Metal oxide samples and their preparation and detection methods
By covering the metal oxide sample with high-purity graphite powder and treating it with dust-free paper, the problems of impurity interference and uneven mixing in the detection of metal oxides were solved, and high-precision elemental composition and content detection was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- NINGXIA ORIENT TANTALUM INDUSTRY CO LTD
- Filing Date
- 2025-06-18
- Publication Date
- 2026-07-17
Abstract
Description
Technical Field
[0001] This invention relates to the field of elemental measurement technology for metal oxides, specifically to a metal oxide sample for glow discharge mass spectrometry, a method for preparing the sample, and a method for detecting the metal oxide sample based on glow discharge mass spectrometry. Background Technology
[0002] Glow discharge mass spectrometry (GDMS) is an analytical method that uses a glow discharge source as an ion source connected to a mass spectrometer for mass spectrometry determination. A glow discharge mass spectrometer consists of two parts: a glow discharge ion source and a mass spectrometer. The glow discharge ion source utilizes ions generated by the ionization of inert gas at thousands of volts to bombard the sample surface, causing sputtering. The sputtered sample atoms diffuse into the plasma for further ionization, and are then collected and detected by the mass spectrometer. This process is highly dependent on the conductivity of the sample. Metal samples, due to their good conductivity, can stably serve as cathodes, ensuring continuous bombardment and uniform ionization by the inert gas. However, metal oxides are insulating materials; their insulating surfaces cannot conduct current. During inert gas bombardment, positive charges accumulate, disrupting plasma stability and causing a sharp drop in ionization efficiency. This makes it difficult to ionize metal oxides, hindering the accurate detection of their elemental composition and content.
[0003] In some scenarios, to measure the elements in metal oxides, non-conductive metal oxide powder and metal powder are mixed in a certain proportion and then pressed into sheet-like samples. The conductivity of the metal matrix is used to simulate a conductive cathode for elemental measurement. However, when the purity of the conductive metal is insufficient, exogenous impurities are introduced, interfering with elemental detection. Furthermore, it is difficult to ensure uniform dispersion of the non-conductive metal oxide powder and metal powder during mixing. Uneven mixing can easily lead to localized insulation and abnormal discharge phenomena, resulting in significant deviations in the detection results. In addition, there may be physical or chemical compatibility issues between the metal powder and the metal oxide, potentially altering the original microstructure or chemical properties of the metal oxide, thus affecting the elemental measurement results. Therefore, when using the above method to measure the elements of metal oxides, the detection accuracy of the elemental composition and content is low, and it cannot truly reflect the overall elemental distribution of the metal oxide. Summary of the Invention
[0004] To address the technical problem that the detection accuracy of elemental composition and content in metal oxides is low and cannot accurately reflect the overall elemental distribution of metal oxides, this invention aims to provide a metal oxide sample for glow discharge mass spectrometry, its preparation method, and a detection method for the metal oxide sample based on glow discharge mass spectrometry. The specific technical solutions adopted are as follows:
[0005] In a first aspect, embodiments of the present invention disclose a method for preparing metal oxide samples for a glow discharge mass spectrometer. The method includes: after cleaning a mold, placing two sheets of cleanroom paper at the bottom of the mold; aligning the ends of a two-section glass tube with the middle of the cleanroom paper at the bottom of the mold and introducing metal oxide powder into the two-section glass tube; slowly lifting the two-section glass tube at a predetermined speed to accumulate the metal oxide powder on the cleanroom paper, forming a powder pile. The powder pile is positioned within the anode cap of the glow discharge mass spectrometer. Within the excitation zone; use a plastic spoon to cover the powder pile with high-purity graphite powder to fill the empty area between the powder pile and the inner wall of the mold and to completely cover the powder pile; use a mold rod to spread the high-purity graphite powder evenly, cover it with a sheet of cleanroom paper, and then press it firmly. Place the mold into a tablet press and press it into shape, then hold the pressure; demold the sample in the mold to obtain a metal oxide sample. The metal oxide sample includes the metal oxide body and one sheet of cleanroom paper and two sheets of cleanroom paper covering the two sides of the metal oxide body. The sample surface with two sheets of cleanroom paper is the sputtering surface.
[0006] Optionally, the powder pile is a semi-ellipsoidal powder pile with a diameter of 1.5 mm to 2.5 mm, an arc of 1 / 3π rad to 1 / 2π rad, a thickness of 2.0 mm to 3.0 mm, and a diameter of the anode cap ranging from 2.0 mm to 3.0 mm.
[0007] Optionally, the purity of the high-purity graphite powder is ≥99.9999%, and the weight ratio of the metal oxide powder to the high-purity graphite powder is between 1:15 and 1:20.
[0008] Optionally, the cleanroom treatment includes wiping the mold base, mold sleeve, mold rod, and mold gasket with a cleanroom cloth, and placing two cleanroom sheets at the bottom of the mold. This includes assembling the mold base and mold sleeve, placing the mold gasket in the center of the mold base, and then placing two cleanroom sheets on top of the mold gasket.
[0009] Optionally, the inner diameter of the mold sleeve is between 20mm and 40mm, the diameter of the mold gasket is between 15mm and 20mm, the diameter of the dust-free paper is between 15mm and 20mm, the diameter of the metal oxide sample is between 20mm and 40mm, and the thickness is between 20mm and 25mm.
[0010] Optionally, the particle size of the metal oxide powder is between 0.5 μm and 3 μm, or the particle size of the metal oxide powder is between 1 μm and 5 μm.
[0011] Optionally, the upper section of the two-section glass tube has a length between 3mm and 5mm, a thickness between 0.1mm and 0.3mm, and a diameter between 2mm and 3mm; the lower section has a length between 50mm and 80mm, a diameter between 1.0mm and 2.0mm, and a thickness between 0.1mm and 0.3mm; the arc of the connection between the upper and lower sections is between 0.785rad and 1.05rad.
[0012] Optionally, after the mold is placed in the tablet press and pressed, the pressure holding value is between 20MPa and 25MPa, and the pressure holding time is between 1min and 2min.
[0013] Secondly, embodiments of the present invention disclose a metal oxide sample, which is prepared using the metal oxide sample preparation method for glow discharge mass spectrometry mentioned in the first aspect. The metal oxide sample includes a metal oxide body and one sheet of cleanroom paper and two sheets of cleanroom paper covering both sides of the metal oxide body. The sample surface with the two sheets of cleanroom paper is the sputtering surface, so as to perform glow discharge mass spectrometry tests on the powder pile area and the surrounding area of the sputtering surface using a glow discharge mass spectrometer. The metal oxide body is composed of a high-purity graphite powder area and a powder pile area of metal oxide. The powder pile area is embedded in the high-purity graphite powder area, and the powder pile area in the sputtering area is exposed outside the high-purity graphite powder area.
[0014] Thirdly, this invention discloses a method for detecting metal oxide samples based on a glow discharge mass spectrometer. The metal oxide sample is prepared using the metal oxide sample preparation method for glow discharge mass spectrometers mentioned in the first aspect. The metal oxide sample includes a metal oxide body and one sheet of cleanroom paper and two sheets of cleanroom paper covering both sides of the metal oxide body. The sample surface with the two sheets of cleanroom paper is the sputtering surface, so that glow discharge mass spectrometry can be used to perform glow discharge mass spectrometry tests on the powder accumulation area and surrounding area of the sputtering surface. The metal oxide body is composed of a high-purity graphite powder area and a powder accumulation area of metal oxide. The powder accumulation area is embedded in the high-purity graphite powder area, and the powder accumulation area is exposed in the sputtering area. Outside the high-purity graphite powder region, the detection method includes: placing a metal oxide sample on the cathode of a glow discharge mass spectrometer, wherein the sample surface containing two sheets of clean paper is used as the sputtering surface, and the powder accumulation area and surrounding area of the sputtering surface correspond to the excitable region of the anode cap of the glow discharge mass spectrometer; placing the metal oxide sample on the cathode of the glow discharge mass spectrometer, wherein the sample surface containing two sheets of clean paper is used as the sputtering surface, and the powder accumulation area and surrounding area of the sputtering surface correspond to the excitable region of the anode cap of the glow discharge mass spectrometer; removing the two sheets of clean paper from the metal oxide sample; and performing glow discharge mass spectrometry tests on the powder accumulation area and surrounding area of the sputtering surface using a glow discharge mass spectrometer.
[0015] By employing the technical solutions disclosed in this invention, the mold undergoes dust-free treatment and is padded with lint-free paper, effectively preventing external dust and impurities from contaminating the sample. This prevents deviations in detection results due to impurity contamination, ensuring the accuracy and purity of the original composition of the metal oxide sample and providing a reliable sample for subsequent glow discharge mass spectrometry testing. The two-section glass tube is slowly lifted at a predetermined speed, allowing the metal oxide powder to form a stable powder pile on the lint-free paper. Precise control of the powder pile within the excitation zone of the glow discharge mass spectrometer's anode cap not only ensures the compatibility of the formed sample with the glow discharge mass spectrometer but also enables the formed sample to achieve a uniform and stable excitation effect during detection, improving the consistency and repeatability of the detection data. High-purity graphite powder, with a purity of ≥99.9999%, covers the powder pile and fills any empty areas. This ensures minimal introduction of impurities, preventing interference with elemental detection. Furthermore, the excellent electrical conductivity of high-purity graphite enhances sample conductivity, improves electron transport efficiency during glow discharge, and stabilizes the discharge. It also reinforces the sample structure, preventing the metal oxide powder from disintegrating. Moreover, the metal oxide powder pile is encapsulated as a whole by the high-purity graphite powder, avoiding the problem of uneven mixing between metal powder and metal oxide powder in existing technologies. This prevents localized insulation and avoids impacting the accuracy of the detection results. Additionally, there are no physical or chemical compatibility issues between the high-purity graphite powder and the metal oxide, ensuring no alteration to the original microstructure or chemical properties of the metal oxide, further minimizing any impact on the accuracy of the detection results. Furthermore, the sample surface containing two sheets of clean paper serves as the sputtering surface. On this surface, the powder accumulation area of the metal oxide is exposed outside the high-purity graphite powder, providing a clear and standardized detection location for glow discharge mass spectrometry, thus improving detection efficiency and result accuracy. In this way, the metal oxide sample prepared using the above method can accurately reflect the overall elemental distribution of the metal oxide. Detailed Implementation
[0016] To further illustrate the technical means and effects adopted by the present invention to achieve its intended purpose, the following provides a detailed description of the specific implementation, structure, features, and effects of a metal oxide sample for detection by glow discharge mass spectrometry, its preparation method, and the detection method of the metal oxide sample based on glow discharge mass spectrometry. In the following description, different "one embodiment" or "another embodiment" do not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics in one or more embodiments can be combined in any suitable form.
[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.
[0018] The following describes in detail the specific scheme of a metal oxide sample for detection by glow discharge mass spectrometry, the preparation method thereof, and the detection method of the metal oxide sample based on glow discharge mass spectrometry provided by the present invention.
[0019] This invention discloses a method for preparing metal oxide samples for glow discharge mass spectrometry, comprising the following steps:
[0020] a) After cleaning the mold, place two sheets of cleanroom paper at the bottom of the mold.
[0021] b) Align the end of the two-section glass tube with the middle of the lint-free paper at the bottom of the mold and pour metal oxide powder into the two-section glass tube. Slowly lift the two-section glass tube at a predetermined speed to accumulate the metal oxide powder on the lint-free paper to form a powder pile. The powder pile is located in the excitation region of the anode cap of the glow discharge mass spectrometer.
[0022] c) Use a plastic spoon to cover the top of the powder pile with high-purity graphite powder to fill the empty area between the powder pile and the inner wall of the mold and to completely cover the powder pile.
[0023] d) Spread the high-purity graphite powder evenly using the mold rod, cover the high-purity graphite powder with a piece of dust-free paper, press it firmly, put the mold into the tablet press, press it into shape, and then hold the pressure.
[0024] e) Demold the sample in the mold to obtain a metal oxide sample. The metal oxide sample includes a metal oxide body and one sheet of cleanroom paper and two sheets of cleanroom paper covering both sides of the metal oxide body. The sample side of the metal oxide sample with the two sheets of cleanroom paper is the sputtering side.
[0025] Specifically, the metal oxides in the embodiments of the present invention include, but are not limited to: iron oxides, such as Fe2O3, copper oxides, such as CuO and Cu2O, tantalum oxides, such as Ta2O5, aluminum oxides, such as Al2O3, and niobium oxides, such as Nb2O5.
[0026] In a further embodiment of the present invention, when preparing the metal oxide sample, preliminary preparation is first performed, which mainly involves preparing the following components:
[0027] The mold, which can be made of coated stainless steel or hard alloy, includes a mold sleeve, a mold gasket, a mold rod, and a mold base. The inner diameter of the mold sleeve is 20mm to 40mm. The mold gasket is a solid circular gasket with a diameter of 15mm to 20mm and a thickness of 10mm to 12mm. The diameter of the mold rod is smaller than the inner diameter of the mold sleeve. The mold base supports the mold sleeve and the mold gasket.
[0028] Cleanroom wipes: Cleanroom wipes can be soaked in 75% alcohol for disinfection. The size of the cleanroom wipes can be from 100mm*100mm to 120mm*120mm. They are used to disinfect and remove dust from molds.
[0029] High-purity graphite powder: purity ≥ 99.9999%.
[0030] Metal oxide 1: Particle size range: 0.5 μm to 3 μm. This metal oxide 1 is non-conductive and refractory.
[0031] Metal oxide 2: Particle size range: 1 μm to 5 μm. This metal oxide 2 is non-conductive and refractory.
[0032] Tableting machine: hydraulic or manual press (pressure range: 5 to 20 tons).
[0033] Auxiliary tools: plastic tweezers, plastic gloves, lint-free cloth (100mm*100mm to 120mm*120mm), nitrile gloves, lint-free paper (diameter: 15mm to 20mm, thickness: 0.05mm to 0.1mm), two-section glass tube (divided into two sections: upper section: length 3mm to 5mm, thickness 0.1mm to 0.3mm, diameter 2mm to 3mm; lower section: length 50mm to 80mm, diameter 1.0mm to 2.0mm, thickness 0.1mm to 0.3mm, with the arc between the upper and lower sections being 1 / 4πrad to 1 / 3πrad to prevent non-metallic powder from remaining inside the glass tube), alcohol (75%, cleaning agent), 5% nitric acid (ρ = 1.42g / mL, analytical grade).
[0034] Furthermore, after completing the preliminary preparations, the mold undergoes a dust-free treatment. Specifically, the mold base, mold sleeve, mold rod, and mold gasket are wiped clean with a lint-free cloth dampened with alcohol. The mold sleeve and mold base are then assembled, and the mold gasket is placed at the center of the bottom of the mold base. Two sheets of lint-free paper are then placed on top of the mold gasket. In an optional embodiment of this invention, the inner diameter of the mold sleeve is between 20mm and 40mm, the diameter of the mold gasket is between 15mm and 20mm, and the diameter of the lint-free paper is between 15mm and 20mm. This dust-free treatment of the mold and the placement of lint-free paper effectively prevents external dust and impurities from contaminating the sample, preventing deviations in the detection results due to impurities, ensuring the accuracy and purity of the original composition of the metal oxide sample, and providing a reliable sample for subsequent glow discharge mass spectrometry testing.
[0035] Furthermore, after assembling the mold, the outlet of the two-section glass tube is aligned with the bottom of the mold. Metal oxide powder is added through the inlet of the upper section of the two-section glass tube. After the metal oxide powder is added, the two-section glass tube is slowly withdrawn at a predetermined speed, and the metal oxide powder is piled up on lint-free paper to form a powder pile to prevent it from scattering. The diameter of the powder pile is within the diameter range of the anode cap, and the predetermined speed can be 1 mm / s. In an optional embodiment of the invention, the upper section of the two-section glass tube has a length between 3 mm and 5 mm, a thickness between 0.1 mm and 0.3 mm, and a diameter between 2 mm and 3 mm; the lower section has a length between 50 mm and 80 mm, a diameter between 1.0 mm and 2.0 mm, and a thickness between 0.1 mm and 0.3 mm. The arc of the connection between the upper and lower sections is between 0.785 rad and 1.05 rad. The powder pile is a semi-ellipsoidal powder pile with a diameter ranging from 1.5 mm to 2.5 mm, an arc ranging from 1 / 3π rad to 1 / 2π rad, and a thickness ranging from 2.0 mm to 3.0 mm. The diameter of the anode cap ranges from 2.0 mm to 3.0 mm. Thus, when pouring metal oxide powder into the bottom of the mold, the arc-designed connection of the two-section glass tube reduces the dead angles for powder accumulation that are easily created by right-angle structures, allowing the powder to flow out of the glass tube more smoothly. This avoids powder residue clogging the pipes, ensuring that the powder can be poured into the mold at a stable flow rate and in a stable state. This maintains the stability and controllability of the powder pile formation process, providing a guarantee for obtaining the required powder pile morphology. During the flow of metal oxide powder, it is prone to splashing due to collisions at right-angle joints. The curved design buffers the impact of the flowing metal oxide powder, guiding it through the joints more smoothly and reducing the probability of outward splashing. This ensures precise powder accumulation on the cleanroom paper at the bottom of the mold while preventing powder loss and contamination of the operating environment, maintaining the cleanliness of the operating space and meeting cleanroom requirements. Furthermore, the semi-ellipsoidal structure allows the metal oxide powder to naturally converge towards the center during accumulation, forming a symmetrical and stable shape, effectively avoiding problems of excessively thick or thin local accumulation. This uniform powder distribution ensures consistent internal stress during subsequent high-purity graphite powder coating and pressurization, improving sample density and structural uniformity, providing a more stable sample for glow discharge mass spectrometry. The semi-ellipsoidal powder stack better matches the shape of the excitable region of the anode cap in the glow discharge mass spectrometer. Compared to irregular shapes, its rounded contours and symmetrical structure allow the sample to obtain a more uniform electric field distribution in the excitation region, ensuring the stability of the glow discharge process, enhancing ion excitation efficiency, thereby improving the intensity and stability of the mass spectrometry detection signal, and improving the accuracy and reliability of the detection data.
[0036] Furthermore, after adding the metal oxide into the mold, a certain amount of high-purity graphite powder is slowly covered on top of the powder pile formed by the metal oxide using a plastic sheet, ensuring close contact and encapsulation of the metal oxide powder pile. The high-purity graphite powder is then spread evenly using a mold rod, and a 15mm to 20mm dust-free paper is placed on top. The mold rod is rotated and inserted into the mold sleeve to compact the graphite powder. In an optional embodiment of this invention, the purity of the high-purity graphite powder is ≥99.9999%, and the weight ratio of the metal oxide powder to the high-purity graphite powder is between 1:15 and 1:20. This ensures that the purity of the high-purity graphite powder is greater than or equal to 99.9999%, preventing the introduction of excessive impurities and avoiding interference with element detection. Furthermore, the high-purity graphite powder has excellent electrical conductivity, which not only enhances the conductivity of the sample and improves the electron transport efficiency during glow discharge, making the discharge more stable, but also strengthens the structure of the formed sample, preventing the metal oxide powder from becoming loose. By spreading high-purity graphite powder with a mold rod, covering it with dust-free paper and compacting it, the sample has uniform density and a dense structure, eliminating internal voids and stress concentration, ensuring the uniformity of the sample's physical properties, and further improving the sensitivity and resolution of glow discharge mass spectrometry, providing high-quality samples for accurate analysis of metal oxide composition.
[0037] Furthermore, after compacting the high-purity graphite powder inside the mold using a mold rod, the mold is placed in a tablet press, the drain valve is tightened, and pressure is applied by shaking the pressure handle to form the tablet and then hold the pressure. The pressure applied by shaking the pressure handle is 20MPa to 25MPa, and the holding time is 1 to 2 minutes. Then, the drain valve is released, the mold is removed, the bottom of the mold is removed, a demolding tool is installed, and the assembled demolding tool is placed in a sample press. The sample is ejected from the mold using the sample press screw. The mold is removed from the tablet press, the demolding tool is removed, and the metal oxide sample is removed from the mold. The sample side containing two sheets of lint-free paper is used as the test area. In the metal oxide sample obtained in this embodiment of the invention, the metal oxide sample includes a metal oxide body and one and two sheets of cleanroom paper covering both sides of the metal oxide body. The sample surface with the two sheets of cleanroom paper is the sputtering surface, so that the powder pile area and surrounding area of the sputtering surface can be tested by glow discharge mass spectrometry. The metal oxide body is composed of a high-purity graphite powder area and a powder pile area of metal oxide. The high-purity graphite powder area is embedded in the powder pile area, and the powder pile area in the sputtering area is exposed outside the high-purity graphite powder area. For example, this embodiment of the invention obtains a semi-ellipsoidal powder pile of circular graphite with a diameter of 20 mm to 40 mm and a thickness of 20 mm to 25 mm, in which metal oxide 1 or metal oxide 2 is embedded. In the circular metal oxide sample, the diameter of the semi-ellipsoidal powder pile of metal oxide is 1.5 mm to 2.5 mm, and the thickness is 2 mm to 3 mm. The arc of the graphite-embedded semi-ellipsoidal powder pile is 1 / 3π rad to 1 / 2π rad, sufficient for 10 to 15 excitations with stable signal. Thus, the semi-ellipsoidal powder pile of circular graphite embedded with metal oxide avoids the problem of uneven mixing between high-purity graphite powder and metal oxide powder, preventing local insulation and avoiding impact on the accuracy of the detection results. Furthermore, there are no physical or chemical compatibility issues between high-purity graphite powder and metal oxide, and it does not change the original microstructure or chemical properties of the metal oxide, further avoiding impact on the accuracy of the detection results. Moreover, using the sample surface with two sheets of clean paper as the sputtering surface, the bottom surface of the metal oxide powder pile in this sample surface is exposed outside the high-purity graphite powder, providing a clear and standardized detection position for glow discharge mass spectrometry, which helps improve detection efficiency and result accuracy. Thus, the metal oxide samples prepared in the above manner can truly reflect the overall elemental distribution of the metal oxide.
[0038] Furthermore, "powder pile and its surroundings" refers to the powder pile region and the surrounding area around the boundary of the powder pile region. The boundary of the surrounding area surrounds the boundary of the powder pile region, and the distance between the boundary of the surrounding area and the boundary of the powder pile region can be 2 mm. Of course, the surrounding area can also be determined according to the diameter of the anode cap of the glow discharge mass spectrometer, which is not limited in this embodiment of the invention.
[0039] By employing the technical solutions disclosed in this invention, the mold undergoes dust-free treatment and is padded with lint-free paper, effectively preventing external dust and impurities from contaminating the sample. This prevents deviations in detection results due to impurity contamination, ensuring the accuracy and purity of the original composition of the metal oxide sample and providing a reliable sample for subsequent glow discharge mass spectrometry testing. The two-section glass tube is slowly lifted at a predetermined speed, allowing the metal oxide powder to form a stable powder pile on the lint-free paper. Precise control of the powder pile within the excitation zone of the glow discharge mass spectrometer's anode cap not only ensures the compatibility of the formed sample with the glow discharge mass spectrometer but also enables the formed sample to achieve a uniform and stable excitation effect during detection, improving the consistency and repeatability of the detection data. High-purity graphite powder, with a purity of ≥99.9999%, covers the powder pile and fills any empty areas. This ensures minimal introduction of impurities, preventing interference with elemental detection. Furthermore, the excellent electrical conductivity of high-purity graphite enhances sample conductivity, improves electron transport efficiency during glow discharge, and stabilizes the discharge. It also reinforces the sample structure, preventing the metal oxide powder from disintegrating. Moreover, the metal oxide powder pile is encapsulated as a whole by the high-purity graphite powder, avoiding the problem of uneven mixing between metal powder and metal oxide powder in existing technologies. This prevents localized insulation and avoids impacting the accuracy of the detection results. Additionally, there are no physical or chemical compatibility issues between the high-purity graphite powder and the metal oxide, ensuring no alteration to the original microstructure or chemical properties of the metal oxide, further minimizing any impact on the accuracy of the detection results. Furthermore, the sample surface containing two sheets of clean paper serves as the sputtering area. The bottom surface of the metal oxide powder pile in this sample surface is exposed outside the high-purity graphite powder, providing a clear and standardized detection location for glow discharge mass spectrometry, thus improving detection efficiency and result accuracy. In this way, the metal oxide sample prepared using the above method can accurately reflect the overall elemental distribution of the metal oxide.
[0040] To further understand the present invention, the preparation method of the metal oxide sample for glow discharge mass spectrometry provided by the present invention will be described in detail below with reference to the embodiments. The scope of protection of the present invention is not limited by the following embodiments.
[0041] Example 1
[0042] 1) Using a 100*100mm lint-free cloth dampened with alcohol, clean the mold base, mold sleeve, mold rod, and mold gasket. Assemble the mold sleeve and mold base. Place the mold gasket in the center of the bottom of the mold base, and then place two 20mm diameter lint-free sheets on top of the mold gasket. The inner diameter of the mold sleeve is 40mm, and the diameter of the mold gasket is 20mm.
[0043] 2) 0.10g of metal oxide 1 is slowly introduced into the dust-free paper of the mold gasket in step 1) through a two-section glass tube with an upper section length of 5mm, a thickness of 0.2mm, and a diameter of 2mm; and a lower section length of 80mm, a diameter of 1mm, and a thickness of 0.2mm, with an intermediate arc of 0.785rad between the upper and lower sections. Then, the two-section glass tube is slowly pulled out at a speed of 1mm / s to form a semi-ellipsoidal powder pile of metal oxide 1 with a diameter of 2mm, an arc of 1 / 2πrad, and a thickness of 2mm.
[0044] 3) Using a plastic sheet, slowly cover the semi-ellipsoidal powder pile formed by metal oxide 1 with a certain amount of high-purity graphite powder (99.9999% purity) on top of the semi-ellipsoidal powder pile obtained in step 2). The weight ratio of metal oxide 1 to high-purity graphite powder is controlled at 1:15. After spreading the high-purity graphite powder evenly with a mold rod, place a 20mm dust-free paper on it, rotate the mold rod, and insert it to compact the graphite powder.
[0045] 4) Place the mold obtained in step 3) into the tablet press, tighten the drain valve, and pressurize by shaking the pressure handle to form the tablet and then hold the pressure. The pressure applied by shaking the pressure handle is 20 MPa, and the holding time is 1 minute. Then loosen the drain valve, remove the mold, remove the bottom of the mold, install the demolding tool, place the assembled demolding tool into the sample press, and use the sample press screw to eject the sample from the mold; remove the mold from the tablet press, remove the demolding tool, and remove the metal oxide sample from the mold; remove the sample surface containing two sheets of dust-free paper from the metal oxide sample as the test area. Finally, a circular metal oxide sample with a diameter of 40 mm and a thickness of 20 mm is obtained, consisting of a semi-ellipsoidal powder pile of graphite embedded with metal oxide 1. The diameter and thickness of the semi-ellipsoidal powder pile of metal oxide 1 in the circular metal oxide sample are 2 mm, and the arc of the semi-ellipsoidal powder pile of graphite embedded with metal oxide 1 is 1 / 2π rad.
[0046] Example 2
[0047] 1) Using a 120mm*120mm lint-free cloth dampened with alcohol, clean the mold base, mold sleeve, mold rod, and mold gasket. Assemble the mold sleeve and mold base. Place the mold gasket in the center of the bottom of the mold base, and then place two 15mm diameter lint-free sheets on top of the mold gasket. The inner diameter of the mold sleeve is 30mm, and the diameter of the mold gasket is 15mm.
[0048] 2) 0.125g of metal oxide 2 is slowly introduced into the dust-free paper of the mold gasket in step 1) through a two-section glass tube with an upper section of 4mm length, 0.1mm thickness, and 3mm diameter; and a lower section of 60mm length, 1mm diameter, and 0.1mm thickness, with the upper and lower sections connected by an arc of 1 / 3πrad. Then, the two-section glass tube is slowly pulled out at a speed of 1mm / s to form a semi-ellipsoidal powder pile of metal oxide 2 with a diameter of 2.5mm, an arc of 1 / 4πrad, and a thickness of 3mm.
[0049] 3) Using a plastic sheet, slowly cover the semi-ellipsoidal powder pile formed by metal oxide 2 with a certain amount of high-purity graphite powder (99.9999% purity) on top of the semi-ellipsoidal powder pile obtained in step 2). The weight ratio of metal oxide 2 to high-purity graphite powder is controlled at 1:20. After spreading the high-purity graphite powder evenly with a mold rod, place a sheet of 15mm diameter dust-free paper on top, rotate the mold rod, and insert it to compact the high-purity graphite powder.
[0050] 4) Place the mold obtained in step 3) into the tablet press, tighten the drain valve, and pressurize by shaking the pressure handle to form the tablet and then hold the pressure. The pressure applied by shaking the pressure handle is 25 MPa, and the holding time is 2 minutes. Then loosen the drain valve, remove the mold, remove the bottom of the mold, install the demolding tool, place the assembled demolding tool into the sample press, and use the sample press screw to eject the sample from the mold; remove the mold from the tablet press, remove the demolding tool, and remove the metal oxide sample from the mold; remove the sample surface containing two sheets of dust-free paper from the metal oxide sample as the test area. Finally, a circular metal oxide sample with a diameter of 30 mm and a thickness of 20 mm is obtained, consisting of a semi-ellipsoidal powder pile of graphite embedded with metal oxide 2. The diameter of the semi-ellipsoidal powder pile of metal oxide 2 in the circular metal oxide sample is 2.5 mm, the thickness is 3 mm, and the arc of the semi-ellipsoidal powder pile of graphite embedded with metal oxide 2 is 1 / 4π rad.
[0051] Furthermore, based on the same inventive concept, this embodiment of the invention also provides a metal oxide sample. The metal oxide sample is prepared using the metal oxide sample preparation method for glow discharge mass spectrometry described above. The metal oxide sample includes a metal oxide body and one sheet of cleanroom paper and two sheets of cleanroom paper covering both sides of the metal oxide body. The sample surface with the two sheets of cleanroom paper is the sputtering surface, so that glow discharge mass spectrometry can be used to perform glow discharge mass spectrometry tests on the powder accumulation area and the surrounding area of the sputtering surface. The metal oxide body is composed of a high-purity graphite powder area and a powder accumulation area of metal oxide. The powder accumulation area is embedded in the high-purity graphite powder area, and the powder accumulation area in the sputtering area is exposed outside the high-purity graphite powder area.
[0052] Specifically, the surrounding area refers to the area surrounding the boundary of the powder pile area. The boundary of the surrounding area surrounds the boundary of the powder pile area, and the distance between the boundary of the surrounding area and the boundary of the powder pile area is 2 mm. Of course, the surrounding area can also be determined according to the diameter of the anode cap of the glow discharge mass spectrometer, which is not limited in this embodiment of the invention.
[0053] It should be noted that the metal oxide sample in the embodiments of the present invention and the metal oxide sample preparation method for glow discharge mass spectrometer in the above embodiments belong to the same inventive concept. The similarities or beneficial effects of the embodiments can be referred to each other, and the embodiments of the present invention will not be repeated here.
[0054] To further understand the present invention, the metal oxide samples provided by the present invention will be described in detail below with reference to the embodiments. The scope of protection of the present invention is not limited by the following embodiments.
[0055] Example 1
[0056] A circular metal oxide sample containing a semi-ellipsoidal powder pile of graphite embedded with metal oxide 1, with a diameter of 40 mm and a thickness of 20 mm. The semi-ellipsoidal powder pile of metal oxide 1 in the circular metal oxide sample has a diameter of 2 mm and a thickness of 2 mm, and the radian of the semi-ellipsoidal powder pile of graphite embedded with metal oxide 1 is 1 / 2π rad.
[0057] Example 2
[0058] A circular metal oxide sample containing a semi-ellipsoidal powder pile of graphite embedded with metal oxide 2, with a diameter of 30 mm and a thickness of 20 mm. The diameter of the semi-ellipsoidal powder pile of metal oxide 2 in the circular metal oxide sample is 2.5 mm and the thickness is 3 mm. The radian of the semi-ellipsoidal powder pile of graphite embedded with metal oxide 2 is 1 / 4π rad.
[0059] Furthermore, based on the same inventive concept, this embodiment of the invention also provides a method for detecting metal oxide samples using a glow discharge mass spectrometer. The metal oxide sample is prepared using the metal oxide sample preparation method for glow discharge mass spectrometer described above. The metal oxide sample includes a metal oxide body and one sheet of cleanroom paper and two sheets of cleanroom paper covering both sides of the metal oxide body. The sample surface with the two sheets of cleanroom paper is the sputtering surface, so that glow discharge mass spectrometry can be used to perform glow discharge mass spectrometry tests on the powder accumulation area and surrounding area of the sputtering surface. The metal oxide body consists of a high-purity graphite powder area and a powder accumulation area of metal oxide. The powder accumulation area is embedded in the high-purity graphite powder area, and the powder accumulation area in the sputtering area is exposed outside the high-purity graphite powder area. The method for detecting metal oxide samples using a glow discharge mass spectrometer includes:
[0060] a) Place the metal oxide sample on the cathode of the glow discharge mass spectrometer, wherein the sample side of the metal oxide sample containing two sheets of clean paper is used as the sputtering surface, and the powder accumulation area in the sputtering area corresponds to the excitable area of the anode cap of the glow discharge mass spectrometer.
[0061] b) Remove two sheets of clean paper from the metal oxide sample.
[0062] c) Glow discharge mass spectrometry was used to perform glow discharge mass spectrometry tests on the powder accumulation area and surrounding area of the sputtered surface.
[0063] Specifically, before testing metal oxide samples, they can be cleaned with 5% nitric acid to ensure that the surface of the metal oxide samples is clean and free of impurities and contaminants, thereby avoiding interference with the detection results of the glow discharge mass spectrometer and improving the detection accuracy of the glow discharge mass spectrometer.
[0064] It is worth noting that the specific implementation process for detecting the elemental content and composition of metal oxides using glow discharge mass spectrometry can be found in known technologies, and will not be repeated here. It should be noted that the metal oxide sample in this embodiment of the invention and the metal oxide sample preparation method for glow discharge mass spectrometry in the above embodiments belong to the same inventive concept. The similarities or beneficial effects of the embodiments can be referred to each other, and will not be repeated here.
[0065] It should be noted that the order of the above embodiments of the present invention is merely for descriptive purposes and does not represent the superiority or inferiority of the embodiments. In some embodiments, multitasking and parallel processing are also possible or may be advantageous.
[0066] The various embodiments in this specification are described in a progressive manner. The same or similar parts between the various embodiments can be referred to each other. Each embodiment focuses on describing the differences from other embodiments.
Claims
1. A method for preparing metal oxide samples for glow discharge mass spectrometry, characterized in that, The method for preparing metal oxide samples for glow discharge mass spectrometry includes: After the mold is cleaned, two sheets of clean paper are placed at the bottom of the mold. Align the ends of the two-section glass tube with the middle of the dust-free paper at the bottom of the mold and introduce metal oxide powder into the two-section glass tube. Slowly pick up the two-section glass tube at a predetermined speed and pile the metal oxide powder on the dust-free paper to form a powder pile. The powder pile is located in the excitable region of the anode cap of the glow discharge mass spectrometer. Use a plastic spoon to cover the powder pile with high-purity graphite powder to fill the empty area between the powder pile and the inner wall of the mold and to completely cover the powder pile. The high-purity graphite powder is spread evenly using a mold rod, covered with a sheet of dust-free paper, and then pressed firmly. The mold is then placed in a tablet press and pressed to form the shape, and the pressure is maintained. The sample in the mold is demolded to obtain a metal oxide sample sheet. The metal oxide sample sheet includes a metal oxide body and one sheet of cleanroom paper and two sheets of cleanroom paper covering both sides of the metal oxide body. The sample sheet surface on which the two sheets of cleanroom paper are placed is the sputtering surface, and the powder pile and the surrounding area are the sputtering area. The two-section glass tube is divided into two sections. The upper section has a length between 3 mm and 5 mm, a thickness between 0.1 mm and 0.3 mm, and a diameter between 2 mm and 3 mm. The lower section has a length between 50 mm and 80 mm, a diameter between 1.0 mm and 2.0 mm, and a thickness between 0.1 mm and 0.3 mm. The arc of the connection between the upper and lower sections is between 0.785 rad and 1.05 rad.
2. The method for preparing metal oxide samples for glow discharge mass spectrometry according to claim 1, characterized in that, The powder pile is a semi-ellipsoidal powder pile with a diameter of 1.5 mm to 2.5 mm, an arc of 1 / 3πrad to 1 / 2πrad, and a thickness of 2.0 mm to 3.0 mm. The diameter of the anode cap is 2.0 mm to 3.0 mm.
3. The method for preparing metal oxide samples for glow discharge mass spectrometry according to claim 1, characterized in that, The purity of the high-purity graphite powder is ≥99.9999%, and the weight ratio of the metal oxide powder to the high-purity graphite powder is between 1:15 and 1:
20.
4. The method for preparing metal oxide samples for glow discharge mass spectrometry according to claim 1, characterized in that, The dust-free treatment includes wiping the mold base, mold sleeve, mold rod, and mold gasket with a dust-free cloth, and placing two sheets of dust-free paper at the bottom of the mold. Assemble the mold base and mold sleeve, insert a mold gasket at the center of the mold base, and then place two sheets of dust-free paper on top of the mold gasket.
5. The method for preparing metal oxide samples for glow discharge mass spectrometry according to claim 4, characterized in that, The inner diameter of the mold sleeve is between 20 mm and 40 mm, the diameter of the mold gasket is between 15 mm and 20 mm, the diameter of the dust-free paper is between 15 mm and 20 mm, the diameter of the metal oxide sample is between 20 mm and 40 mm, and the thickness is between 20 mm and 25 mm.
6. The method for preparing metal oxide samples for glow discharge mass spectrometry according to claim 1, characterized in that, The particle size of the metal oxide powder is between 0.5 μm and 3 μm, or the particle size of the metal oxide powder is between 1 μm and 5 μm.
7. The method for preparing metal oxide samples for glow discharge mass spectrometry according to claim 1, characterized in that, After the mold is placed in the tablet press and pressed, the holding pressure is between 20 MPa and 25 MPa, and the holding time is between 1 min and 2 min.
8. A metal oxide sample, characterized in that, The metal oxide sample is prepared using the metal oxide sample preparation method for glow discharge mass spectrometry according to any one of claims 1-7. The metal oxide sample includes a metal oxide body and one sheet of cleanroom paper and two sheets of cleanroom paper covering both sides of the metal oxide body. The sample surface on which the two sheets of cleanroom paper are placed is the sputtering surface, so that glow discharge mass spectrometry can be used to perform glow discharge mass spectrometry tests on the powder accumulation area and the surrounding area of the sputtering surface. The metal oxide body is composed of a high-purity graphite powder area and a powder accumulation area of metal oxide. The powder accumulation area is embedded in the high-purity graphite powder area, and the powder accumulation area in the sputtering area is exposed outside the high-purity graphite powder area.
9. A method for detecting metal oxide samples based on glow discharge mass spectrometry, characterized in that, The metal oxide sample is prepared using the metal oxide sample preparation method for glow discharge mass spectrometry according to any one of claims 1-7. The metal oxide sample includes a metal oxide body and one sheet of cleanroom paper and two sheets of cleanroom paper corresponding to both sides of the metal oxide body. The sample surface on which the two sheets of cleanroom paper are placed is the sputtering surface, so that glow discharge mass spectrometry can be used to perform glow discharge mass spectrometry testing on the powder accumulation region of the sputtering surface. The metal oxide body is composed of a high-purity graphite powder region and a powder accumulation region of metal oxide. The powder accumulation region is embedded within the high-purity graphite powder region, and the powder accumulation region is exposed outside the high-purity graphite powder region in the sputtering region. The detection method includes: A metal oxide sample is placed on the cathode of a glow discharge mass spectrometer. The sample surface containing two sheets of clean paper is used as the sputtering surface. The powder accumulation area in the sputtering surface corresponds to the excitable region of the anode cap of the glow discharge mass spectrometer. Remove two sheets of clean paper from the metal oxide sample; The powder pile and surrounding area in the sputtered surface were tested using glow discharge mass spectrometry.