Pretreatment method and detection method for detecting vanadium-zirconium-iron alloy sample by glow discharge mass spectrometry

Abstract

The invention provides a pretreatment method and a detection method for detecting a vanadium-zirconium-iron alloy sample by glow discharge mass spectrometry, and the pretreatment method comprises the following steps: sequentially carrying out first acid pickling, first water washing, second acid pickling, second water washing, alcohol washing and drying on a vanadium-zirconium-iron alloy to obtain the vanadium-zirconium-iron alloy sample; a first pickling solution of the first pickling is a mixed solution of first nitric acid, first hydrofluoric acid and water; a second pickling solution of the second pickling is a mixed solution of second nitric acid, second hydrofluoric acid and an organic solvent. By adopting a method of combining first pickling and second pickling of a specific pickling solution, an oxide film, impurities and pollutants on the surface of the vanadium-zirconium-iron alloy are quickly and thoroughly removed on the premise of ensuring that pollution is not introduced in the sample preparation process, so that the influence of the impurities on glow discharge mass spectrometry detection is avoided, and the detection accuracy is improved. And the problem of matrix element deficiency or impurity element dissolution caused by too long cleaning time is solved, so that the detection accuracy and the detection efficiency of the glow discharge mass spectrum are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of analysis and detection, and relates to a pretreatment method and a detection method for glow discharge mass spectrometry detection of vanadium-zirconium-iron alloy samples. Background Art

[0002] At present, the methods for analyzing trace impurity elements in metals include inductively coupled plasma optical emission spectroscopy (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), X-ray fluorescence spectroscopy (XRF), gas analyzer infrared detection (CEMS) and secondary ion mass spectrometry (SIMS), but these methods are cumbersome and difficult to master, have long processes and are prone to pollution.

[0003] Glow discharge mass spectrometry (GDMS) can directly analyze solid samples, and has the advantages of high sensitivity, high resolution, small matrix effect, and full element analysis. Metallic matrices are advantageous for GDMS analysis due to their good electrical conductivity, such as metal copper, iron, zinc, lead, aluminum, gallium, tantalum, cobalt, titanium, cadmium, antimony or germanium. Among the sample types analyzed by GDMS, bulk metals are the most ideal. Glow discharge mass spectrometry is currently one of the most effective methods for direct trace and ultra-trace impurity element analysis of conductive solid materials.

[0004] CN103884772A discloses a method for determining trace impurities in high-purity indium. The method comprises: (1) cutting a sample into sheets, first cleaning the oil stains on the surface of the sample with toluene, then cleaning with ultrapure water, corroding with 50% (volume concentration) nitric acid for 8 minutes, repeatedly rinsing with ultrapure water, storing in methanol, and drying under an infrared lamp before analysis; (2) placing the sample in a sample holder, pushing it into an ion source cavity, and when the vacuum degree reaches 2.2 to 2.4 mbar, adjusting the discharge voltage and discharge current to 0.9 to 1.2 kV and 40 to 45 mA respectively, sputtering for about 30 to 40 minutes, generally taking the signal stability of Na, Fe and Ca, which are easy to introduce contamination, as the standard, so as to eliminate the contamination that may be generated during the sample preparation process; (3) adjusting the discharge voltage to 0.9 to 1.2 kV and the discharge current to 40 to 45 mA, performing high-voltage discharge, collecting the ion signal of the element to be measured, and calculating the concentration of the impurity element to be measured according to the quantitative analysis principle of a glow discharge mass spectrometer.

[0005] Although the above determination method is simple and easy to operate, has little interference and a short process, it only uses a single nitric acid for cleaning. If the cleaning time is too long, there is a risk of dissolving impurities in the sample, causing deviations in the test results.

[0006] In summary, providing a pretreatment method and a detection method for vanadium-zirconium-iron alloy samples by glow discharge mass spectrometry can simply, quickly and accurately detect the impurity content without the problem of missing matrix elements or dissolution of impurity elements, is a problem that technical personnel in this field urgently need to solve. Summary of the invention

[0007] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a pretreatment method and a detection method for vanadium-zirconium-iron alloy samples by glow discharge mass spectrometry, so as to ensure that the oxide film, impurities and pollutants on the surface of the vanadium-zirconium-iron alloy are quickly and thoroughly removed without introducing contamination during the sample preparation process, thereby avoiding the influence of impurities on glow discharge mass spectrometry detection.

[0008] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a pretreatment method for glow discharge mass spectrometry detection of vanadium-zirconium-iron alloy samples, the pretreatment method comprising:

[0010] The vanadium-zirconium-iron alloy is sequentially subjected to a first acid wash, a first water wash, a second acid wash, a second water wash, an alcohol wash and drying to obtain a vanadium-zirconium-iron alloy sample;

[0011] The first pickling solution of the first pickling is a mixed solution of first nitric acid, first hydrofluoric acid and water;

[0012] The second pickling solution of the second pickling is a mixed solution of second nitric acid, second hydrofluoric acid and an organic solvent.

[0013] In the present invention, in order to avoid introducing contamination, the pretreatment process of the vanadium-zirconium-iron alloy should be carried out in a fume hood. The water is deionized water or pure water, and the purity of other reagents used is above the top grade. In both the first pickling and the second pickling, the vanadium-zirconium-iron alloy to be tested is placed in a cleaned polytetrafluoroethylene container.

[0014] The pretreatment method provided by the present invention adopts a method combining a first pickling and a second pickling with a specific pickling solution to ensure that the oxide film, impurities and pollutants on the surface of the vanadium-zirconium-iron alloy are quickly and thoroughly removed without introducing pollution during the sample preparation process, thereby avoiding the influence of impurities on the glow discharge mass spectrometry detection, and there will be no problem of missing matrix elements or dissolution of impurity elements due to too long cleaning time, thereby improving the detection accuracy and detection efficiency of the glow discharge mass spectrometry.

[0015] As a preferred technical solution of the present invention, before the first pickling, the following steps are further performed: machining the vanadium-zirconium-iron alloy to obtain a sample size required for glow discharge mass spectrometry detection.

[0016] In the present invention, the size of the vanadium-zirconium-iron alloy sample obtained after machining is 20 mm×20 mm×10 mm (length×width×height).

[0017] As a preferred technical solution of the present invention, the volume ratio of the first nitric acid, the first hydrofluoric acid and water is 1:1:(3-5), for example, it can be 1:1:3.2, 1:1:3.5, 1:1:3.8, 1:1:4, 1:1:4.2, 1:1:4.5, 1:1:4.6 or 1:1:4.8, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0018] In the present invention, if the first pickling is repeated only several times, the required pickling time is too long, and there is a risk of dissolving impurities in the vanadium-zirconium-iron alloy sample, which affects the accuracy of the glow discharge mass spectrometry detection result.

[0019] Preferably, the mass concentration of the first nitric acid is 60%-68%, for example, it can be 60.5%, 61%, 61.5%, 62%, 62.5%, 63%, 63.5%, 64%, 65%, 66% or 67%, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0020] Preferably, the mass concentration of the first hydrofluoric acid is 38%-42%, for example, it can be 38.5%, 39%, 39.5%, 40%, 40.5%, 41% or 41.5%, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0021] As a preferred technical solution of the present invention, the time for the first pickling is 40-70s, for example, it can be 42s, 45s, 46s, 48s, 50s, 52s, 55s, 56s, 58s, 60s, 62s, 65s, 66s or 68s, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0022] Preferably, the first pickling method is ultrasonic cleaning.

[0023] Preferably, the frequency of the ultrasonic cleaning is 10-40 kHz, for example, 15 kHz, 20 kHz, 25 kHz, 30 kHz, 35 kHz or 38 kHz, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0024] As a preferred technical solution of the present invention, the organic solvent includes methanol and / or ethanol.

[0025] Preferably, the volume ratio of the second nitric acid, the second hydrofluoric acid and the organic solvent is 1:1:(6-8), for example, it can be 1:1:6.2, 1:1:6.5, 1:1:6.8, 1:1:7, 1:1:7.2, 1:1:7.5, 1:1:7.6 or 1:1:7.8, but is not limited to the listed values, and other unlisted values ​​within the numerical range are equally applicable.

[0026] Preferably, the mass concentration of the second nitric acid is 36%-42%, for example, it can be 36.5%, 37%, 37.5%, 38%, 38.5%, 39%, 39.5%, 40% or 41%, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0027] Preferably, the mass concentration of the second hydrofluoric acid is 5%-10%, for example, it can be 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9% or 9.5%, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0028] In the present invention, by controlling the concentrations of the second nitric acid and the second hydrofluoric acid and the volume ratio range of the second nitric acid, the second hydrofluoric acid and the organic solvent, the cleaning speed can be accelerated, and the pickling process can be easily controlled to avoid over-pickling, avoid the dissolution of the base metal to the greatest extent, and improve the surface quality of the sample, thereby improving the cleaning effect.

[0029] In the present invention, the pickling solution used in the first pickling process and the second pickling process only needs to ensure that the surface of the vanadium-zirconium-iron alloy sample to be tested can be covered during the washing process, and the amount of the pickling solution used in the present invention is not specifically limited.

[0030] As a preferred technical solution of the present invention, the time for the second pickling is 20-50s, for example, it can be 25s, 30s, 35s, 40s, 45s or 48s, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0031] Preferably, the second pickling method is ultrasonic cleaning.

[0032] Preferably, the frequency of the ultrasonic cleaning is 10-40 kHz, for example, 15 kHz, 20 kHz, 25 kHz, 30 kHz, 35 kHz or 38 kHz, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0033] As a preferred technical solution of the present invention, the first water washing and the second water washing are both performed by flushing.

[0034] Preferably, the number of times of the first water washing and the second water washing are both ≥ 3 times, for example, 3 times, 4 times, 5 times or 6 times.

[0035] Preferably, the alcohol washing liquid of the alcohol washing comprises ethanol.

[0036] Preferably, the alcohol washing is performed by flushing.

[0037] Preferably, the drying is performed using a baking lamp.

[0038] In a second aspect, the present invention provides a glow discharge mass spectrometry detection method for a vanadium-zirconium-iron alloy sample, the detection method comprising:

[0039] The vanadium-zirconium-iron alloy sample obtained by the pretreatment method described in the first aspect is fixed by a sample fixture, then loaded into the sample chamber of a glow discharge mass spectrometer, evacuated and pushed into the discharge chamber, and then cooled and pre-sputtered before detection.

[0040] As a preferred technical solution of the present invention, the vacuum is evacuated to a vacuum degree of ≤5×10 -7 mbar.

[0041] Preferably, the cooling time is ≥10 min, for example, it can be 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min or 19 min, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0042] Preferably, the pre-sputtering time is 10-20 min, for example, it can be 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min or 19 min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0043] As a preferred technical solution of the present invention, the discharge voltage of the discharge chamber during the detection is 1000-1200V, for example, it can be 1020V, 1050V, 1060V, 1080V, 1100V, 1120V, 1150V, 1160V or 1180V, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0044] Preferably, the discharge current of the discharge chamber during the detection is 1.8-2.2 mA, for example, it can be 1.85 mA, 1.9 mA, 1.95 mA, 2 mA, 2.05 mA, 2.1 mA or 2.15 mA, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0045] Preferably, the resolution of the glow discharge mass spectrometer during the detection is 4000-5000, for example, it can be 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800 or 4900, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0046] In the present invention, when conducting glow discharge mass spectrometry testing of vanadium-zirconium-iron alloy samples, by adjusting the test parameters of discharge voltage, discharge current and resolution, a stronger test signal can be obtained with high sensitivity, and the test accuracy of elements can reach ppb level.

[0047] The numerical range described in the present invention not only includes the point values ​​listed above, but also includes any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0048] Compared with the prior art, the present invention has the following beneficial effects:

[0049] (1) The pretreatment method provided by the present invention adopts a method combining the first pickling and the second pickling with a specific pickling solution to ensure that the oxide film, impurities and pollutants on the surface of the vanadium-zirconium-iron alloy are quickly and thoroughly removed without introducing pollution during the sample preparation process, thereby avoiding the influence of impurities on the glow discharge mass spectrometry detection, and there will be no problem of missing matrix elements or dissolution of impurity elements due to too long cleaning time, thereby improving the detection accuracy and detection efficiency of the glow discharge mass spectrometry;

[0050] (2) The detection method provided by the present invention realizes the detection of impurity content in vanadium-zirconium-iron alloy samples by controlling the test parameters of discharge voltage, discharge current and resolution during detection, and has high sensitivity, low detection limit and high stability of detection results. DETAILED DESCRIPTION

[0051] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0052] In the following examples and comparative examples, water is all deionized water, and the purity of other reagents used is above the top grade; the first pickling and the second pickling are both performed by placing the vanadium-zirconium-iron alloy to be tested into a cleaned polytetrafluoroethylene container; the drying is performed by using a baking lamp. The vanadium-zirconium-iron alloys in Examples 1-3 are not the same piece, and the vanadium-zirconium-iron alloys in Example 1, Examples 4-9, and Comparative Examples 1-4 are the same piece.

[0053] Example 1

[0054] This embodiment provides a pretreatment method for glow discharge mass spectrometry detection of vanadium-zirconium-iron alloy samples, the pretreatment method comprising:

[0055] The vanadium-zirconium-iron alloy is machined to a sample with a size of 20 mm×20 mm×10 mm, and then the vanadium-zirconium-iron alloy is sequentially subjected to a first pickling for 60 s, a first water washing for 3 times, a second pickling for 40 s, a second water washing for 3 times, an ethanol rinse, and drying;

[0056] Wherein, the first pickling solution of the first pickling is a mixed solution of first nitric acid, first hydrofluoric acid and water in a volume ratio of 1:1:4; the mass concentration of the first nitric acid is 65%; the mass concentration of the first hydrofluoric acid is 40%;

[0057] The second pickling solution of the second pickling is a mixed solution of second nitric acid, second hydrofluoric acid and methanol in a volume ratio of 1:1:7; the mass concentration of the second nitric acid is 40%; the mass concentration of the second hydrofluoric acid is 8%;

[0058] The first pickling and the second pickling are both carried out by ultrasonic cleaning; the frequency of the ultrasonic cleaning is 20 kHz.

[0059] Example 2

[0060] This embodiment provides a pretreatment method for glow discharge mass spectrometry detection of vanadium-zirconium-iron alloy samples, the pretreatment method comprising:

[0061] The vanadium-zirconium-iron alloy was machined to a sample with a size of 20 mm×20 mm×10 mm, and then the vanadium-zirconium-iron alloy was sequentially subjected to a first acid wash for 70 s, a first water wash for 3 times, a second acid wash for 50 s, a second water wash for 3 times, an ethanol rinse, and drying;

[0062] Wherein, the first pickling solution of the first pickling is a mixed solution of first nitric acid, first hydrofluoric acid and water in a volume ratio of 1:1:5; the mass concentration of the first nitric acid is 68%; the mass concentration of the first hydrofluoric acid is 38%;

[0063] The second pickling solution of the second pickling is a mixed solution of second nitric acid, second hydrofluoric acid and methanol in a volume ratio of 1:1:8; the mass concentration of the second nitric acid is 36%; the mass concentration of the second hydrofluoric acid is 10%;

[0064] The first pickling and the second pickling are both carried out by ultrasonic cleaning; the frequency of the ultrasonic cleaning is 20 kHz.

[0065] Example 3

[0066] This embodiment provides a pretreatment method for glow discharge mass spectrometry detection of vanadium-zirconium-iron alloy samples, the pretreatment method comprising:

[0067] The vanadium-zirconium-iron alloy is machined to a sample with a size of 20 mm×20 mm×10 mm, and then the vanadium-zirconium-iron alloy is sequentially subjected to a first pickling for 40 seconds, a first water washing for 3 times, a second pickling for 25 seconds, a second water washing for 3 times, an ethanol rinse, and drying;

[0068] Wherein, the first pickling solution of the first pickling is a mixed solution of first nitric acid, first hydrofluoric acid and water in a volume ratio of 1:1:3; the mass concentration of the first nitric acid is 60%; the mass concentration of the first hydrofluoric acid is 42%;

[0069] The second pickling solution of the second pickling is a mixed solution of second nitric acid, second hydrofluoric acid and methanol in a volume ratio of 1:1:6; the mass concentration of the second nitric acid is 42%; the mass concentration of the second hydrofluoric acid is 5%;

[0070] The first pickling and the second pickling are both carried out by ultrasonic cleaning; the frequency of the ultrasonic cleaning is 40 kHz.

[0071] Example 4

[0072] This embodiment provides a pretreatment method for glow discharge mass spectrometry detection of vanadium-zirconium-iron alloy samples. Except that the second pickling solution is a mixed solution of second nitric acid, second hydrofluoric acid and methanol in a volume ratio of 1:1:4, other conditions are the same as those in Example 1.

[0073] Example 5

[0074] This embodiment provides a pretreatment method for glow discharge mass spectrometry detection of vanadium-zirconium-iron alloy samples. Except that the second pickling solution is a mixed solution of second nitric acid, second hydrofluoric acid and methanol in a volume ratio of 1:1:10, other conditions are the same as those in Example 1.

[0075] Example 6

[0076] This embodiment provides a pretreatment method for detecting vanadium-zirconium-iron alloy samples by glow discharge mass spectrometry. Except that the mass concentration of the second nitric acid is 65%, other conditions are the same as those in Embodiment 1.

[0077] Example 7

[0078] This embodiment provides a pretreatment method for detecting vanadium-zirconium-iron alloy samples by glow discharge mass spectrometry. Except that the mass concentration of the second hydrofluoric acid is 40%, other conditions are the same as those in Embodiment 1.

[0079] Example 8

[0080] This embodiment provides a pretreatment method for detecting vanadium-zirconium-iron alloy samples by glow discharge mass spectrometry. Except that the second pickling time is 10 seconds, other conditions are the same as those in Embodiment 1.

[0081] Example 9

[0082] This embodiment provides a pretreatment method for detecting vanadium-zirconium-iron alloy samples by glow discharge mass spectrometry. Except that the second pickling time is 70 seconds, other conditions are the same as those in Embodiment 1.

[0083] Comparative Example 1

[0084] This comparative example provides a pretreatment method for glow discharge mass spectrometry detection of vanadium-zirconium-iron alloy samples. Except that the second acid wash is not performed and the first acid wash is repeated twice, other conditions are the same as those in Example 1.

[0085] Comparative Example 2

[0086] This comparative example provides a pretreatment method for glow discharge mass spectrometry detection of vanadium-zirconium-iron alloy samples. Except that the first acid wash is not performed and the second acid wash is repeated twice, other conditions are the same as those in Example 1.

[0087] Comparative Example 3

[0088] This comparative example provides a pretreatment method for glow discharge mass spectrometry detection of vanadium-zirconium-iron alloy samples, except that the second pickling solution does not include the second hydrofluoric acid and the content of the second nitric acid is increased accordingly, other conditions are the same as those in Example 1.

[0089] Comparative Example 4

[0090] This comparative example provides a pretreatment method for glow discharge mass spectrometry detection of vanadium-zirconium-iron alloy samples, except that the second pickling solution does not include the second nitric acid and the content of the second hydrofluoric acid is increased accordingly, other conditions are the same as those in Example 1.

[0091] Application Example 1

[0092] This application example provides a glow discharge mass spectrometry detection method for a vanadium-zirconium-iron alloy sample, the detection method comprising:

[0093] The vanadium-zirconium-iron alloy sample obtained in Example 1 was fixed by a sample fixture and then placed in the sample chamber of a glow discharge mass spectrometer and evacuated to a vacuum degree of 4×10 -7 mbar and then pushed into the discharge chamber, followed by cooling for 10 min and pre-sputtering for 15 min before testing;

[0094] Among them, during detection, the resolution of the glow discharge mass spectrometer is 4000-5000, the discharge voltage of the discharge chamber is 1100V, and the discharge current is 2mA.

[0095] Application Example 2-9

[0096] The above application example provides a glow discharge mass spectrometry detection method for a vanadium-zirconium-iron alloy sample, which is the same as application example 1 except that the vanadium-zirconium-iron alloy sample is replaced by the vanadium-zirconium-iron alloy sample prepared in Example 2-9.

[0097] Application Example 10

[0098] The above application example provides a glow discharge mass spectrometry detection method for a vanadium-zirconium-iron alloy sample. Except that the discharge current of the discharge chamber during the detection is 1.5 mA, other conditions are the same as those in Application Example 1.

[0099] Application Example 11

[0100] The above application example provides a glow discharge mass spectrometry detection method for a vanadium-zirconium-iron alloy sample. Except that the discharge current of the discharge chamber during the detection is 2.5 mA, other conditions are the same as those in Application Example 1.

[0101] Comparative Application Examples 1-4

[0102] The above comparative application example provides a glow discharge mass spectrometry detection method for a vanadium-zirconium-iron alloy sample, which is the same as application example 1 except that the vanadium-zirconium-iron alloy sample is replaced by the vanadium-zirconium-iron alloy sample prepared in comparative examples 1-4.

[0103] The average content of impurities and the maximum relative error results of the five repeated tests in the above application examples and comparative application examples are shown in Table 1.

[0104] Table 1

[0105]

[0106] From Table 1, we can see that:

[0107] (1) The pretreatment method provided in Application Examples 1-3 of the present invention ensures that the oxide film, impurities and pollutants on the surface of the vanadium-zirconium-iron alloy are quickly and thoroughly removed without introducing contamination during the sample preparation process, and the problem of missing matrix elements or dissolution of impurity elements due to too long cleaning time will not occur. The detection method provided can realize the analysis of the impurity content in the vanadium-zirconium-iron alloy sample, with a low detection limit and stable results;

[0108] (2) By comparing Application Example 1 with Application Examples 4-7, it can be seen that when the amount of organic solvent in the second pickling solution is too small or the acid concentration is too high, the vanadium zirconium iron alloy sample reacts with the pickling solution too quickly due to the high acid concentration, causing the surface of the vanadium zirconium iron alloy sample to become rough and easily adsorb impurities, affecting the glow discharge mass spectrometry detection results; when the amount of organic solvent in the second pickling solution is too large, the oxide film and impurities on the surface of the vanadium zirconium iron alloy cannot be removed well, resulting in a decrease in the accuracy of the glow discharge mass spectrometry detection results;

[0109] (3) By comparing Application Example 1 with Application Examples 8-9, it can be seen that when the second pickling time is too short or too long, it is not conducive to controlling the pickling effect of the sample, thereby causing the accuracy of the glow discharge mass spectrometry detection result to decrease;

[0110] (4) By comparing Application Example 1 with Application Examples 10-11, it can be seen that when the discharge current is too low during the detection process, the sputtering speed of the sample is too slow, resulting in a long time for the result to stabilize, which prolongs the detection time and affects the accuracy of the glow discharge mass spectrometry detection; when the discharge current is too high during the detection process, the sputtering speed of the sample is too fast, the sample surface heats up, resulting in unstable detection results, affecting the glow discharge mass spectrometry detection;

[0111] (5) From the comparison between Application Example 1 and Comparative Application Examples 1-2, it can be seen that when only the first pickling or the second pickling is repeated, the oxide film and impurities on the surface of the vanadium-zirconium-iron alloy cannot be completely removed, which prolongs the analysis time and results in low accuracy of the glow discharge mass spectrometry detection results;

[0112] (6) From the comparison between Application Example 1 and Comparative Application Examples 3-4, it can be seen that when the second pickling solution contains only a single type of acid, it cannot effectively remove impurities on the surface of the vanadium-zirconium-iron alloy, prolonging the analysis time and resulting in low accuracy of the glow discharge mass spectrometry detection results.

[0113] The applicant declares that the above is only a specific implementation mode 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 thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for pre-treatment of vanadium-zirconium-iron alloy samples by glow discharge mass spectrometry, characterized in that: The pre-treatment method comprises: The vanadium-zirconium-iron alloy is sequentially subjected to a first acid wash, a first water wash, a second acid wash, a second water wash, an alcohol wash and drying to obtain a vanadium-zirconium-iron alloy sample; The first pickling solution of the first pickling is a mixed solution of first nitric acid, first hydrofluoric acid and water; The second pickling solution of the second pickling is a mixed solution of second nitric acid, second hydrofluoric acid and an organic solvent.

2. The pre-treatment method according to claim 1, characterized in that: Before the first pickling, the following steps are also performed: machining the vanadium-zirconium-iron alloy to obtain a sample size required for glow discharge mass spectrometry detection.

3. The pre-treatment method according to claim 1 or 2, characterized in that: The volume ratio of the first nitric acid, the first hydrofluoric acid and water is 1:1:(3-5); Preferably, the mass concentration of the first nitric acid is 60%-68%; Preferably, the mass concentration of the first hydrofluoric acid is 38%-42%.

4. The pre-treatment method according to any one of claims 1 to 3, characterized in that: The first pickling time is 40-70s; Preferably, the first pickling method is ultrasonic cleaning; Preferably, the frequency of the ultrasonic cleaning is 10-40 kHz.

5. The pre-treatment method according to any one of claims 1 to 4, characterized in that: The organic solvent includes methanol and / or ethanol; Preferably, the volume ratio of the second nitric acid, the second hydrofluoric acid and the organic solvent is 1:1:(6-8); Preferably, the mass concentration of the second nitric acid is 36%-42%; Preferably, the mass concentration of the second hydrofluoric acid is 5%-10%.

6. The pre-treatment method according to any one of claims 1 to 5, characterized in that: The second pickling time is 20-50s; Preferably, the second pickling method is ultrasonic cleaning; Preferably, the frequency of the ultrasonic cleaning is 10-40 kHz.

7. The pre-treatment method according to any one of claims 1 to 6, characterized in that: The first water washing and the second water washing are both rinsed; Preferably, the first water washing and the second water washing are performed ≥ 3 times; Preferably, the alcohol washing liquid of the alcohol washing comprises ethanol; Preferably, the alcohol washing method is flushing; Preferably, the drying is performed using a baking lamp.

8. A glow discharge mass spectrometry detection method for vanadium-zirconium-iron alloy samples, characterized in that: The detection method comprises: The vanadium-zirconium-iron alloy sample obtained by the pretreatment method according to any one of claims 1 to 7 is fixed by a sample fixture, then loaded into the sample chamber of a glow discharge mass spectrometer, pushed into the discharge chamber after evacuation, and tested after cooling and pre-sputtering.

9. The detection method according to claim 8, characterized in that: The vacuum is evacuated to a vacuum degree of ≤5×10 -7 mbar; Preferably, the cooling time is ≥10 min; Preferably, the pre-sputtering time is 10-20 min.

10. The detection method according to claim 8 or 9, characterized in that: During the detection, the discharge voltage of the discharge chamber is 1000-1200V; Preferably, the discharge current of the discharge chamber during the detection is 1.8-2.2 mA; Preferably, the resolution of the glow discharge mass spectrometer during the detection is 4000-5000.

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