CN115524390A - Glow discharge mass spectrum detection method for niobium powder - Google Patents

Glow discharge mass spectrum detection method for niobium powder Download PDF

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CN115524390A
CN115524390A CN202211203594.7A CN202211203594A CN115524390A CN 115524390 A CN115524390 A CN 115524390A CN 202211203594 A CN202211203594 A CN 202211203594A CN 115524390 A CN115524390 A CN 115524390A
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cleaning
sample
solution
niobium
rinsing
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姚力军
潘杰
叶科奇
钟伟华
石春红
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Ningbo Jiangfeng Electronic Material Co Ltd
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Ningbo Jiangfeng Electronic Material Co Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/68—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using electric discharge to ionise a gas
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/34—Purifying; Cleaning

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  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention provides a glow discharge mass spectrometry detection method of niobium powder, which comprises the following steps: loading niobium powder into an indium sheet with sample loading pits, and carrying out static pressure on the niobium powder to obtain a niobium sample; the niobium sample is sequentially cooled and sputtered in a glow discharge mass spectrum, the discharge voltage is 1.4-1.6 KV, the discharge current is 1.8-2.2 mA in a direct current mode, the resolution of the instrument is adjusted to 3400-4000, the signal intensity of the element to be detected is collected, and the mass fraction of the element to be detected is calculated by applying a relative sensitivity factor; the detection method avoids the introduction of impurities as much as possible in the sample preparation process, so that the detection degree of a sample to be detected is higher, the precision of glow discharge mass spectrometry is higher, and the purity of the niobium alloy for the target is ensured.

Description

Glow discharge mass spectrum detection method for niobium powder
Technical Field
The invention belongs to the technical field of sample analysis and detection, and particularly relates to a glow discharge mass spectrometry detection method for niobium powder.
Background
Niobium is an off-white metal with a melting point of 2468 ℃, a boiling point of 4742 ℃ and a density of 8.57g/cm 3 High purity niobium metal having paramagnetic properties is more ductile but will vary with impurity levelsThe niobium alloy used for sputtering target material has purity requirement higher than 99.95%, and because of small crystal grain size, good recrystallization texture and three axial consistencies, the oxide film formed by the material as cathode sputtering target material has uniform quality, does not react with other substances in the air, has lasting protection effect and is widely applied to optical fibers, semiconductor wafers and integrated circuits, and has wide prospect in thin film solar cells and displays; however, since the niobium powder absorbs oxygen during the sintering process, the sintered molybdenum-niobium green body has high oxygen content and low density, and therefore, the detection accuracy of the niobium alloy needs to reach a high level to meet the requirement of the purity of the target material.
Glow Discharge Mass Spectrometry (GDMS) belongs to a direct solid analysis technology, has the advantages of high sensitivity, high resolution, small matrix effect, full-element analysis and the like, is the best means for analyzing high-purity metal solid samples, and is suitable for analyzing high-purity metal niobium for target materials. At present, the most used glow discharge mass spectra internationally comprise Nu Astrum, element GD, VG9000 and the like, wherein the Nu Astrum and the VG9000 are refrigerated by liquid nitrogen and can reach-180 ℃ at the lowest, and the method is relatively suitable for testing low-melting-point samples. GDMS provides information on various elements by allowing direct detection of inorganic powders, coatings/substrates, and non-conductive materials with little sample preparation. Concentration information of main elements and trace elements including the plating layer and the substrate can be provided.
CN110542604B discloses a pretreatment method for high-purity indium sample for glow discharge mass spectrometry, which comprises the steps of firstly carrying out ultrasonic corrosion on a high-purity indium sample to be detected, then carrying out ultrasonic cleaning and blow-drying on the corroded sample in sequence, placing the blow-dried sample between two nonmetal hard plates, acting an external force on the nonmetal hard plate at the upper part to ensure that the sample generates a plane at the bottom of the sample after being extruded, continuously acting the external force on the hard plate at the upper part until the plane at the bottom of the sample is continuously enlarged to meet the size required by a glow discharge mass spectrometer test, stopping the external force, taking out a sheet-shaped sample between the two nonmetal hard plates, and cleaning and blow-drying the sheet to obtain a sample sheet to be detected which meets the test requirement.
CN103884772A discloses a method for determining trace impurities in high-purity indium, which comprises the steps of: (1) Cutting the sample into pieces, cleaning oil stain on the surface of the sample with toluene, cleaning with ultrapure water, corroding with 50% (volume concentration) nitric acid for 8min, repeatedly washing with ultrapure water, storing in methanol, taking out before analysis, and drying under an infrared lamp. (2) Putting a sample into a sample clamp, pushing the sample into an ion source cavity, adjusting the discharge voltage and the discharge current to be 0.9-1.2 kV and 40-45 mA respectively when the vacuum degree reaches 2.2-2.4 mbar, and sputtering for about 30-40 min, generally taking the signal stability of Na, fe and Ca which are easy to introduce pollution as the standard, so as to eliminate the possible pollution in the sample preparation process. (3) Adjusting the discharge voltage to be 0.9-1.2 kV and the discharge current to be 40-45 mA, performing high-voltage discharge, collecting an ion signal of an element to be detected, and calculating the concentration of the impurity element to be detected according to the quantitative analysis principle of a glow discharge mass spectrometer. The method is simple and easy to operate, has less interference and short flow, can well meet the requirement of measuring trace impurities in high-purity indium, but is more complex, and the cleaning solution also has potential harm to human bodies.
CN114034762A discloses a testing method for glow discharge mass spectrometry detection of low melting point materials, comprising the following steps: step one, manufacturing a metal carrier; step two, obtaining a treated metal carrier; step three, obtaining a liquid low-melting-point material, and then pouring a proper amount of the liquid low-melting-point material into the circular groove; step four, sequentially rinsing the surface of the solidified sample to be detected with deionized water and ethanol for three times, then naturally airing and filling the sample into a sample cup; and step five, after the ion source chamber is cooled, the sample cup is connected with the electrode and pushed into the ion source chamber, and impurity components of the sample cup are detected. The method avoids complex pretreatment, thereby improving the analysis efficiency, avoiding impurity interference caused by pretreatment in the analysis of the components of the high-purity low-melting-point material, and ensuring the accuracy of the analysis result; however, there is room for improvement in the effect of removing the impurity elements.
Therefore, it is necessary to develop a glow discharge mass spectrometry detection method for niobium alloy with higher purity requirement.
Disclosure of Invention
Aiming at the problems of complicated steps, poor cleaning effect, incomplete impurity removal and the like in the prior art, the invention provides a glow discharge mass spectrometry detection method for niobium powder, which ensures that pollution is not introduced as much as possible in the sample preparation process, thereby carrying out high-precision analysis on impurity elements of the niobium powder.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a glow discharge mass spectrometry detection method of niobium powder, which comprises the following steps:
and loading the niobium powder into an indium sheet with a sample loading pit, and carrying out static pressure on the niobium powder to obtain a niobium sample. The niobium sample is sequentially cooled and sputtered in a glow discharge mass spectrum, the discharge voltage is 1.4-1.6 KV, the discharge current is 1.8-2.2 mA in a direct current mode, the resolution of the instrument is adjusted to 3400-4000, the signal intensity of the element to be detected is collected, and the mass fraction of the element to be detected is calculated by applying a relative sensitivity factor.
The glow discharge mass spectrometry detection method of the niobium powder provided by the invention adopts the indium sheet as the niobium powder carrier to be detected, has low indium melting point, is suitable for processing various shapes, is not easy to react with high-melting-point metal, is easy to be distinguished from niobium during testing, is not easy to cause result error, can obtain stronger test signals by setting the test parameters during glow discharge mass spectrometry testing, has high sensitivity, and can ensure that the element test accuracy can reach ppb level.
In the glow discharge mass spectrometry detection method of niobium powder provided by the invention, the sputtering of the niobium sample is performed in a direct current mode, the discharge voltage is 1.4-1.6 KV, for example, 1.4KV, 1.45KV, 1.5KV, 1.55KV or 1.6KV, but is not limited to the enumerated values, other non-enumerated values in the numerical range are also applicable, the discharge current is 1.8-2.2 mA, for example, 1.8mA, 1.9mA, 2.0mA, 2.1mA or 2.2mA, but is not limited to the enumerated values, other non-enumerated values in the numerical range are also applicable, and the instrument resolution is adjusted to be 3400-3400, 3500, 3600, 3700, 3800, 3900 or 4000, but is not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
Preferably, the loading wells have a diameter of 0.6 to 0.8mm, for example 0.6mm, 0.65mm, 0.7mm, 0.75mm or 0.8mm, but are not limited to the values listed and other values not listed in this range are equally applicable.
Preferably, the depth of the loading wells is 0.25 to 0.35mm, for example 0.25mm, 0.28mm, 0.3mm, 0.32mm or 0.35mm, but is not limited to the values listed, and other values not listed within this range are equally applicable.
In the invention, in order to avoid introducing pollution, the sample preparation process is carried out in a fume hood, the purity of the used reagent is higher than the top grade purity, and the water is deionized water or ultrapure water.
Preferably, the sample loading pit is obtained by rotationally grinding a niobium block in the center of an indium sheet.
Preferably, the shape of the niobium block comprises a conical shape.
Preferably, the indium pieces are in a molten state during milling.
Preferably, the indium pieces are protected from puncture after grinding.
Preferably, the shape of the indium sheet comprises a circle.
Preferably, the indium sheet has a thickness of 1.95 to 2.05mm, for example 1.95mm, 1.98mm, 2mm, 2.02mm or 2.05mm, but is not limited to the values recited, and other values not recited within this range are equally applicable.
Preferably, before the powder is loaded, the indium sheet with the sample loading pits is also subjected to first cleaning.
Preferably, the first cleaning comprises a first cleaning and a second rinsing performed sequentially.
Preferably, the first cleaning stage comprises acid cleaning and deionized water rinsing which are sequentially carried out.
Preferably, the pickled container material comprises polytetrafluoroethylene.
Preferably, the cleaning solution for pickling comprises HNO 3 And (3) solution.
Preferably, the HNO in the acid washing 3 The concentration of the solution is 65 to 68 wt.%, and may be, for example, 65 wt.%, 65.5 wt.%, 66 wt.%, 66.5 wt.%, 67 wt.%, 67.5 wt.%, or 68 wt.%, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the time for the acid washing is 3 to 4min, for example, 3min, 3.2min, 3.5min, 3.8min or 4min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the number of deionized water rinses in the one wash stage is 3 to 5, such as 3, 4 or 5, but not limited to the recited values, and other values not recited within the recited range are equally applicable.
Preferably, the number of washing steps in the washing step is 3 to 4, for example 3 or 4, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the rinsing liquid of the second-stage rinsing in the first cleaning comprises ethanol.
Preferably, the number of second rinses in the first wash is from 1 to 2, for example 1 or 2, but is not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the means for loading the niobium powder into the loading well comprises a spatula.
Preferably, the material of the medicine spoon comprises polytetrafluoroethylene.
Preferably, the spoon is subjected to a second wash prior to filling.
Preferably, the second cleaning comprises a first cleaning and a second rinsing performed sequentially.
Preferably, the first cleaning in the second cleaning comprises mixed acid cleaning and deionized water rinsing which are sequentially carried out.
Preferably, the material of the mixed pickling container comprises polytetrafluoroethylene.
Preferably, the cleaning solution of the mixed pickling comprises HNO 3 Mixed acid prepared by the solution and the HF solution.
Preferably, the mixed acid contains HNO 3 The mass ratio of the solution to the HF solution is 1 (0.95 to 1.05), and may be, for example, 1.
Preferably, the mixed acid wash is medium HNO 3 The concentration of the solution is 65 to 68 wt.%, and may be, for example, 65 wt.%, 65.5 wt.%, 66 wt.%, 66.5 wt.%, 67 wt.%, 67.5 wt.%, or 68 wt.%, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the concentration of the HF solution in the mixed acid wash is 40 to 45 wt.%, and may be, for example, 40 wt.%, 41 wt.%, 42 wt.%, 43 wt.%, 44 wt.%, or 45 wt.%, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the time for the mixed pickling is 3 to 4min, for example, 3min, 3.2min, 3.5min, 3.8min or 4min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the number of deionized water rinses in the second cleaning is 3 to 5, such as 3, 4, or 5, but not limited to the recited values, and other values not recited within the recited range are equally applicable.
Preferably, the number of the first washing in the second washing is 1 to 2, for example, 1 or 2, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the rinse liquid of the second-stage rinsing in the second cleaning comprises ethanol.
Preferably, the number of second rinses in the second wash is from 1 to 2, for example 1 or 2, but not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, after the second cleaning, the medicine spoon is dried.
Preferably, the drying apparatus includes a lamp.
The invention respectively cleans the indium sheet and the polytetrafluoroethylene spoon with the sample-carrying pits, removes impurities introduced by the sample as much as possible, and obviously improves the detection efficiency and the data validity of the glow discharge mass spectrometer.
Preferably, the pressure of the static pressure is 8 to 12MPa, for example 8MPa, 9MPa, 10MPa, 11MPa or 12MPa, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the static pressure is applied for a period of 8 to 12min, for example 8min, 9min, 10min, 11min or 12min, but not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the indium sheet with the sample loading pits is placed into a mold after being powdered, and then is subjected to static pressure.
Preferably, the material of the mold comprises polytetrafluoroethylene.
Preferably, the niobium sample after hydrostatic pressing is held in a sample holder and loaded into the instrument sample chamber, after which it is evacuated and pushed into the discharge chamber of the glow discharge mass spectrometer.
Preferably, after evacuation, the vacuum in the sample chamber of the instrument is 1.0X 10 -3 Pa-1.0×10 -2 Pa, for example, may be 1.0X 10 -3 Pa、2.0×10 -3 Pa、5.0×10 -3 Pa or 1.0X 10 -2 Pa, but is not limited to the recited values, and other values within the range are equally applicable.
Preferably, the cooling temperature is from-200 ℃ to-190 ℃, and may be, for example, -200 ℃, -198 ℃, -195 ℃, -192 ℃ or-190 ℃, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the cooling time is 8 to 12min, for example 8min, 9min, 10min, 11min or 12min, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the time for the acquisition is 120 to 150min, for example 120min, 130min, 140min or 150min, but is not limited to the values listed, and other values not listed in the range of values are also applicable.
As a preferred technical solution of the present invention, the detection method includes the steps of:
the method comprises the following steps of obtaining a sample loading pit with the diameter of 0.6-0.8 mm and the depth of 0.25-0.35 mm by rotationally grinding a conical niobium block at the center of a circular indium sheet in a molten state, ensuring that the indium sheet is not punctured after grinding, and carrying out first cleaning on the indium sheet with the sample loading pit, wherein the first cleaning comprises the following steps: with HNO successively 3 Cleaning the solution in a polytetrafluoroethylene container for 3-4 min, rinsing with deionized water for 3-5 times, repeating the cleaning and rinsing processes for 3-4 times, and finally rinsing with ethanol for 1-2 times; performing a second cleaning of the teflon spoons, the second cleaning comprising: with HNO successively 3 Cleaning the mixed acid prepared from the solution and the HF solution in a polytetrafluoroethylene container for 3-4 min, wherein HNO is contained in the mixed acid 3 The mass ratio of the solution to the HF solution is 1 (0.95-1.05), deionized water is used for rinsing for 3-5 times, ethanol is used for rinsing for 1-2 times, and finally baking is carried out by a baking lamp, wherein the HNO is 3 The concentration of the solution is 65-68 wt%, and the concentration of the HF solution is 40-45 wt%; loading niobium powder into the indium sheet subjected to the first cleaning by using a polytetrafluoroethylene spoon subjected to the second cleaning, and carrying out static pressure on the niobium powder at the pressure of 8-12 MPa for 8-12 min to obtain a niobium sample; the niobium sample after static pressure is fixed by a sample clamp, and is put into an instrument sample chamber, and then is vacuumized until the vacuum degree is 1.0 multiplied by 10 -3 Pa-1.0×10 -2 Pa, pushing the instrument sample chamber into a discharge chamber of the glow discharge mass spectrum; the niobium sample is sequentially cooled and sputtered at the temperature of-200 to-190 ℃ for 8 to 12min in glow discharge mass spectrometryAnd in a direct current mode, the discharge voltage is 1.4-1.6 KV, the discharge current is 1.8-2.2 mA, the resolution of the instrument is adjusted to 3400-4000, the signal intensity of the element to be detected is acquired for 120-150 min, and the mass fraction of the element to be detected is calculated by applying a relative sensitivity factor.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the glow discharge mass spectrum detection method of the niobium powder, the indium sheet is taken as the sample carrying sheet of the niobium powder, other impurities are not introduced as far as possible in the sample preparation process, the sample is cleaned by the acid cleaning solution and is repeatedly rinsed, the residual impurities contacting the sample are removed as far as possible, and the accuracy of a detection result is ensured;
(2) The glow discharge mass spectrum detection method of the niobium powder provided by the invention adopts Nu Astrum glow discharge mass spectrum, the sample freezing and sputtering are integrally completed, the sample preparation process almost without impurities is matched, the detection precision reaches the ppm level, and the niobium alloy for the target material meets the purity requirement.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The technical solution of the present invention is further explained by the following embodiments.
In one embodiment, the present invention provides a glow discharge mass spectrometry detection method of niobium powder, comprising the steps of:
the method comprises the following steps of obtaining a sample loading pit with the diameter of 0.6-0.8 mm and the depth of 0.25-0.35 mm by rotationally grinding a conical niobium block at the center of a circular indium sheet in a molten state, ensuring that the indium sheet is not punctured after grinding, and carrying out first cleaning on the indium sheet with the sample loading pit, wherein the first cleaning comprises the following steps: with HNO in sequence 3 Cleaning the solution in a polytetrafluoroethylene container for 3-4 min, rinsing with deionized water for 3-5 times, repeating the cleaning and rinsing processes for 3-4 times, and finally rinsing with ethanol for 1-2 times; second cleaning the teflon spoonAnd the second cleaning comprises: with HNO in sequence 3 Cleaning a mixed acid prepared from a solution and an HF solution in a polytetrafluoroethylene container for 3-4 min, wherein the mass ratio of the HNO3 solution to the HF solution in the mixed acid is 1 (0.95-1.05), rinsing for 3-5 times by using deionized water, rinsing for 1-2 times by using ethanol, and finally drying by using a baking lamp, wherein the HNO is prepared from the solution and the HF solution 3 A concentration of the solution is 65-68% by weight, a concentration of the HF solution is 40-45%; loading niobium powder into the indium sheet subjected to the first cleaning by using a polytetrafluoroethylene spoon subjected to the second cleaning, and carrying out static pressure on the niobium powder at the pressure of 8-12 MPa for 8-12 min to obtain a niobium sample; the niobium sample after static pressure is fixed by a sample clamp and is put into an instrument sample chamber, and then the sample chamber is vacuumized until the vacuum degree is 1.0 multiplied by 10 -3 Pa-1.0×10 -2 Pa, pushing the instrument sample chamber into a discharge chamber of the glow discharge mass spectrum; the niobium sample is sequentially cooled and sputtered at the temperature of-200 to-190 ℃ for 8 to 12min in a glow discharge mass spectrum, the discharge voltage is 1.4 to 1.6KV, the discharge current is 1.8 to 2.2mA in a direct current mode, the resolution of an instrument is adjusted to 3400 to 4000, the signal intensity of an element to be detected is acquired for 120 to 150min, and the mass fraction of the element to be detected is calculated by using a relative sensitivity factor.
It is understood that processes or substitutions and variations of conventional data provided by embodiments of the present invention are within the scope and disclosure of the present invention.
Example 1
The embodiment provides a glow discharge mass spectrometry detection method of niobium powder, which comprises the following steps:
the method comprises the following steps of obtaining a sample loading pit with the diameter of 0.7mm and the depth of 0.3mm by rotationally grinding a conical niobium block at the center of a circular indium sheet in a molten state, ensuring that the indium sheet is not punctured after grinding, and carrying out first cleaning on the indium sheet with the sample loading pit, wherein the first cleaning comprises the following steps: with HNO in sequence 3 Cleaning the solution in a polytetrafluoroethylene container for 4min, rinsing with deionized water for 5 times, repeating the cleaning and rinsing processes for 5 times, and finally rinsing with ethanol for 2 times; second cleaning the teflon spoonWashing, the second washing comprises: with HNO in sequence 3 Cleaning for 3min in a polytetrafluoroethylene container by using mixed acid prepared from solution and HF solution, wherein HNO in the mixed acid 3 The mass ratio of the solution to the HF solution is 1, deionized water is used for rinsing for 5 times, ethanol is used for rinsing for 2 times, and finally baking is carried out by using a baking lamp, wherein the HNO solution is prepared by mixing HNO solution and HF solution in a ratio of 1 3 The concentration of the solution is 66wt%, and the concentration of the HF solution is 43wt%; loading niobium powder into the indium sheet subjected to the first cleaning by using a polytetrafluoroethylene spoon subjected to the second cleaning, and carrying out static pressure on the niobium powder for 8min under the pressure of 12MPa to obtain a niobium sample; the niobium sample after static pressure is fixed by a sample clamp, and is put into an instrument sample chamber, and then is vacuumized until the vacuum degree is 1.0 multiplied by 10 -3 Pa, pushing the instrument sample chamber into a discharge chamber of the glow discharge mass spectrum; and sequentially cooling and sputtering the niobium sample in a glow discharge mass spectrum at the temperature of-200 ℃ for 8min, under a direct current mode, the discharge voltage is 1.6KV, the discharge current is 1.8mA, the resolution of the instrument is adjusted to be 3400-4000, the signal intensity of the element to be detected is collected for 120min, and the mass fraction of the element to be detected is calculated by using a relative sensitivity factor.
This example gives data for analytical tests with a maximum relative error of 4.3% for five replicates over the analysis time.
Example 2
The embodiment provides a glow discharge mass spectrometry detection method of niobium powder, which comprises the following steps:
the method comprises the following steps of carrying out rotary grinding on the center of a circular indium sheet in a molten state by a conical niobium block to obtain a sample loading pit with the diameter of 0.6mm and the depth of 0.35mm, ensuring that the indium sheet is not punctured after grinding, and carrying out first cleaning on the indium sheet with the sample loading pit, wherein the first cleaning comprises the following steps: with HNO in sequence 3 Cleaning the solution in a polytetrafluoroethylene container for 3min, rinsing with deionized water for 4 times, repeating the cleaning and rinsing processes for 3 times, and finally rinsing with ethanol for 1 time; performing a second cleaning of the teflon spatula, the second cleaning comprising: with HNO in sequence 3 The mixed acid prepared by the solution and the HF solution is carried out for 3min in a polytetrafluoroethylene containerCleaning, HNO in the mixed acid 3 The mass ratio of the solution to the HF solution is 1.95, deionized water is used for rinsing for 3 times, ethanol is used for rinsing for 1 time, and finally baking is carried out by a baking lamp, wherein the HNO solution is prepared by the steps of 3 The concentration of the solution was 68% by weight, and the concentration of the HF solution was 45%; loading niobium powder into the indium sheet subjected to the first cleaning by using a polytetrafluoroethylene spoon subjected to the second cleaning, and carrying out static pressure on the niobium powder for 12min under the pressure of 8MPa to obtain a niobium sample; the niobium sample after static pressure is fixed by a sample clamp and is put into an instrument sample chamber, and then the sample chamber is vacuumized until the vacuum degree is 1.0 multiplied by 10 -2 Pa, pushing the instrument sample chamber into a discharge chamber of the glow discharge mass spectrum; and sequentially cooling and sputtering the niobium sample in glow discharge mass spectrometry at-190 ℃ for 10min, under the direct current mode, the discharge voltage is 1.4KV, the discharge current is 2.2mA, the resolution of the instrument is adjusted to 3400-4000, the signal intensity of the element to be detected is acquired for 150min, and the mass fraction of the element to be detected is calculated by applying a relative sensitivity factor.
This example gives data from analytical tests over an analytical time, with a maximum relative error of 5.6% for five replicates.
Example 3
The embodiment provides a glow discharge mass spectrometry detection method of niobium powder, which comprises the following steps:
the method comprises the following steps of rotationally grinding the center of a circular indium sheet in a molten state by a conical niobium block to obtain a sample loading pit with the diameter of 0.8mm and the depth of 0.25mm, ensuring that the indium sheet is not punctured after grinding, and carrying out first cleaning on the indium sheet with the sample loading pit, wherein the first cleaning comprises the following steps: with HNO in sequence 3 Cleaning the solution in a polytetrafluoroethylene container for 3min, rinsing with deionized water for 3 times, repeating the cleaning and rinsing processes for 3 times, and finally rinsing with ethanol for 2 times; performing a second cleaning of the teflon spatula, the second cleaning comprising: with HNO successively 3 Cleaning the mixed acid prepared from the solution and the HF solution in a polytetrafluoroethylene container for 3min, wherein HNO is contained in the mixed acid 3 The mass ratio of the solution to the HF solution was 1.05, and the solution was rinsed 3 times with deionized water and then with ethyl alcoholRinsing with alcohol for 1 time, and oven drying with baking lamp, HNO 3 The concentration of the solution was 65% by weight, the concentration of the HF solution was 40%; loading niobium powder into the indium sheet subjected to the first cleaning by using a polytetrafluoroethylene spoon subjected to the second cleaning, and performing static pressure on the niobium powder at the pressure of 10MPa for 10min to obtain a niobium sample; the niobium sample after static pressure is fixed by a sample clamp, and is put into an instrument sample chamber, and then is vacuumized until the vacuum degree is 5.0 multiplied by 10 -3 Pa, pushing the instrument sample chamber into a discharge chamber of the glow discharge mass spectrum; and sequentially cooling and sputtering the niobium sample in a glow discharge mass spectrum at the temperature of-190 ℃ for 10min, under the direct current mode, the discharge voltage is 1.5KV, the discharge current is 2mA, the resolution of the instrument is adjusted to be 3400-4000, the signal intensity of the element to be detected is acquired for 130min, and the mass fraction of the element to be detected is calculated by using a relative sensitivity factor.
This example gives data from analytical tests over an analytical time, with a maximum relative error of 4.5% for five replicates.
Example 4
This example provides a glow discharge mass spectrometry method for detecting niobium powder, which differs from example 1 only in that HNO is present in the mixed acid during the second cleaning 3 The mass ratio of the solution to the HF solution is 1.2.
This example gives data for analytical tests with a maximum relative error of 4.4% for five replicates over the analysis time.
Example 5
This example provides a glow discharge mass spectrometry method for detecting niobium powder, which differs from example 1 only in that HNO is present in the mixed acid during the second cleaning 3 The mass ratio of the solution to the HF solution was 1.2.
This example gives data from analytical tests over an analytical time, with a maximum relative error of 5.7% for five replicates.
Comparative example 1
The comparative example provides a glow discharge mass spectrometry detection method for niobium powder, which is the same as that of example 1 except that the indium sheet is not pickled.
The comparative example tests, the instrument was completely stable, and the data of the analytical test were obtained with a maximum relative error of 15.1% for five repetitions.
Comparative example 2
The comparative example provides a glow discharge mass spectrometry detection method of niobium powder, and the sample preparation method is the same as that of example 1 except that indium sheets are not subjected to acid washing and are replaced by ethanol washing.
In the comparative example test, the instrument is completely stable, the data of the analysis test can be obtained, and the maximum relative error is 16.8 percent after five times of repetition.
In conclusion, the glow discharge mass spectrometry detection method for the niobium powder avoids the introduction of impurities, has high data accuracy, and has the maximum relative error within 5.7 percent after being repeated for five times; the testing method can obtain stronger signals through specific testing parameters, has high sensitivity and is suitable for auxiliary preparation of high-purity metal for the target material.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. A glow discharge mass spectrometry detection method of niobium powder is characterized by comprising the following steps:
loading niobium powder into an indium sheet with sample loading pits, and carrying out static pressure on the niobium powder to obtain a niobium sample; the niobium sample is sequentially cooled and sputtered in a glow discharge mass spectrum, the discharge voltage is 1.4-1.6 KV, the discharge current is 1.8-2.2 mA in a direct current mode, the resolution of the instrument is adjusted to 3400-4000, the signal intensity of the element to be detected is collected, and the mass fraction of the element to be detected is calculated by applying a relative sensitivity factor.
2. The detection method according to claim 1, wherein the diameter of the loading well is 0.6 to 0.8mm;
preferably, the depth of the sample loading pit is 0.25-0.35 mm;
preferably, the sample loading pit is obtained by rotationally grinding a niobium block in the center of an indium sheet;
preferably, the shape of the niobium block comprises a conical shape;
preferably, the indium sheet is in a molten state during grinding;
preferably, the shape of the indium sheet comprises a circle;
preferably, the thickness of the indium sheet is 1.95 to 2.05mm.
3. The detection method according to claim 1 or 2, wherein before the powder is charged, a first cleaning is further performed on the indium sheet having the loading pits;
preferably, the first cleaning comprises a first cleaning and a second rinsing performed sequentially.
4. The detection method according to claim 3, wherein one stage of the first cleaning comprises acid washing and deionized water rinsing sequentially;
preferably, the pickled container material comprises polytetrafluoroethylene;
preferably, the cleaning solution for pickling comprises HNO 3 A solution;
preferably, the HNO in acid wash 3 The concentration of the solution is 65.0 to 68.0 weight percent;
preferably, the pickling time is 3-4 min;
preferably, the number of times of rinsing by deionized water in the first-stage cleaning is 3-5 times;
preferably, the number of times of the first-stage cleaning in the first-stage cleaning is 3-4.
5. The detection method according to claim 3 or 4, wherein a rinse liquid of the second-stage rinsing in the first cleaning includes ethanol;
preferably, the number of times of the second rinsing in the first cleaning is 1 to 2 times.
6. The test method as claimed in any one of claims 1 to 5, wherein the means for loading the niobium powder into the loading well comprises a spoon;
preferably, the material of the medicine spoon comprises polytetrafluoroethylene.
7. The test method of claim 6, wherein the spoon is subjected to a second wash prior to loading;
preferably, the second cleaning comprises a first-stage cleaning and a second-stage rinsing which are sequentially carried out;
preferably, the first cleaning in the second cleaning comprises mixed acid cleaning and deionized water rinsing which are sequentially carried out;
preferably, the material of the mixed pickling container comprises polytetrafluoroethylene;
preferably, the cleaning solution of the mixed pickling comprises HNO 3 Mixed acid prepared by the solution and the HF solution;
preferably, HNO in the mixed acid 3 The mass ratio of the solution to the HF solution is 1 (0.95-1.05);
preferably, the HNO in mixed acid washing 3 The concentration of the solution is 65.0-68.0 wt%;
preferably, the concentration of the HF solution in the mixed acid washing is 40.0-45.0 wt%;
preferably, the time of the mixed acid washing is 3-4 min;
preferably, the number of times of rinsing with deionized water in the second cleaning is 3-5 times;
preferably, the number of times of the first-stage cleaning in the second cleaning is 1-2 times;
preferably, the rinsing liquid of the second-stage rinsing in the second cleaning comprises ethanol;
preferably, the number of times of the second-stage rinsing in the second cleaning is 1-2 times;
preferably, after the second cleaning, the medicine spoon is dried;
preferably, the drying apparatus includes a lamp.
8. The method of any one of claims 1 to 7, wherein the static pressure is 8 to 12MPa;
preferably, the static pressure time is 8-12 min;
preferably, the indium sheet with the sample loading pit is placed into a die after being powdered, and then is subjected to static pressure;
preferably, the material of the mould comprises polytetrafluoroethylene;
preferably, the niobium sample after static pressure is fixed by a sample clamp, and is loaded into an instrument sample chamber, and then is vacuumized and pushed into a discharge chamber of a glow discharge mass spectrum;
preferably, after evacuation, the vacuum in the sample chamber of the instrument is 1.0X 10 -3 Pa-1.0×10 -2 Pa。
9. The method according to any one of claims 1 to 8, wherein the temperature of the cooling is-200 to-190 ℃;
preferably, the cooling time is 8-12 min;
preferably, the time for collecting is 120-150 min.
10. The detection method according to any one of claims 1 to 9, characterized in that it comprises the steps of:
the method comprises the following steps of obtaining a sample loading pit with the diameter of 0.6-0.8 mm and the depth of 0.25-0.35 mm by rotationally grinding a conical niobium block at the center of a circular indium sheet in a molten state, ensuring that the indium sheet is not punctured after grinding, and carrying out first cleaning on the indium sheet with the sample loading pit, wherein the first cleaning comprises the following steps: with HNO successively 3 Cleaning the solution in a polytetrafluoroethylene container for 3-4 min, rinsing with deionized water for 3-5 times, repeating the cleaning and rinsing processes for 3-4 times, and finally rinsing with ethanol for 1-2 times; performing a second cleaning of the teflon spatula, the second cleaning comprising: with HNO successively 3 Mixed acid prepared from solution and HF solution in polytetrafluoroethylene containerCleaning for 3-4 min in the device, wherein HNO is in the mixed acid 3 The mass ratio of the solution to the HF solution is 1 (0.95-1.05), deionized water is used for rinsing for 3-5 times, ethanol is used for rinsing for 1-2 times, and finally baking is carried out by a baking lamp, wherein HNO is generated 3 The concentration of the solution is 65-68 wt%, and the concentration of the HF solution is 40-45 wt%; loading niobium powder into the indium sheet subjected to the first cleaning by using a polytetrafluoroethylene medicine spoon subjected to the second cleaning, and carrying out static pressure on the niobium powder at the pressure of 8-12 MPa for 8-12 min to obtain a niobium sample; the niobium sample after static pressure is fixed by a sample clamp, and is put into an instrument sample chamber, and then is vacuumized until the vacuum degree is 1.0 multiplied by 10 -3 Pa-1.0×10 -2 Pa, pushing the instrument sample chamber into a discharge chamber of the glow discharge mass spectrum; the niobium sample is sequentially cooled and sputtered at the temperature of-200 to-190 ℃ for 8 to 12min in a glow discharge mass spectrum, the discharge voltage is 1.4 to 1.6KV, the discharge current is 1.8 to 2.2mA in a direct current mode, the resolution of an instrument is adjusted to 3400 to 4000, the signal intensity of an element to be detected is acquired for 120 to 150min, and the mass fraction of the element to be detected is calculated by using a relative sensitivity factor.
CN202211203594.7A 2022-09-29 2022-09-29 Glow discharge mass spectrum detection method for niobium powder Pending CN115524390A (en)

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