A sample preparation method and detection method for detecting carbon content in an aluminum sample by glow discharge mass spectrometry

Abstract

The application provides a sample preparation method and a detection method for detecting the carbon content in an aluminum sample by using a glow discharge mass spectrometer. The sample preparation method comprises the following steps: sequentially performing acid washing, water washing and argon ion polishing treatment on a high-purity aluminum sample to obtain an aluminum sample to be detected; the acid washing and the water washing are alternately performed at least three times; and the acid washing solution is a mixed solution of nitric acid, hydrofluoric acid and water. The sample preparation method is designed by combining the acid washing, the water washing and the argon ion polishing treatment, and the mixed solution of the nitric acid, the hydrofluoric acid and the water is used as the acid washing solution, so that the impurities on the surface of the high-purity aluminum sample are efficiently removed, the influence of the impurities on the detection result of the glow discharge mass spectrometer is avoided, and the stability of the detection result of the glow discharge mass spectrometer is favorable. The detection method realizes the detection of the trace carbon element in the aluminum sample by controlling the discharge voltage and the discharge current range during the detection, and has the advantages of high sensitivity, low detection limit and high result stability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of analytical chemistry, and particularly relates to a sample preparation method and a detection method for detecting an aluminum sample by using a glow discharge mass spectrometry. BACKGROUND

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

[0003] Glow discharge mass spectrometry (GDMS) can be used to directly analyze solid samples. Metal substrates with good electrical conductivity are the advantageous field of application of GDMS analysis. For example, copper, iron, zinc, lead, aluminum, gallium, tantalum, cobalt, titanium, cadmium, antimony, or germanium, etc. Among the sample types for GDMS analysis, the most ideal is a bulk metal. Glow discharge mass spectrometry is one of the most effective methods for directly analyzing trace and ultra-trace impurity elements in conductive solid materials.

[0004] CN103884772A discloses a method for determining trace impurity elements in high-purity indium by using glow discharge mass spectrometry. The steps are as follows: (1) the sample is cut into a sheet, the oil stains on the surface of the sample are cleaned with toluene, the sample is then cleaned with ultrapure water, and is corroded with 50% (by volume) nitric acid for 8 minutes. After repeated washing with ultrapure water, the sample is stored in methanol. Before analysis, the sample is taken out and dried under an infrared lamp. (2) The sample is placed in a sample holder and pushed into an ion source cavity. When the vacuum degree reaches 2.2-2.4 mbar, the discharge voltage and the discharge current are adjusted to 0.9-1.2 kV and 40-45 mA, respectively. Sputtering is performed for about 30-40 minutes. Generally, the signals of Na, Fe, and Ca, which are prone to introduce contamination, are stable, so as to eliminate the contamination that may be generated during the sample preparation. (3) The discharge voltage is adjusted to 0.9-1.2 kV, and the discharge current is adjusted to 40-45 mA. High-voltage discharge is performed, and the ion signals of the elements to be detected are collected. According to the quantitative analysis principle of the glow discharge mass spectrometer, the concentration of the impurity elements to be detected is calculated. However, toluene is used to clean the high-purity indium, which is harmful to human health, and the sensitivity and resolution are low.

[0005] In addition, toluene can interfere with the detection of trace carbon elements in metals, so the above method cannot be used to detect the content of trace carbon elements in metals. Therefore, there is an urgent need to develop a sample preparation method and a detection method for removing impurities on the surface of high-purity aluminum, so as to realize the detection of trace carbon content in aluminum samples. SUMMARY

[0006] To solve the above technical problems, the application provides a sample preparation method and a detection method for detecting carbon content in an aluminum sample by glow discharge mass spectrometry.

[0007] To achieve the above technical effects, the application adopts the following technical solutions:

[0008] In a first aspect, the application provides a sample preparation method for detecting carbon content in an aluminum sample by glow discharge mass spectrometry, which comprises:

[0009] The high-purity aluminum sample is sequentially subjected to acid washing, water washing, and argon ion polishing treatment to obtain an aluminum sample to be detected;

[0010] The acid washing and water washing are alternately performed at least three times.

[0011] The acid washing solution for the acid washing is a mixed solution of nitric acid, hydrofluoric acid, and water.

[0012] The sample preparation method provided by the application efficiently removes impurities on the surface of the high-purity aluminum sample by combining acid washing, water washing, and argon ion polishing treatment and using a mixed solution of nitric acid, hydrofluoric acid, and water as the acid washing solution, without introducing impurities, thereby avoiding the influence of impurities on the detection results of the glow discharge mass spectrometry, stabilizing the detection results of the glow discharge mass spectrometry, and improving the detection accuracy of the glow discharge mass spectrometry.

[0013] As a preferred technical solution of the application, the purity of the high-purity aluminum sample is greater than or equal to 99.99%, for example, 99.992%, 99.994%, 99.995%, 99.996%, 99.998%, or 99.999%, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0014] Preferably, the carbon content in the high-purity aluminum sample is less than or equal to 5 mg / kg, for example, 4.5 mg / kg, 4 mg / kg, 3.5 mg / kg, 3.2 mg / kg, 3 mg / kg, or 2.5 mg / kg, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0015] In the application, ethanol or other carbon-containing cooling liquids cannot be used to cool the sample during the process of making the high-purity aluminum into a block-shaped aluminum sample. The high-purity aluminum sample includes a block-shaped aluminum sample, the size of which can be designed according to the requirements of the glow discharge mass spectrometry detection equipment.

[0016] As a preferred technical scheme of the present application, the volume ratio of nitric acid, hydrofluoric acid and water in the pickling solution is 1:(0.8-1.2):(3.5-4.5), for example, it can be 1:0.82:3.6, 1:0.85:3.7, 1:0.87:3.8, 1:0.9:3.9, 1:1:4, 1:1.05:4.1, 1:1.1:4.2 or 1:1.15:4.3, etc., but not limited to the listed values, other values not listed in the value range are also applicable.

[0017] In the present application, as long as the pickling solution used in the pickling process can cover the surface of the aluminum sample to be tested during the washing process, the amount of pickling solution is not specifically limited in the present application.

[0018] Preferably, the mass concentration of nitric acid is 65%-68%, for example, it can be 65.5%, 66%, 66.5%, 67%, 67.5% or 67.8%, etc., but not limited to the listed values, other values not listed in the value range are also applicable.

[0019] Preferably, the mass concentration of hydrofluoric acid is ≥30%, for example, it can be 32%, 35%, 37%, 39%, 40% or 45%, etc., but not limited to the listed values, other values not listed in the value range are also applicable.

[0020] As a preferred technical scheme of the present application, the pickling time is 1-3min, for example, it can be 1.2min, 1.4min, 1.5min, 1.7min, 1.9min, 2min, 2.2min, 2.4min, 2.5min, 2.7min or 2.9min, etc., but not limited to the listed values, other values not listed in the value range are also applicable.

[0021] Preferably, the pickling method is ultrasonic cleaning.

[0022] In the present application, when pickling, the aluminum sample is placed in a polytetrafluoroethylene beaker and then placed in an ultrasonic cleaning machine for cleaning.

[0023] Preferably, the frequency of ultrasonic cleaning is 35-45kHz, for example, it can be 36kHz, 37kHz, 38kHz, 39kHz, 40kHz, 41kHz, 42kHz, 43kHz or 44kHz, etc., but not limited to the listed values, other values not listed in the value range are also applicable.

[0024] As a preferred technical scheme of the present application, the water washing method is flushing.

[0025] Preferably, after water washing, the argon ion polishing treatment further includes drying.

[0026] In the present application, the drying method is to dry the sample by blowing high-purity nitrogen, and the purity of the nitrogen is ≥99.99%.

[0027] As a preferred technical solution of the present application, the argon ion polishing treatment uses an argon ion beam with a purity of ≥99.999%, for example, it can be 99.999%, 99.9992%, 99.9994%, 99.9996%, 99.9998%, or 99.9999%, etc., but not limited to the listed values, and other values not listed within the value range are also applicable.

[0028] In the present application, the number of ion guns for the argon ion polishing treatment is 2.

[0029] Preferably, the vacuum degree of the argon ion polishing treatment is ≤10 -1 pa, for example, it can be 9×10 -2 pa, 7×10 - 2 pa, 5×10 -2 pa, 3×10 -2 pa, or 10 -3 pa, etc., but not limited to the listed values, and other values not listed within the value range are also applicable.

[0030] As a preferred technical solution of the present application, the argon ion polishing treatment includes first argon ion polishing, second argon ion polishing, third argon ion polishing, and fourth argon ion polishing performed in sequence.

[0031] Preferably, the voltage of the first argon ion polishing is 2.8-3.2kV, for example, it can be 2.82kV, 2.85kV, 2.87kV, 2.9kV, 2.95kV, 3kV, 3.05kV, 3.1kV, or 3.15kV, etc., but not limited to the listed values, and other values not listed within the value range are also applicable.

[0032] Preferably, the current of the first argon ion polishing is 0.28-0.32mA, for example, it can be 0.282mA, 0.285mA, 0.287mA, 0.29mA, 0.295mA, 0.3mA, 0.305mA, 0.31mA, or 0.315mA, etc., but not limited to the listed values, and other values not listed within the value range are also applicable.

[0033] Preferably, the first argon ion polishing is performed for a time of 1.5-2.5 min, for example, it can be 1.6 min, 1.7 min, 1.8 min, 1.9 min, 2 min, 2.1 min, 2.2 min, or 2.3 min, etc., but not limited to the listed values, other values not listed in the range of values are also applicable.

[0034] Preferably, the second argon ion polishing is performed at a voltage of 4.8-5.2 kV, for example, it can be 4.82 kV, 4.85 kV, 4.87 kV, 4.9 kV, 4.95 kV, 5 kV, 5.05 kV, 5.1 kV, or 5.15 kV, etc., but not limited to the listed values, other values not listed in the range of values are also applicable.

[0035] Preferably, the second argon ion polishing is performed at a current of 0.28-0.32 mA, for example, it can be 0.282 mA, 0.285 mA, 0.287 mA, 0.29 mA, 0.295 mA, 0.3 mA, 0.305 mA, 0.31 mA, or 0.315 mA, etc., but not limited to the listed values, other values not listed in the range of values are also applicable.

[0036] Preferably, the second argon ion polishing is performed for a time of 1.5-2.5 min, for example, it can be 1.6 min, 1.7 min, 1.8 min, 1.9 min, 2 min, 2.1 min, 2.2 min, or 2.3 min, etc., but not limited to the listed values, other values not listed in the range of values are also applicable.

[0037] Preferably, the third argon ion polishing is performed at a voltage of 6.8-7.2 kV, for example, it can be 6.82 kV, 6.85 kV, 6.87 kV, 6.9 kV, 6.95 kV, 7 kV, 7.05 kV, 7.1 kV, or 7.15 kV, etc., but not limited to the listed values, other values not listed in the range of values are also applicable.

[0038] Preferably, the third argon ion polishing is performed at a current of 0.28-0.32 mA, for example, it can be 0.282 mA, 0.285 mA, 0.287 mA, 0.29 mA, 0.295 mA, 0.3 mA, 0.305 mA, 0.31 mA, or 0.315 mA, etc., but not limited to the listed values, other values not listed in the range of values are also applicable.

[0039] Preferably, the third argon ion polishing time is 35-45 min, for example, it can be 36 min, 37 min, 38 min, 39 min, 40 min, 41 min, 42 min or 44 min, etc., but not only limited to the listed values, other values not listed in the value range are also applicable.

[0040] Preferably, the fourth argon ion polishing voltage is 4.8-5.2 kV, for example, it can be 4.82 kV, 4.85 kV, 4.87 kV, 4.9 kV, 4.95 kV, 5 kV, 5.05 kV, 5.1 kV or 5.15 kV, etc., but not only limited to the listed values, other values not listed in the value range are also applicable.

[0041] Preferably, the fourth argon ion polishing current is 0.28-0.32 mA, for example, it can be 0.282 mA, 0.285 mA, 0.287 mA, 0.29 mA, 0.295 mA, 0.3 mA, 0.305 mA, 0.31 mA or 0.315 mA, etc., but not only limited to the listed values, other values not listed in the value range are also applicable.

[0042] Preferably, the fourth argon ion polishing time is 10-20 min, for example, it can be 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min or 19 min, etc., but not only limited to the listed values, other values not listed in the value range are also applicable.

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

[0044] The high-purity aluminum sample with a purity of ≥99.99% is sequentially subjected to acid washing, water washing and argon ion polishing treatment to obtain an aluminum sample to be detected;

[0045] The carbon content in the high-purity aluminum sample is ≤5 mg / kg;

[0046] The acid washing and water washing are alternately performed at least three times;

[0047] The acid washing solution of the acid washing is a mixed solution of nitric acid, hydrofluoric acid and water with a volume ratio of 1:(0.8-1.2):(3.5-4.5); the acid washing time is 1-3 min; the acid washing mode is ultrasonic cleaning; and the ultrasonic cleaning frequency is 35-45 kHz;

[0048] The water washing mode is flushing; and after the water washing, the argon ion polishing treatment further comprises drying;

[0049] The argon ion polishing treatment comprises a first argon ion polishing, a second argon ion polishing, a third argon ion polishing and a fourth argon ion polishing in sequence; the argon ion polishing treatment adopts an argon ion beam with a purity of ≥99.999%; the vacuum degree of the argon ion polishing treatment is ≤10 -1 pa;

[0050] The voltage of the first argon ion polishing is 2.8-3.2kV, the current is 0.28-0.32mA, and the time is 1.5-2.5min;

[0051] The voltage of the second argon ion polishing is 4.8-5.2kV, the current is 0.28-0.32mA, and the time is 1.5-2.5min;

[0052] The voltage of the third argon ion polishing is 6.8-7.2kV, the current is 0.28-0.32mA, and the time is 35-45min;

[0053] The voltage of the fourth argon ion polishing is 4.8-5.2kV, the current is 0.28-0.32mA, and the time is 10-20min.

[0054] In a second aspect, the present application provides a detection method for detecting the content of carbon in an aluminum sample by using a glow discharge mass spectrometer, which comprises:

[0055] The aluminum sample processed by the sample preparation method of the first aspect is placed in a sample chamber of a glow discharge mass spectrometer, and after vacuumizing, it is pushed into a discharge chamber, and after cooling and pre-sputtering in sequence, detection is performed to obtain the content of carbon element in the aluminum sample.

[0056] The pre-sputtering time is 50-70min, and when detection is performed, the aluminum metal matrix and the carbon element are selected for direct current glow discharge mass spectrometry analysis to obtain the content of carbon element in the aluminum sample.

[0057] The detection method provided by the present application has less interference, simple steps, good precision, and can meet the requirements of metal micro-carbon element analysis.

[0058] As a preferred technical solution of the present application, the content of carbon in the high-purity aluminum sample is ≤5mg / kg, for example, it can be 4.5mg / kg, 4mg / kg, 3.5mg / kg, 3.2mg / kg, 3mg / kg or 2.5mg / kg, etc., but not limited to the listed values, and other values not listed in the value range are also applicable.

[0059] Preferably, the vacuum degree is ≤5×10 -7 mbar, for example, it can be 4×10 -7 mbar, 3×10 -7 mbar, 2x10 -7 mbar or 1x10 -7 mbar, etc., but not only limited to the listed values, other values not listed in the range of values are also applicable.

[0060] Preferably, the discharge voltage of the glow discharge mass spectrometer is 1150-1250V, for example, it can be 1160V, 1170V, 1180V, 1190V, 1200V, 1210V, 1220V, 1230V or 1240V, etc., but not only limited to the listed values, other values not listed in the range of values are also applicable.

[0061] Preferably, the discharge current of the glow discharge mass spectrometer is 2.8-3.2mA, for example, it can be 2.82mA, 2.85mA, 2.87mA, 2.9mA, 2.95mA, 3mA, 3.05mA, 3.1mA or 3.15mA, etc., but not only limited to the listed values, other values not listed in the range of values are also applicable.

[0062] Preferably, the vacuum degree of the detection area is ≤5x10 -9 mbar, for example, it can be 4x10 -9 mbar, 3x10 -9 mbar, 2x10 -9 mbar or 1x10 -9 mbar, etc., but not only limited to the listed values, other values not listed in the range of values are also applicable.

[0063] Compared with the prior art, the present application has the following beneficial effects:

[0064] (1) The sample preparation method provided by the present application combines acid washing, water washing and argon ion polishing treatment, and uses a mixed solution of nitric acid, hydrofluoric acid and water as the acid washing solution, to efficiently remove impurities on the surface of the high-purity aluminum sample, avoiding the influence of impurities on the detection results of the glow discharge mass spectrometer, and being conducive to the stability of the detection results of the glow discharge mass spectrometer.

[0065] (2) The detection method provided by the present application controls the range of discharge voltage and discharge current during detection, realizes the detection of trace carbon elements in the aluminum sample, has high sensitivity, low detection limit of carbon elements, and high result stability. DETAILED DESCRIPTION

[0066] In order to facilitate the understanding of the present application, the present application lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present application, and should not be regarded as a specific limitation on the present application.

[0067] The carbon content in the high-purity aluminum sample in the following examples and comparative examples is 5 mg / kg.

[0068] Example 1

[0069] The embodiment provides a sample preparation method for detecting carbon content in an aluminum sample by using a glow discharge mass spectrometer, and the sample preparation method comprises the following steps:

[0070] A high-purity aluminum sample with a purity of 99.99% is sequentially subjected to acid washing, water washing and argon ion polishing treatment to obtain an aluminum sample to be detected;

[0071] The acid washing and water washing are alternately performed three times;

[0072] The acid washing solution for the acid washing is a mixed solution of nitric acid, hydrofluoric acid and water with a volume ratio of 1:1:4; the mass concentration of the nitric acid is 67%; and the mass concentration of the hydrofluoric acid is 38%;

[0073] The acid washing time is 2 min; the acid washing mode is ultrasonic cleaning; and the ultrasonic cleaning frequency is 40 kHz;

[0074] The water washing mode is flushing; and after the water washing, the argon ion polishing treatment further comprises the following step: blowing the aluminum sample dry by using nitrogen;

[0075] The argon ion polishing treatment comprises sequentially performed first argon ion polishing, second argon ion polishing, third argon ion polishing and fourth argon ion polishing;

[0076] The argon ion polishing treatment adopts an argon ion beam with a purity of 99.9992%; and the vacuum degree of the argon ion polishing treatment is 7x10 -2 pa;

[0077] The voltage of the first argon ion polishing is 3 kV, the current is 0.3 mA, and the time is 2 min;

[0078] The voltage of the second argon ion polishing is 5 kV, the current is 0.3 mA, and the time is 2 min;

[0079] The voltage of the third argon ion polishing is 7 kV, the current is 0.3 mA, and the time is 40 min;

[0080] The voltage of the fourth argon ion polishing is 5 kV, the current is 0.3 mA, and the time is 15 min.

[0081] Example 2

[0082] The embodiment provides a sample preparation method for detecting carbon content in an aluminum sample by using a glow discharge mass spectrometer, and the sample preparation method comprises the following steps:

[0083] A high-purity aluminum sample with a purity of 99.992% is sequentially subjected to acid washing, water washing and argon ion polishing treatment to obtain an aluminum sample to be detected;

[0084] The acid washing and water washing are alternately performed three times;

[0085] The acid washing solution of the acid washing is a mixed solution of nitric acid, hydrofluoric acid and water with a volume ratio of 1:0.8:4.2; the mass concentration of the nitric acid is 65%; and the mass concentration of the hydrofluoric acid is 40%;

[0086] The acid washing time is 1.5 min; the acid washing mode is ultrasonic cleaning; and the ultrasonic cleaning frequency is 40 kHz;

[0087] The water washing mode is flushing; and after the water washing, the argon ion polishing treatment further comprises: blowing the aluminum sample dry with nitrogen;

[0088] The argon ion polishing treatment comprises sequentially performed first argon ion polishing, second argon ion polishing, third argon ion polishing and fourth argon ion polishing;

[0089] The argon ion polishing treatment adopts an argon ion beam with a purity of 99.999%; and the vacuum degree of the argon ion polishing treatment is 5×10 -2 pa;

[0090] The voltage of the first argon ion polishing is 3.2 kV, the current is 0.3 mA, and the time is 1.5 min;

[0091] The voltage of the second argon ion polishing is 5.18 kV, the current is 0.3 mA, and the time is 1.6 min;

[0092] The voltage of the third argon ion polishing is 7.2 kV, the current is 0.3 mA, and the time is 35 min;

[0093] The voltage of the fourth argon ion polishing is 5.2 kV, the current is 0.3 mA, and the time is 11 min.

[0094] Embodiment 3

[0095] The embodiment provides a sample preparation method for detecting carbon content in an aluminum sample by glow discharge mass spectrometry, and the sample preparation method comprises the following steps:

[0096] A high-purity aluminum sample with a purity of 99.99% is sequentially subjected to acid washing, water washing and argon ion polishing treatment to obtain an aluminum sample to be detected;

[0097] The acid washing and water washing are alternately performed three times;

[0098] The pickling acid solution is a mixed solution of nitric acid, hydrofluoric acid and water in a volume ratio of 1:1.2:4; the mass concentration of the nitric acid is 68%; and the mass concentration of the hydrofluoric acid is 38%;

[0099] The pickling time is 3 minutes; the pickling mode is ultrasonic cleaning; and the ultrasonic cleaning frequency is 40 kHz.

[0100] The water washing mode is flushing; and after the water washing, the argon ion polishing treatment further comprises blowing the aluminum sample dry with nitrogen.

[0101] The argon ion polishing treatment comprises sequentially performed first, second, third and fourth argon ion polishing.

[0102] The argon ion polishing treatment adopts an argon ion beam with a purity of 99.999%; and the vacuum degree of the argon ion polishing treatment is 1x10 -2 pa.

[0103] The voltage of the first argon ion polishing is 2.8 kV, the current is 0.3 mA, and the time is 2.5 minutes.

[0104] The voltage of the second argon ion polishing is 4.85 kV, the current is 0.3 mA, and the time is 2.4 minutes.

[0105] The voltage of the third argon ion polishing is 6.8 kV, the current is 0.3 mA, and the time is 45 minutes.

[0106] The voltage of the fourth argon ion polishing is 4.85 kV, the current is 0.3 mA, and the time is 20 minutes.

[0107] Example 4

[0108] The embodiment provides a sample preparation method for detecting carbon content in an aluminum sample by using a glow discharge mass spectrometer, wherein, except that the pickling solution is a mixed solution of nitric acid and hydrofluoric acid in a volume ratio of 1:1, other conditions are the same as those in Example 1.

[0109] Example 5

[0110] The embodiment provides a sample preparation method for detecting carbon content in an aluminum sample by using a glow discharge mass spectrometer, wherein, except that the time of the third argon ion polishing is 25 minutes, other conditions are the same as those in Example 1.

[0111] Example 6

[0112] The embodiment provides a sample preparation method for detecting carbon content in an aluminum sample by using a glow discharge mass spectrometer, wherein, except that the time of the third argon ion polishing is 60 minutes, other conditions are the same as those in Example 1.

[0113] Example 7

[0114] The present example provides a sample preparation method for detecting the carbon content in an aluminum sample by glow discharge mass spectrometry, wherein the argon ion polishing treatment does not include the third argon ion polishing, and other conditions are the same as those in Example 1.

[0115] Example 8

[0116] The present example provides a sample preparation method for detecting the carbon content in an aluminum sample by glow discharge mass spectrometry, wherein the argon ion polishing treatment does not include the fourth argon ion polishing, and other conditions are the same as those in Example 1.

[0117] Example 9

[0118] The present example provides a sample preparation method for detecting the carbon content in an aluminum sample by glow discharge mass spectrometry, wherein the argon ion polishing treatment includes the first argon ion polishing and the second argon ion polishing in sequence, and other conditions are the same as those in Example 1.

[0119] Comparative Example 1

[0120] The present comparative example provides a sample preparation method for detecting the carbon content in an aluminum sample by glow discharge mass spectrometry, wherein the acid washing and water washing are not alternated for three times, but are adjusted to be: after three times of acid washing, water washing is performed, and other conditions are the same as those in Example 1.

[0121] Comparative Example 2

[0122] The present comparative example provides a sample preparation method for detecting the carbon content in an aluminum sample by glow discharge mass spectrometry, wherein the argon ion polishing treatment is not performed, and other conditions are the same as those in Example 1.

[0123] Application Example 1

[0124] The present application example provides a detection method for detecting the carbon content in an aluminum sample by glow discharge mass spectrometry, which comprises: placing the aluminum sample treated by the sample preparation method of Example 1 in the sample chamber of a glow discharge mass spectrometer, vacuumizing to a vacuum degree of 4x10 -7 mbar, and then pushing into the discharge chamber, sequentially performing cooling and pre-sputtering for 1h, and then performing detection to obtain the content of carbon element in the aluminum sample; wherein the discharge voltage of the glow discharge mass spectrometer is 1200V, the discharge current is 3mA, and the vacuum degree of the detection area is 3x10 -9 mbar.

[0125] Application Examples 2-9

[0126] The application example provides a detection method for detecting the carbon content in an aluminum sample by using glow discharge mass spectrometry. Except that the aluminum sample is replaced by the aluminum sample prepared in the embodiment 2-9, other conditions are the same as those in the application example 1.

[0127] Application Example 10

[0128] The application example provides a detection method for detecting the carbon content in an aluminum sample by using glow discharge mass spectrometry. Except that the discharge voltage of the glow discharge mass spectrometer is controlled to be 1100 V in the detection, other conditions are the same as those in the application example 1.

[0129] Application Example 11

[0130] The application example provides a detection method for detecting the carbon content in an aluminum sample by using glow discharge mass spectrometry. Except that the discharge voltage of the glow discharge mass spectrometer is controlled to be 1350 V in the detection, other conditions are the same as those in the application example 1.

[0131] Application Example 12

[0132] The application example provides a detection method for detecting the carbon content in an aluminum sample by using glow discharge mass spectrometry. Except that the discharge current of the glow discharge mass spectrometer is controlled to be 2 mA in the detection, other conditions are the same as those in the application example 1.

[0133] Application Example 13

[0134] The application example provides a detection method for detecting the carbon content in an aluminum sample by using glow discharge mass spectrometry. Except that the discharge current of the glow discharge mass spectrometer is controlled to be 4 mA in the detection, other conditions are the same as those in the application example 1.

[0135] Comparative Application Examples 1-2

[0136] The comparative application example provides a detection method for detecting the carbon content in an aluminum sample by using glow discharge mass spectrometry. Except that the aluminum sample is replaced by the aluminum sample prepared in the comparative example 1-2, other conditions are the same as those in the application example 1.

[0137] The application examples and the comparative application examples are analyzed by using glow discharge mass spectrometry, and the parallel detection is performed for 4 times. The test time is 10 min, 20 min, 30 min and 60 min respectively. The content of the carbon element in the aluminum sample is A1, A2, A3 and A4 respectively. The results are shown in Table 1.

[0138] Table 1

[0139]

[0140]

[0141] From Table 1, it can be known that:

[0142] (1) The sample preparation method provided by the application can efficiently remove impurities on the surface of high-purity aluminum samples by combining acid washing, water washing and argon ion polishing treatment and using a mixed solution of nitric acid, hydrofluoric acid and water as the acid washing solution, thereby avoiding the influence of impurities on the detection results of glow discharge mass spectrometry, and the detection method provided by the application can realize the content detection of trace carbon elements in aluminum samples, has a low detection limit and stable results;

[0143] (2) It can be known from the comparison of application examples 1 and 4 that when the acid washing solution does not contain water, the aluminum sample reacts too fast with the acid washing solution, the surface of the aluminum sample becomes rough, impurities are easily adsorbed, the glow discharge mass spectrometry detection is affected, and the detection results are unstable;

[0144] (3) It can be known from the comparison of application examples 1 and 5-6 that when the third argon ion polishing time is too short, the impurities on the surface of the high-purity aluminum sample cannot be removed well, the accuracy of the glow discharge mass spectrometry detection results is reduced, and the stability is also reduced; when the third argon ion polishing time is too long, the detection results are not affected, but the experimental time is prolonged;

[0145] (4) It can be known from the comparison of application examples 1 and 7-9 and the comparison of application example 2 that when the argon ion polishing treatment is not performed or the argon ion polishing treatment does not include the first argon ion polishing, the second argon ion polishing, the third argon ion polishing and the fourth argon ion polishing performed in sequence, the synergistic effect between rough polishing and fine polishing cannot be achieved, the impurities on the surface of the aluminum sample cannot be effectively removed, the accuracy of the carbon element in the glow discharge mass spectrometry detection results is affected, and the stability is also reduced;

[0146] (5) It can be known from the comparison of application examples 1 and 10-13 that when the discharge voltage is too low during the detection process, the sputtering sample speed is too slow, the time to reach the stable results is long, the accuracy of the carbon element in the glow discharge mass spectrometry detection results is affected; when the discharge voltage is too high during the detection process, the sputtering sample speed is too fast, the sample surface is heated, the detection results are unstable, and the glow discharge mass spectrometry detection is affected; when the discharge current is too low during the detection process, the sputtering sample speed is too slow, the time to reach the stable results is long, the detection time is prolonged, and the accuracy of the carbon element in the glow discharge mass spectrometry detection results is affected; when the discharge current is too high during the detection process, the sputtering sample speed is too fast, the sample surface is heated, the detection results are unstable, and the glow discharge mass spectrometry detection is affected;

[0147] (6) It can be known from the comparison of application examples 1 and the comparison application example 1 that when the acid washing and water washing are not alternately performed, the impurities on the surface of the aluminum sample cannot be effectively removed, and the accuracy of the glow discharge mass spectrometry detection results is low.

[0148] The applicant states that the above description is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and it should be understood by those skilled in the art that any changes or replacements within the technical scope disclosed by the present application can be easily thought out by those skilled in the art, and all of them fall within the protection scope and disclosure scope of the present application.

Claims

1. A method for preparing a sample for the determination of the carbon content in an aluminum sample by glow discharge mass spectrometry, characterized in that The sample preparation method comprises: The high-purity aluminum sample is sequentially subjected to acid washing, water washing and argon ion polishing treatment to obtain an aluminum sample to be detected; The acid washing and water washing are alternately performed at least three times; The acid washing solution for the acid washing is a mixed solution of nitric acid, hydrofluoric acid and water; The argon ion polishing treatment comprises sequentially performed first, second, third and fourth argon ion polishing; The voltage of the first argon ion polishing is 2.8-3.2 kV; The current of the first argon ion polishing is 0.28-0.32 mA; The time of the first argon ion polishing is 1.5-2.5 min; The voltage of the second argon ion polishing is 4.8-5.2 kV; The current of the second argon ion polishing is 0.28-0.32 mA; The time of the second argon ion polishing is 1.5-2.5 min; The voltage of the third argon ion polishing is 6.8-7.2 kV; The current of the third argon ion polishing is 0.28-0.32 mA; The time of the third argon ion polishing is 35-45 min; The voltage of the fourth argon ion polishing is 4.8-5.2 kV; The current of the fourth argon ion polishing is 0.28-0.32 mA; The time of the fourth argon ion polishing is 10-20 min.

2. The sample preparation method of claim 1, wherein The purity of the high-purity aluminum sample is ≥99.99%.

3. The sample preparation method of claim 1, wherein The carbon content in the high-purity aluminum sample is ≤5 mg / kg.

4. The sample preparation method of claim 1, wherein In the acid washing solution, the volume ratio of nitric acid, hydrofluoric acid and water is 1:(0.8-1.2):(3.5-4.5).

5. The sample preparation method of claim 4, wherein The mass concentration of the nitric acid is 65%-68%.

6. The method of claim 4, wherein, The mass concentration of the hydrofluoric acid is ≥30%.

7. The method of claim 1, wherein The time of the acid washing is 1-3 min.

8. The sample preparation method of claim 1, wherein The acid washing is performed in the form of ultrasonic cleaning.

9. The method of claim 8, wherein, The frequency of the ultrasonic cleaning is 35-45 kHz.

10. The method of claim 1, wherein, The water washing is performed in the form of flushing.

11. The sample preparation method of claim 1, wherein After the water washing, the argon ion polishing treatment is further performed after drying.

12. The method of claim 1, wherein, The argon ion polishing treatment adopts an argon ion beam with a purity of ≥99.999%.

13. The method of claim 1, wherein, The vacuum degree of the argon ion polishing treatment is ≤10 - 1 pa.

14. A method of detecting the carbon content in an aluminum sample by glow discharge mass spectrometry, characterized by, The detection method comprises: The aluminum sample treated by the sample preparation method according to any one of claims 1-13 is placed in a sample chamber of a glow discharge mass spectrometer, is vacuumized and is pushed into a discharge chamber, is sequentially subjected to cooling and pre-sputtering and is then detected to obtain the content of carbon elements in the aluminum sample.

15. The detection method of claim 14, wherein, the vacuuming to a vacuum degree of ≤ 5 x 10 - 7 mbar.

16. The method of claim 14, wherein, The discharge voltage of the glow discharge mass spectrometer is 1150-1250 V.

17. The method of claim 14, wherein, The discharge current of the glow discharge mass spectrometer is 2.8-3.2 mA.

18. The method of claim 14, wherein, The vacuum degree of the detection area is ≤5x10 -9 mbar.

Images