Sample preparation method for glow discharge mass spectrometry detection

Abstract

The invention relates to a sample preparation method for glow discharge mass spectrometry detection, which comprises the following steps: (1) carrying out machining drilling, hot extrusion, impurity removal treatment and vacuum heat treatment on a tantalum cast ingot to obtain a hollow columnar tantalum tube with the outer diameter of 3.4-3.6 mm, the inner diameter of 3-3.1 mm and the length of 12-17mm; (2) pickling, rinsing, cleaning and drying the hollow columnar tantalum tube obtained in the step (1) to obtain a pretreated tantalum tube; and (3) sleeving a sample with the pretreated tantalum tube obtained in the step (2) to obtain a sample to be detected. By controlling the technological parameters and the length of the pretreated tantalum tube in the machining process, cathode and anode short circuit caused by scraps generated by sample sputtering can be effectively prevented, the cleaning and maintenance frequency of the glow discharge chamber is reduced, and the service time of equipment is prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of solid analysis, and in particular to a sample preparation method for glow discharge mass spectrometry detection. Background Art

[0002] Glow discharge mass spectrometry (GDMS) is a direct solid analysis technology with the advantages of high sensitivity, high resolution, small matrix effect and full element analysis. It is currently the best means of analyzing high-purity metal solid samples. Glow discharge mass spectrometry consists of two parts: a glow discharge ion source and a mass spectrometer. The glow discharge ion source uses ions generated by the ionization of an inert gas under high pressure to impact the sample surface to cause sputtering. The sample atoms generated by sputtering diffuse into the plasma for further ionization, and are then collected and detected by the mass spectrometer.

[0003] The glow discharge sample forms currently used mainly include powder, block and rod. In order to better use GDMS to analyze samples of various forms, researchers have conducted in-depth research. CN 113358442A discloses a method for preparing and testing ammonium paratungstate powder for glow discharge mass spectrometry. A groove is opened on the surface of a high-purity indium sheet and cleaned, and the ammonium paratungstate powder is transferred to the groove using a medicine spoon. After compacting using a press, the sample to be tested is obtained. The test signal obtained by the sample preparation method is strong and highly sensitive, but the preparation of the powder sample is still prone to introduce impurities, thereby reducing the accuracy of the detection.

[0004] CN 111964997A discloses a method for preparing a sample of high-purity silver for detection by glow discharge mass spectrometry, wherein the length of the high-purity silver sample is 6-8 mm and the width is 3-5 mm; the method comprises: sequentially acid washing, first rinsing, second rinsing, drying and sample pressing the high-purity silver sample to obtain the silver sample to be detected. The invention realizes glow discharge mass spectrometry detection of fine silver samples and avoids the introduction of impurities, but the debris sputtered from the sample easily enters the gap between the sample and the glow discharge chamber for insulation, causing a short circuit between the cathode and cathode of the sample and the glow discharge chamber, thereby increasing the number of cleaning and maintenance of the glow discharge chamber.

[0005] CN 108212912A discloses a method for cleaning a ceramic sheet for a glow discharge mass spectrometer, comprising: providing a ceramic sheet for a glow discharge mass spectrometer; performing a first cleaning process on the ceramic sheet; performing a second cleaning process on the ceramic sheet after the first cleaning process, wherein the second cleaning process comprises an ultrasonic cleaning process; and performing a drying process on the ceramic sheet at a preset temperature after the second cleaning process. The invention cleans the insulating components in the glow discharge chamber to reduce the occurrence of anode-cathode short circuits, but still requires frequent cleaning, which consumes time and maintenance costs.

[0006] In view of the shortcomings of the existing technology, it is urgently necessary to provide a sample preparation method that can reduce the maintenance times of the glow discharge chamber and extend the service life of the equipment. Summary of the invention

[0007] The object of the present invention is to provide a sample preparation method for glow discharge mass spectrometry detection, by sheathing a tantalum tube with high purity and good mechanical properties on the sample and controlling a reasonable sheathing length, effectively preventing anode and cathode short circuits caused by debris generated by sample sputtering, reducing the number of cleaning and maintenance times of the glow discharge chamber and extending the service life of the equipment.

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

[0009] The present invention provides a sample preparation method for glow discharge mass spectrometry detection, the sample preparation method comprising the following steps:

[0010] (1) The tantalum ingot is machined, drilled, hot extruded, impurity-removed and vacuum heat treated to obtain a hollow cylindrical tantalum tube with an outer diameter of 3.4-3.6 mm, an inner diameter of 3-3.1 mm and a length of 12-17 mm;

[0011] (2) The hollow cylindrical tantalum tube obtained in step (1) is pickled, rinsed, cleaned and dried to obtain a pretreated tantalum tube;

[0012] (3) The pretreated tantalum tube obtained in step (2) is placed on the sample to obtain a sample to be tested.

[0013] The sample preparation method provided by the present invention can obtain a pretreated tantalum tube with high purity and good mechanical properties by controlling the process parameters in the processing process, especially adding the steps of impurity removal treatment and vacuum heat treatment, and combining the surface treatment steps of pickling, rinsing and cleaning; by strictly controlling the length of the pretreated tantalum tube, when the pretreated tantalum tube is sleeved on the sample, on the one hand, it does not affect the sputtering effect of the sample, and on the other hand, the tantalum tube is not easy to produce large pieces of debris after being sputtered. At the same time, sleeved on the sample can effectively prevent the cathode short circuit caused by the debris generated by the sputtering of the sample, thereby reducing the cleaning and maintenance times of the glow discharge chamber and extending the service life of the equipment.

[0014] The outer diameter of the hollow cylindrical tantalum tube is 3.4-3.6 mm, for example, 3.4 mm, 3.45 mm, 3.5 mm, 3.55 mm or 3.6 mm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0015] The inner diameter of the hollow cylindrical tantalum tube is 3-3.1 mm, for example, 3 mm, 3.02 mm, 3.05 mm, 3.08 mm or 3.1 mm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0016] The length of the hollow cylindrical tantalum tube is 12-17 mm, for example, 12 mm, 13 mm, 14 mm, 15 mm or 17 mm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0017] Preferably, the machining and drilling in step (1) is performed under the protection of an inert gas, and the inert gas includes argon.

[0018] The machining and drilling is performed under the protection of an inert gas, which can effectively prevent the tantalum ingot from being oxidized by contacting air during the machining process, thereby improving the surface quality of the tantalum ingot.

[0019] Preferably, the temperature of the hot extrusion in step (1) is 450-500°C, for example, 450°C, 465°C, 480°C, 490°C or 500°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0020] The hot extrusion step can deform the tantalum ingot, thereby obtaining a hollow cylindrical tantalum tube with fine and uniform grains.

[0021] Preferably, the solution used for the impurity removal treatment in step (1) comprises hydrochloric acid and nitric acid in a volume ratio of (2.5-3.5):1, for example, it can be 2.5:1, 2.8:1, 3:1, 3.2:1 or 3.5:1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0022] Preferably, the concentration of the hydrochloric acid is 36-38wt%, for example, 36wt%, 36.5wt%, 37wt%, 37.5wt% or 38wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0023] Preferably, the concentration of the nitric acid is 68-70wt%, for example, 68wt%, 68.5wt%, 69wt%, 69.5wt% or 70wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0024] The impurity removal treatment can remove impurities generated by the previous machining and hot extrusion processes, which is beneficial to the subsequent vacuum heat treatment step; the solution used for the impurity removal treatment is a mixture of concentrated hydrochloric acid and concentrated nitric acid, and a reasonable ratio is set, which can effectively remove impurities, thereby improving the detection accuracy and data validity of the glow discharge mass spectrometer.

[0025] Preferably, the temperature of the vacuum heat treatment in step (1) is 1000-1200°C, for example, it can be 1000°C, 1050°C, 1100°C, 1150°C or 1200°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0026] Preferably, the time of the vacuum heat treatment in step (1) is 100-150 min, for example, 100 min, 115 min, 130 min, 140 min or 150 min, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0027] The vacuum heat treatment step can improve the purity and internal structure performance of the tantalum tube, reduce surface contamination, and eliminate residual stress in the material processing process, thereby improving the mechanical properties of the tantalum tube and preventing large pieces of debris from falling during sputtering.

[0028] Preferably, the length of the hollow cylindrical tantalum tube in step (1) is 14.5-15.5 mm, for example, 14.5 mm, 14.8 mm, 15 mm, 15.2 mm or 15.5 mm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0029] The length of the hollow cylindrical tantalum tube is controlled within a reasonable range, which can obtain a good sample sputtering effect and prevent the debris generated by the sputtering of the sample from entering the gaps in the insulating material to cause a short circuit. If the length is too long, the sputtering process of the sample will be hindered. If the length is too short, the debris generated by the sputtering of the sample will still enter the gaps, thereby causing a short circuit and increasing the number of cleaning and maintenance times for the glow discharge chamber.

[0030] Preferably, the pickling solution used in step (2) comprises hydrochloric acid and nitric acid in a volume ratio of (2.5-3.5):1, for example, it can be 2.5:1, 2.8:1, 3:1, 3.2:1 or 3.5:1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0031] Preferably, the pickling time in step (2) is 4-5 min, for example, 4 min, 4.2 min, 4.5 min, 4.8 min or 5 min, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0032] Preferably, the rinsing solution in step (2) comprises deionized water.

[0033] Preferably, the rinsing time in step (2) is 2-2.5 min, for example, 2 min, 2.2 min, 2.3 min, 2.4 min or 2.5 min, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0034] Preferably, the cleaning solution in step (2) comprises anhydrous ethanol.

[0035] Preferably, the cleaning in step (2) includes ultrasonic cleaning.

[0036] The ultrasonic cleaning can effectively improve the cleaning effect of the hollow cylindrical tantalum tube and can better remove residual impurities compared to conventional cleaning methods.

[0037] Preferably, the frequency of the ultrasonic cleaning is 25-30 KHz, for example, 25 KHz, 26 KHz, 28 KHz, 29 KHz or 30 KHz, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0038] Preferably, the drying temperature in step (2) is 80-100°C, for example, 80°C, 85°C, 90°C, 95°C or 100°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0039] Preferably, the drying time in step (2) is 60-90 min, for example, 60 min, 65 min, 70 min, 80 min or 90 min, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0040] Preferably, the length of the sample in step (3) is 19-21 mm, for example, 19 mm, 19.5 mm, 20 mm, 20.5 mm or 21 mm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0041] Preferably, the diameter of the sample in step (3) is 2-3 mm, for example, 2 mm, 2.2 mm, 2.5 mm, 2.8 mm or 3 mm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0042] Preferably, the pretreated tantalum tube sleeve in step (3) is arranged at the end away from the sputtering of the sample.

[0043] As a preferred technical solution of the sample preparation method of the present invention, the sample preparation method comprises the following steps:

[0044] (1) The tantalum ingot is machined and drilled, hot extruded at 450-500°C, treated with impurities removal, and vacuum heat treated at 1000-1200°C for 100-150 min under inert gas protection to obtain a hollow cylindrical tantalum tube with an outer diameter of 3.4-3.6 mm, an inner diameter of 3-3.1 mm, and a length of 12-17 mm;

[0045] The solution used for the impurity removal treatment includes hydrochloric acid and nitric acid in a volume ratio of (2.5-3.5):1; the concentration of the hydrochloric acid is 36-38wt%; the concentration of the nitric acid is 68-70wt%;

[0046] (2) The hollow cylindrical tantalum tube obtained in step (1) is acid-washed for 4-5 minutes, rinsed with deionized water for 2-2.5 minutes, cleaned with anhydrous ethanol, and dried at 80-100° C. for 60-90 minutes to obtain a pretreated tantalum tube;

[0047] The pickling solution includes hydrochloric acid and nitric acid in a volume ratio of (2.5-3.5):1; the cleaning includes 25-30KHz ultrasonic cleaning;

[0048] (3) placing the pretreated tantalum tube obtained in step (2) at the end away from the sputtering of the sample to obtain a sample to be tested;

[0049] The samples had a length of 19-21 mm and a diameter of 2-3 mm.

[0050] Compared with the prior art, the present invention has the following beneficial effects:

[0051] The sample preparation method provided by the present invention can obtain a pretreated tantalum tube with high purity and good mechanical properties by controlling the process parameters in the processing process and combining the surface treatment steps of pickling, rinsing and cleaning; by strictly controlling the length of the pretreated tantalum tube, the sputtering effect of the sample is not affected when the pretreated tantalum tube is sleeved on the sample, and the tantalum tube is not prone to produce large pieces of debris after being sputtered, and can effectively prevent the short circuit of the anode and cathode caused by the debris generated by the sputtering of the sample, the number of cleaning and maintenance times of the glow discharge chamber can be reduced by 3 times compared with when the pretreated tantalum tube is not sleeved, the use time of the equipment can be extended by 3 times compared with when the pretreated tantalum tube is not sleeved, and the sample can obtain a stronger signal with higher sensitivity by glow discharge mass spectrometry detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 It is a schematic diagram of the structure of the sample to be tested provided in Example 1 of the present invention.

[0053] Among them: 1. Sample to be tested. DETAILED DESCRIPTION

[0054] 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.

[0055] Example 1

[0056] This embodiment provides a sample preparation method for glow discharge mass spectrometry detection, the sample preparation method comprising the following steps:

[0057] (1) The tantalum ingot was machined and drilled, hot extruded at 480°C, treated with impurities removal, and vacuum heat treated at 1100°C for 130 min under argon protection to obtain a hollow cylindrical tantalum tube with an outer diameter of 3.5 mm, an inner diameter of 3.05 mm, and a length of 15 mm;

[0058] The solution used for the impurity removal treatment includes hydrochloric acid and nitric acid in a volume ratio of 3:1; the concentration of the hydrochloric acid is 37wt%; the concentration of the nitric acid is 69wt%;

[0059] (2) The hollow cylindrical tantalum tube obtained in step (1) was acid-washed for 4.5 minutes, rinsed with deionized water for 2.3 minutes, cleaned with anhydrous ethanol, and dried at 90° C. for 70 minutes to obtain a pretreated tantalum tube;

[0060] The pickling solution includes hydrochloric acid and nitric acid in a volume ratio of 3:1; the cleaning includes 28KHz ultrasonic cleaning;

[0061] (3) The pretreated tantalum tube obtained in step (2) is placed at the end away from the sample sputtering to obtain a sample 1 to be tested, such as Figure 1 As shown; the length of the sample is 20 mm and the diameter is 2.5 mm.

[0062] The glow discharge mass spectrometry detection of the obtained samples can obtain a strong signal with high sensitivity; the cleaning and maintenance times of the glow discharge chamber are reduced by 3 times compared with the case without the pre-treated tantalum tube, and the service life of the equipment is extended by 3 times compared with the case without the pre-treated tantalum tube.

[0063] Example 2

[0064] This embodiment provides a sample preparation method for glow discharge mass spectrometry detection, the sample preparation method comprising the following steps:

[0065] (1) The tantalum ingot was machined and drilled, hot extruded at 465°C, treated with impurities removal, and vacuum heat treated at 1050°C for 140 min under argon protection to obtain a hollow cylindrical tantalum tube with an outer diameter of 3.45 mm, an inner diameter of 3.02 mm, and a length of 15 mm;

[0066] The solution used for the impurity removal treatment includes hydrochloric acid and nitric acid in a volume ratio of 2.8:1; the concentration of the hydrochloric acid is 37.5wt%; the concentration of the nitric acid is 68.5wt%;

[0067] (2) The hollow cylindrical tantalum tube obtained in step (1) was acid-washed for 4.2 minutes, rinsed with deionized water for 2.2 minutes, cleaned with anhydrous ethanol, and dried at 85° C. for 80 minutes to obtain a pretreated tantalum tube;

[0068] The pickling solution includes hydrochloric acid and nitric acid in a volume ratio of 2.8:1; the cleaning includes 26KHz ultrasonic cleaning;

[0069] (3) The pretreated tantalum tube obtained in step (2) is placed at the end away from the sample sputtering to obtain a sample 1 to be tested; the length of the sample is 19.5 mm and the diameter is 2.2 mm.

[0070] The glow discharge mass spectrometry detection of the obtained samples can obtain a strong signal with high sensitivity; the cleaning and maintenance times of the glow discharge chamber are reduced by 3 times compared with the case without the pre-treated tantalum tube, and the service life of the equipment is extended by 2 times compared with the case without the pre-treated tantalum tube.

[0071] Example 3

[0072] This embodiment provides a sample preparation method for glow discharge mass spectrometry detection, the sample preparation method comprising the following steps:

[0073] (1) The tantalum ingot was machined and drilled, hot extruded at 490°C, treated with impurities removal, and vacuum heat treated at 1150°C for 115 min under argon protection to obtain a hollow cylindrical tantalum tube with an outer diameter of 3.55 mm, an inner diameter of 3.08 mm, and a length of 15 mm;

[0074] The solution used for the impurity removal treatment includes hydrochloric acid and nitric acid in a volume ratio of 3.2:1; the concentration of the hydrochloric acid is 36.5wt%; the concentration of the nitric acid is 69.5wt%;

[0075] (2) The hollow cylindrical tantalum tube obtained in step (1) was acid-washed for 4.8 minutes, rinsed with deionized water for 2.4 minutes, cleaned with anhydrous ethanol, and dried at 95° C. for 65 minutes to obtain a pretreated tantalum tube;

[0076] The pickling solution includes hydrochloric acid and nitric acid in a volume ratio of 3.2:1; the cleaning includes 29KHz ultrasonic cleaning;

[0077] (3) The pretreated tantalum tube obtained in step (2) is placed at the end away from the sample sputtering to obtain a sample 1 to be tested; the length of the sample is 20.5 mm and the diameter is 2.8 mm.

[0078] The glow discharge mass spectrometry detection of the obtained samples can obtain a strong signal with high sensitivity; the cleaning and maintenance times of the glow discharge chamber are reduced by 3 times compared with the case without the pre-treated tantalum tube, and the service life of the equipment is extended by 2 times compared with the case without the pre-treated tantalum tube.

[0079] Example 4

[0080] This embodiment provides a sample preparation method for glow discharge mass spectrometry detection, the sample preparation method comprising the following steps:

[0081] (1) The tantalum ingot was machined and drilled, hot extruded at 450°C, treated with impurities removal, and vacuum heat treated at 1000°C for 150 min under argon protection to obtain a hollow cylindrical tantalum tube with an outer diameter of 3.4 mm, an inner diameter of 3 mm, and a length of 14.5 mm;

[0082] The solution used for the impurity removal treatment includes hydrochloric acid and nitric acid in a volume ratio of 2.5:1; the concentration of the hydrochloric acid is 38wt%; the concentration of the nitric acid is 68wt%;

[0083] (2) The hollow cylindrical tantalum tube obtained in step (1) was acid-washed for 4 minutes, rinsed with deionized water for 2 minutes, cleaned with anhydrous ethanol, and dried at 80° C. for 90 minutes to obtain a pretreated tantalum tube;

[0084] The pickling solution includes hydrochloric acid and nitric acid in a volume ratio of 2.5:1; the cleaning includes 25KHz ultrasonic cleaning;

[0085] (3) The pretreated tantalum tube obtained in step (2) is placed at the end away from the sample sputtering to obtain a sample 1 to be tested; the length of the sample is 19 mm and the diameter is 2 mm.

[0086] The glow discharge mass spectrometry detection of the obtained sample can obtain a strong signal with high sensitivity; the cleaning and maintenance times of the glow discharge chamber are reduced by 2 times compared with the case without the pre-treated tantalum tube, and the service life of the equipment is extended by 2 times compared with the case without the pre-treated tantalum tube.

[0087] Example 5

[0088] This embodiment provides a sample preparation method for glow discharge mass spectrometry detection, the sample preparation method comprising the following steps:

[0089] (1) The tantalum ingot was machined and drilled, hot extruded at 500°C, treated with impurities, and vacuum heat treated at 1200°C for 100 min under argon protection to obtain a hollow cylindrical tantalum tube with an outer diameter of 3.6 mm, an inner diameter of 3.1 mm, and a length of 15.5 mm;

[0090] The solution used for the impurity removal treatment includes hydrochloric acid and nitric acid in a volume ratio of 3.5:1; the concentration of the hydrochloric acid is 36wt%; the concentration of the nitric acid is 70wt%;

[0091] (2) The hollow cylindrical tantalum tube obtained in step (1) was acid-washed for 5 minutes, rinsed with deionized water for 2.5 minutes, cleaned with anhydrous ethanol, and dried at 100° C. for 60 minutes to obtain a pretreated tantalum tube;

[0092] The pickling solution includes hydrochloric acid and nitric acid in a volume ratio of 3.5:1; the cleaning includes 30KHz ultrasonic cleaning;

[0093] (3) The pretreated tantalum tube obtained in step (2) is placed at the end away from the sample sputtering to obtain a sample 1 to be tested; the length of the sample is 21 mm and the diameter is 3 mm.

[0094] The glow discharge mass spectrometry detection of the obtained sample can obtain a strong signal with high sensitivity; the cleaning and maintenance times of the glow discharge chamber are reduced by 2 times compared with the case without the pre-treated tantalum tube, and the service life of the equipment is extended by 2 times compared with the case without the pre-treated tantalum tube.

[0095] Example 6

[0096] This embodiment provides a sample preparation method for glow discharge mass spectrometry detection, which is different from Embodiment 1 in that, except for adjusting the temperature of the vacuum heat treatment in step (1) to 900° C., the rest is the same as Embodiment 1.

[0097] Since the vacuum heat treatment temperature during the processing of the pretreated tantalum tube is too low, its internal organization is reduced and a small amount of impurities exist on the surface, which reduces the signal intensity that can be obtained when the sample is tested for glow discharge mass spectrometry, and the sensitivity is average; the mechanical properties of the pretreated tantalum tube are reduced, and the size of its fallen debris increases, which reduces the number of cleaning and maintenance times of the glow discharge chamber by 2 times compared with when the pretreated tantalum tube is not installed, and the service life of the equipment is extended by 2 times compared with when the pretreated tantalum tube is not installed.

[0098] Example 7

[0099] This embodiment provides a sample preparation method for glow discharge mass spectrometry detection, which is different from Embodiment 1 in that, except for adjusting the temperature of the vacuum heat treatment in step (1) to 1300° C., the rest is the same as Embodiment 1.

[0100] Since the vacuum heat treatment temperature during the processing of the pretreated tantalum tube is too high, the organization is also deteriorated, which reduces the signal intensity that can be obtained when the sample is tested by glow discharge mass spectrometry, and the sensitivity is average; the cleaning and maintenance times of the glow discharge chamber are reduced by 2 times compared with when the pretreated tantalum tube is not installed, and the service life of the equipment is extended by 2 times compared with when the pretreated tantalum tube is not installed.

[0101] Example 8

[0102] This embodiment provides a sample preparation method for glow discharge mass spectrometry detection, which is different from Embodiment 1 in that, except for adjusting the length of the hollow cylindrical tantalum tube in step (1) to 12 mm, the rest is the same as Embodiment 1.

[0103] The length of the hollow cylindrical tantalum tube is relatively short, and the length of the sample not covered when it is set on the sample is relatively large. Therefore, it is easier for debris to enter the gap of the insulating material during sputtering of the sample to be tested, which can easily cause a short circuit between the anode and cathode. The cleaning and maintenance times of the glow discharge chamber are reduced by 1 times compared to when the pre-treated tantalum tube is not set, and the service life of the equipment is extended by 1 times compared to when the pre-treated tantalum tube is not set.

[0104] Example 9

[0105] This embodiment provides a sample preparation method for glow discharge mass spectrometry detection, which is different from Embodiment 1 in that, except for adjusting the length of the hollow cylindrical tantalum tube in step (1) to 17 mm, the rest is the same as Embodiment 1.

[0106] The length of the hollow cylindrical tantalum tube is relatively large, and the length of the sample not covered when it is sleeved on the sample is relatively small, which will affect the sputtering of the sample, thereby reducing the signal intensity and sensitivity of the sample to be tested when performing glow discharge mass spectrometry detection; the number of cleaning and maintenance times of the glow discharge chamber and the use time of the equipment have no significant changes compared with Example 1.

[0107] Example 10

[0108] This embodiment provides a sample preparation method for glow discharge mass spectrometry detection. The difference from Embodiment 1 is that the solution used for the impurity removal treatment in step (1) is adjusted to a volume ratio of nitric acid to hydrofluoric acid of 3:1, and the solution used for the pickling in step (2) is adjusted to a volume ratio of nitric acid to hydrofluoric acid of 3:1. The rest is the same as Embodiment 1.

[0109] When the solution used for the impurity removal treatment and pickling is a mixture of nitric acid and hydrofluoric acid, the effect of removing surface impurities is slightly reduced compared to a mixture of hydrochloric acid and nitric acid. Therefore, fewer impurities will be introduced during the sputtering process of the sample to be tested, thereby reducing the accuracy of glow discharge mass spectrometry detection; the number of cleaning and maintenance times of the glow discharge chamber and the use time of the equipment are not significantly changed compared to Example 1.

[0110] Embodiment 11

[0111] This embodiment provides a sample preparation method for glow discharge mass spectrometry detection. The difference from Embodiment 1 is that the ultrasonic cleaning in step (2) is replaced by conventional cleaning, and the rest is the same as Embodiment 1.

[0112] The ultrasonic cleaning is replaced by conventional cleaning, and its effect of removing surface impurities is slightly reduced. Therefore, fewer impurities will be introduced during the sputtering process of the sample to be tested, thereby reducing the accuracy of glow discharge mass spectrometry detection; the cleaning and maintenance times of the glow discharge chamber and the use time of the equipment have no significant changes compared with Example 1.

[0113] Comparative Example 1

[0114] This comparative example provides a sample preparation method for glow discharge mass spectrometry detection, which is different from Example 1 in that, except for adjusting the length of the hollow cylindrical tantalum tube in step (1) to 10 mm, the rest is the same as Example 1.

[0115] The length of the hollow cylindrical tantalum tube is too short, and the length of the sample not covered when it is set on the sample is too long. Therefore, debris generated during sputtering of the sample to be tested enters the gaps in the insulating material, resulting in frequent short circuits between the anode and cathode. The cleaning and maintenance times of the glow discharge chamber are similar to those when the pre-treated tantalum tube is not set, and the service life of the equipment is similar to that when the pre-treated tantalum tube is not set.

[0116] Comparative Example 2

[0117] This comparative example provides a sample preparation method for glow discharge mass spectrometry detection, which is different from Example 1 in that, except for adjusting the length of the hollow cylindrical tantalum tube in step (1) to 18 mm, the rest is the same as Example 1.

[0118] The length of the hollow cylindrical tantalum tube is too long, and the length of the tube not covering the sample when it is sleeved on the sample is too short, which has a great influence on the sputtering of the sample and makes it impossible to perform glow discharge mass spectrometry detection.

[0119] Comparative Example 3

[0120] This comparative example provides a sample preparation method for glow discharge mass spectrometry detection, which differs from Example 1 in that step (1) does not involve impurity removal, and the rest is the same as Example 1.

[0121] Without impurity removal treatment, more impurities will be introduced during the sputtering process of the sample to be tested, significantly reducing the accuracy of glow discharge mass spectrometry detection; more impurities will be deposited during the sputtering of the sample to be tested, which will also reduce the cleaning and maintenance times of the glow discharge chamber and the use time of the equipment compared to Example 1.

[0122] Comparative Example 4

[0123] This comparative example provides a sample preparation method for glow discharge mass spectrometry detection, which differs from Example 1 in that step (1) does not involve vacuum heat treatment, and the rest is the same as Example 1.

[0124] No vacuum heat treatment will significantly reduce the mechanical properties of the pretreated tantalum tube, causing large pieces of debris to fall into the gaps in the insulating material during sputtering, resulting in frequent short circuits between the anode and cathode. The cleaning and maintenance times of the glow discharge chamber are similar to those when the pretreated tantalum tube is not installed, and the service life of the equipment is similar to that when the pretreated tantalum tube is not installed.

[0125] In summary, the sample preparation method provided by the present invention can obtain a pretreated tantalum tube with high purity and good mechanical properties by controlling the process parameters in the processing process and combining the surface treatment steps of pickling, rinsing and cleaning; by strictly controlling the length of the pretreated tantalum tube, the sputtering effect of the sample is not affected when the pretreated tantalum tube is sleeved on the sample, and the tantalum tube is not prone to produce large pieces of debris after being sputtered, and can also effectively prevent the anode and cathode short circuit caused by the debris generated by the sputtering of the sample. The number of cleaning and maintenance times of the glow discharge chamber can be reduced by 3 times compared with when the pretreated tantalum tube is not sleeved, and the use time of the equipment can be extended by 3 times compared with when the pretreated tantalum tube is not sleeved, and the sample can obtain a stronger signal with higher sensitivity by glow discharge mass spectrometry detection.

[0126] The above description 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 are within the protection scope and disclosure scope of the present invention.

Claims

1. A sample preparation method for glow discharge mass spectrometry detection, characterized in that: The sample preparation method comprises the following steps: (1) The tantalum ingot is machined, drilled, hot extruded, impurity-removed and vacuum heat treated to obtain a hollow cylindrical tantalum tube with an outer diameter of 3.4-3.6 mm, an inner diameter of 3-3.1 mm and a length of 12-17 mm; (2) The hollow cylindrical tantalum tube obtained in step (1) is pickled, rinsed, cleaned and dried to obtain a pretreated tantalum tube; (3) The pretreated tantalum tube obtained in step (2) is placed on the sample to obtain a sample to be tested.

2. The sample preparation method according to claim 1, characterized in that: The machining and drilling in step (1) is performed under the protection of an inert gas, wherein the inert gas comprises argon; Preferably, the temperature of the hot extrusion in step (1) is 450-500°C.

3. The sample preparation method according to claim 1 or 2, characterized in that: The solution used for the impurity removal treatment in step (1) comprises hydrochloric acid and nitric acid in a volume ratio of (2.5-3.5):1; Preferably, the concentration of the hydrochloric acid is 36-38wt%; Preferably, the concentration of the nitric acid is 68-70 wt %.

4. The sample preparation method according to any one of claims 1 to 3, characterized in that: The temperature of the vacuum heat treatment in step (1) is 1000-1200° C. Preferably, the vacuum heat treatment time in step (1) is 100-150 minutes.

5. The sample preparation method according to any one of claims 1 to 4, characterized in that: The length of the hollow cylindrical tantalum tube in step (1) is 14.5-15.5 mm.

6. The sample preparation method according to any one of claims 1 to 5, characterized in that: The pickling solution in step (2) comprises hydrochloric acid and nitric acid in a volume ratio of (2.5-3.5):1; Preferably, the pickling time in step (2) is 4-5 minutes; Preferably, the rinsing solution in step (2) comprises deionized water; Preferably, the rinsing time in step (2) is 2-2.5 min.

7. The sample preparation method according to any one of claims 1 to 6, characterized in that: The cleaning solution in step (2) comprises anhydrous ethanol; Preferably, the cleaning in step (2) comprises ultrasonic cleaning; Preferably, the frequency of the ultrasonic cleaning is 25-30 KHz.

8. The sample preparation method according to any one of claims 1 to 7, characterized in that: The drying temperature in step (2) is 80-100° C. Preferably, the drying time in step (2) is 60-90 minutes.

9. The sample preparation method according to any one of claims 1 to 8, characterized in that: The length of the sample in step (3) is 19-21 mm; Preferably, the diameter of the sample in step (3) is 2-3 mm; Preferably, the pretreated tantalum tube sleeve in step (3) is arranged at the end away from the sputtering of the sample.

10. The sample preparation method according to any one of claims 1 to 9, characterized in that: The sample preparation method comprises the following steps: (1) The tantalum ingot is machined and drilled, hot extruded at 450-500°C, treated with impurities removal, and vacuum heat treated at 1000-1200°C for 100-150 min under inert gas protection to obtain a hollow cylindrical tantalum tube with an outer diameter of 3.4-3.6 mm, an inner diameter of 3-3.1 mm, and a length of 12-17 mm; The solution used for the impurity removal treatment includes hydrochloric acid and nitric acid in a volume ratio of (2.5-3.5):1; the concentration of the hydrochloric acid is 36-38wt%; the concentration of the nitric acid is 68-70wt%; (2) The hollow cylindrical tantalum tube obtained in step (1) is acid-washed for 4-5 minutes, rinsed with deionized water for 2-2.5 minutes, cleaned with anhydrous ethanol, and dried at 80-100° C. for 60-90 minutes to obtain a pretreated tantalum tube; The pickling solution includes hydrochloric acid and nitric acid in a volume ratio of (2.5-3.5):1; the cleaning includes 25-30KHz ultrasonic cleaning; (3) placing the pretreated tantalum tube obtained in step (2) at the end away from the sputtering of the sample to obtain a sample to be tested; The samples had a length of 19-21 mm and a diameter of 2-3 mm.

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