare the first pickling solution according to the volume ratio of water, nitric acid and mixed acid solution of 1:1:0.5. S3. Prepare the second pickling solution according to the volume ratio of water, nitric acid and mixed acid solution of 1:1:4. S4. The AlSiCu alloy sample to be tested with an initial purity of 5N (size 20mm×20mm×10mm) was immersed in the first pickling solution and subjected to the first ultrasonic cleaning at 180W for 2min. Then, it was rinsed with water 6 times. After that, it was immersed in the second pickling solution and subjected to the second ultrasonic cleaning at 180W for 1min. Then, it was rinsed with water 6 times and then with ethanol 2 times. Finally, it was baked at 80℃ for 20min to obtain the pretreated sample. S5. The pretreated sample is analyzed by glow discharge mass spectrometry, and the vacuum is first evacuated to a final vacuum level of 10. - 7 Pa, then cooled at -170℃ for 20 min, followed by pre-sputtering for 15 min, then sputtering for 40 min, and then detected by glow discharge mass spectrometry under the conditions of voltage 1 kV, current 2 mA, and resolution 4500.

[0052] Example 3 This embodiment provides a method for detecting AlSiCu alloys using a glow discharge mass spectrometer, the method comprising the following steps: S1. A mixed acid solution is prepared according to the volume ratio of nitric acid, hydrofluoric acid, and water of 1:1:6; the mass concentration of nitric acid and hydrofluoric acid used in this embodiment is 12.5%; S2. Prepare the first pickling solution according to the volume ratio of water, nitric acid and mixed acid solution of 1:1:2. S3. Prepare the second pickling solution according to the volume ratio of water, nitric acid and mixed acid solution of 1:1:1. S4. The AlSiCu alloy sample to be tested with an initial purity of 5N (size 20mm×20mm×10mm) was immersed in the first pickling solution and subjected to the first ultrasonic cleaning at 120W for 3min. Then, it was rinsed with water 5 times. After that, it was immersed in the second pickling solution and subjected to the second ultrasonic cleaning at 120W for 0.5min. Then, it was rinsed with water 5 times and then with ethanol once. Finally, it was baked at 100℃ for 15min to obtain the pretreated sample. S5. The pretreated sample is analyzed by glow discharge mass spectrometry, and the vacuum is first evacuated to a final vacuum level of 10. - 7 Pa, then cooled at -170℃ for 20 min, followed by pre-sputtering for 15 min, then sputtering for 40 min, and then detected by glow discharge mass spectrometry under the conditions of voltage 1 kV, current 2 mA, and resolution 4500.

[0053] Comparative Example 1 This comparative example provides a method for detecting AlSiCu alloys using a glow discharge mass spectrometer. The only difference from Example 1 is that the first pickling solution in step S2 is replaced with the mixed acid solution in step S1, and the second pickling solution in step S3 is replaced with the mixed acid solution in step S1.

[0054] Comparative Example 2 This comparative example provides a method for detecting AlSiCu alloys using a glow discharge mass spectrometer. The only difference from Example 1 is the adjustment of the amount of mixed acid solution added, so that the volume ratio of water, nitric acid and mixed acid solution in step S2 is 1:1:0.1.

[0055] Comparative Example 3 This comparative example provides a method for detecting AlSiCu alloys using a glow discharge mass spectrometer. The only difference from Example 1 is the adjustment of the amount of mixed acid solution added, so that the volume ratio of water, nitric acid and mixed acid solution in step S2 is 1:1:4.

[0056] Comparative Example 4 This comparative example provides a method for detecting AlSiCu alloys using a glow discharge mass spectrometer. The only difference from Example 1 is the adjustment of the amount of mixed acid solution added, so that the volume ratio of water, nitric acid and mixed acid solution in step S3 is 1:1:0.5.

[0057] Comparative Example 5 This comparative example provides a method for detecting AlSiCu alloys using a glow discharge mass spectrometer. The only difference from Example 1 is the adjustment of the amount of mixed acid solution added, so that the volume ratio of water, nitric acid and mixed acid solution in step S3 is 1:1:6.

[0058] Comparative Example 6 This comparative example provides a method for detecting AlSiCu alloys using a glow discharge mass spectrometer. The only difference from Example 1 is that the first ultrasonic cleaning is omitted, and the AlSiCu alloy sample to be tested is directly immersed in the second acid cleaning solution for the second ultrasonic cleaning.

[0059] Comparative Example 7 This comparative example provides a method for detecting AlSiCu alloys using glow discharge mass spectrometry. The only difference from Example 1 is that a second ultrasonic cleaning and a second rinsing are not performed; instead, the sample after the first rinsing is directly baked.

[0060] The results of glow discharge mass spectrometry analysis of the pretreated samples obtained in the above embodiments and comparative examples are shown in Table 1.

[0061] Table 1 As shown in Table 1, the method provided by this invention can effectively reduce the introduction and residue of chlorine on the alloy surface, reduce the total impurity content, and shorten the sputtering time in the GDMS detection process to within 80 minutes.

[0062] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for detecting AlSiCu alloys using glow discharge mass spectrometry, characterized in that, The method Includes the following steps: S1. Prepare a mixed acid solution with a volume ratio of nitric acid, hydrofluoric acid and water of 1:1:(4-6); S2, prepare the first pickling solution according to the volume ratio of water, nitric acid and mixed acid solution of 1:1:(0.5-2); S3. Prepare the second pickling solution according to the volume ratio of water, nitric acid and mixed acid solution of 1:1:(1-4); S4. The AlSiCu alloy sample to be tested is immersed in the first pickling solution for the first ultrasonic cleaning, then rinsed first, then immersed in the second pickling solution for the second ultrasonic cleaning, then rinsed second, and then baked to obtain the pretreated sample. S5, the pretreated sample is detected by glow discharge mass spectrometry.

2. The method according to claim 1, characterized in that, The mass concentration of the nitric acid is 12.5-16.7%; Preferably, the mass concentration of the hydrofluoric acid is 12.5-16.7%.

3. The method according to claim 1 or 2, characterized in that, The AlSiCu alloy sample to be tested was in block form; Preferably, the length of the AlSiCu alloy sample to be tested is ≤20cm; Preferably, the width of the AlSiCu alloy sample to be tested is ≤20cm; Preferably, the thickness of the AlSiCu alloy sample to be tested is ≤10cm.

4. The method according to any one of claims 1-3, characterized in that, The power of the first ultrasonic cleaning is 120-180W; Preferably, the first ultrasonic cleaning time is 2-3 minutes.

5. The method according to any one of claims 1-4, characterized in that, The washing solution for the first rinse includes water; Preferably, the first rinsing is performed 5-6 times.

6. The method according to any one of claims 1-5, characterized in that, The power of the second ultrasonic cleaning is 120-180W; Preferably, the second ultrasonic cleaning time is 0.5-1 min.

7. The method according to any one of claims 1-6, characterized in that, The second rinsing includes a water rinse and an ethanol rinse performed sequentially; Preferably, the water washing is performed 5-6 times; Preferably, the ethanol washing is performed 1-2 times.

8. The method according to any one of claims 1-7, characterized in that, The baking temperature is 80-100℃; Preferably, the baking time is 15-20 minutes.

9. The method according to any one of claims 1-8, characterized in that, The glow discharge mass spectrometer detection includes sequential vacuuming, cooling, pre-sputtering, and sputtering.

10. The method according to claim 9, characterized in that, The final vacuum level of the vacuuming process is 10. -7 Up to 10 -6 Pa; Preferably, the refrigeration temperature is -180 to -175°C; Preferably, the cooling time is 10-30 minutes; Preferably, the pre-sputtering time is 10-20 minutes; Preferably, the sputtering time is 30-60 minutes; Preferably, the voltage used for detection by the glow discharge mass spectrometer is 1-1.1 kV; Preferably, the current used in the glow discharge mass spectrometer during detection is 1-3 mA; Preferably, the resolution of the glow discharge mass spectrometer is 4000-5000.

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