CN115261634A - Low-potassium molybdenum substrate, preparation method and application - Google Patents
Low-potassium molybdenum substrate, preparation method and application Download PDFInfo
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 243
- 239000011733 molybdenum Substances 0.000 title claims abstract description 151
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 151
- 239000011591 potassium Substances 0.000 title claims abstract description 124
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 124
- 239000000758 substrate Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 53
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 35
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 238000004140 cleaning Methods 0.000 claims abstract description 21
- 238000003908 quality control method Methods 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000010894 electron beam technology Methods 0.000 claims abstract description 15
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 238000006722 reduction reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002923 metal particle Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 abstract description 31
- 238000004458 analytical method Methods 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- 239000013062 quality control Sample Substances 0.000 description 12
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 7
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 6
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 5
- 238000009614 chemical analysis method Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/22—Remelting metals with heating by wave energy or particle radiation
- C22B9/228—Remelting metals with heating by wave energy or particle radiation by particle radiation, e.g. electron beams
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/3103—Atomic absorption analysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/045—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling
- B22F2009/046—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling by cutting
Abstract
The invention provides a low-potassium molybdenum matrix, a preparation method and application, wherein the method comprises the steps of preparing a low-potassium molybdenum rod in a sintering and electron beam smelting mode, then carrying out cutting and chemical cleaning on the low-potassium molybdenum rod to prepare molybdenum matrix raw material particles, and finally carrying out reduction and screening on the molybdenum matrix raw material particles to prepare the low-potassium molybdenum matrix, wherein the potassium content in the low-potassium molybdenum matrix is less than 0.0002%, and the low-potassium molybdenum matrix can be used as a molybdenum matrix for quality control detection of molybdenum powder products and molybdenum trioxide products. The preparation method of the low-potassium molybdenum substrate can prepare the high-purity low-potassium molybdenum substrate with the potassium content of less than 0.0002% by adopting a process of combining sintering, electron beam melting and chemical cleaning. The low-potassium molybdenum substrate is easy to store, stable in property, not easy to pollute and difficult to meet the long-time production requirement. The linear correlation coefficient of an analysis working curve drawn by adopting the low-potassium molybdenum matrix is greater than 0.9995, the linear correlation is good, and the reliability and the authenticity of the detection data of the potassium content in the molybdenum chemical industry and molybdenum metal products can be improved.
Description
Technical Field
The invention belongs to the technical field of molybdenum chemical industry and molybdenum metal production, relates to quality control detection of molybdenum chemical industry and molybdenum metal products, and particularly relates to a low-potassium molybdenum substrate, a preparation method and application.
Background
The molybdenum chemical industry and molybdenum metal products mainly comprise ammonium molybdate, high-purity molybdenum trioxide, molybdenum powder, molybdenum plates, molybdenum wires, molybdenum electrodes and the like, and analysis and detection are indispensable important links in the production and scientific research of the molybdenum chemical industry and molybdenum metal products. The potassium content is an important index for measuring the quality of molybdenum chemical products and molybdenum metal products, and is also one of important indexes concerned by scientific researchers. With the rapid development of the molybdenum industry, the demand on the potassium content in molybdenum chemical industry and molybdenum metal products is higher and higher at present, and the potassium content needs to reach ppm level or even ppb level.
At present, the existing method for measuring the content of potassium in molybdenum chemical industry and molybdenum metal products adopts flame atomic absorption spectrometry for measuring the content of potassium in a molybdenum chemical analysis method, the national standard of which is GB/T4325-2013, and the method is suitable for measuring the content of potassium in molybdenum powder, molybdenum bars, molybdenum trioxide and ammonium molybdate, and the measuring range is 0.0010-0.150%. The method comprises the following steps: the sample was decomposed with hydrogen peroxide, cesium chloride was used as a deionizing agent, and potassium amount was calculated by measuring potassium absorbance at a wavelength of 766.5nm by an air-acetylene flame atomic absorption spectrometer under matrix matching conditions.
The requirements of the measuring method on the molybdenum substrate are as follows: the applied samples have basically the same properties and contain no or very little potassium element to be detected. When analyzing the sample, the amount of the molybdenum matrix in the standard solution should be the same as the amount of the molybdenum matrix in the sample. Based on the influence of the molybdenum matrix, when a blank experiment is carried out along with the sample, the blank should be added with the molybdenum matrix with the same amount as the sample. In order to eliminate physical interference and chemical interference, ensure the accuracy of measurement and reduce the measurement error caused by the difference of matrix compositions, molybdenum matrixes with consistent compositions must be used in the measurement process, which is commonly called matrix matching. According to the determination method, a molybdenum matrix is required to be added when a working curve is prepared and a blank experiment is carried out.
However, the existing molybdenum substrate has the following drawbacks:
firstly, the content of potassium in the existing molybdenum substrate is more than 0.0002%, which is difficult to meet the detection requirement, and the molybdenum substrate adopted in the determination is not in line with the requirement, so that the reliability and accuracy of the detection data are reduced, and further misjudgment or misjudgment on molybdenum chemical industry and molybdenum metal products is caused.
Secondly, the existing molybdenum substrate is not storage-resistant, and the properties are not stable enough in the storage and use processes, so that the molybdenum substrate is easy to be polluted and difficult to meet the long-time production requirements.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a low-potassium molybdenum substrate, a preparation method and application, and solves the technical problem that the reliability and accuracy of detection data are not high because the molybdenum substrate does not meet the detection requirement in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a low-potassium molybdenum substrate specifically comprises the following steps:
step one, preparing a low-potassium molybdenum rod;
pressing molybdenum powder into molybdenum rod blanks, and sintering the pressed molybdenum rod blanks to obtain sintered molybdenum rods; then carrying out vacuum electron beam melting on the sintered molybdenum rod to obtain a low-potassium molybdenum rod;
step two, preparing molybdenum substrate raw material particles;
cutting the low-potassium molybdenum rod prepared in the step one to prepare scrap-shaped molybdenum metal particles; then, cleaning the scrap-shaped molybdenum metal particles by using nitric acid and water, and drying after cleaning to prepare molybdenum matrix raw material particles;
step three, preparing a low-potassium molybdenum substrate;
carrying out reduction reaction on the molybdenum matrix raw material prepared in the step two to prepare reduced molybdenum matrix raw material particles; and sieving the reduced molybdenum matrix raw material particles to obtain the low-potassium molybdenum matrix.
The invention also has the following technical characteristics:
specifically, the content of potassium in the low-potassium molybdenum matrix is less than 0.0002%.
Specifically, in the step one, the sintering temperature of the sintering is 1500-1910 ℃, and the sintering time is 6-8 h.
Specifically, in the first step, the melting power of an electron gun for vacuum electron beam melting is 100-120 Kw, the main high-voltage is 25-35 Kv, the current of the electron beam is 2.0-4.0A, the filament voltage is 4-6V, and the speed of an electrode rod is 100-150 mm/min.
Specifically, in the second step, the volume ratio of the nitric acid to the water is 1.
Specifically, in the second step, the cleaning time is 1-2 h.
Specifically, in the third step, the hydrogen flow rate of the reduction reaction is 10 to 20m3The temperature of the reduction furnace is 850-950 ℃.
The invention also discloses a low-potassium molybdenum substrate, which is prepared by adopting the preparation method of the low-potassium molybdenum substrate.
The invention also protects the application of the low-potassium molybdenum matrix as a molybdenum matrix in quality control detection of molybdenum powder products and molybdenum trioxide products.
Compared with the prior art, the invention has the following technical effects:
the preparation method of the low-potassium molybdenum substrate adopts the process of combining sintering, electron beam melting and chemical cleaning, and can prepare the high-purity low-potassium molybdenum substrate with the potassium content of less than 0.0002 percent.
And (II) the low-potassium molybdenum matrix prepared by the method is easy to store, stable in property, not easy to pollute and difficult to meet the long-time production requirement.
(III) when the low-potassium molybdenum matrix is used as a molybdenum matrix in the quality control detection process of molybdenum powder products and molybdenum trioxide products, the linear correlation coefficient of a drawn analysis working curve is larger than 0.9995, the linear relation is good, the reliability and authenticity of potassium content detection data in molybdenum chemical industry and molybdenum metal products can be improved, and quality accidents and quality disputes caused by inaccurate detection data are reduced.
The method can solve the current situation that the molybdenum matrix is deficient when the molybdenum industry analyzes and detects the content of potassium in the molybdenum chemical industry and molybdenum metal products, saves the analysis cost and achieves the purposes of cost reduction and efficiency improvement.
The method (V) is favorable for ensuring the accuracy and consistency of detection results, can improve the mutual confidence of technical indexes of products in import and export trades, and has extremely important significance for the production, development, use and the like of molybdenum chemical industry and molybdenum metal products.
Drawings
FIG. 1 is a schematic flow diagram of a method for preparing a low-potassium molybdenum substrate.
Fig. 2 is an analysis operation graph drawn in the quality control test of application example 1.
Fig. 3 is an analysis operation graph plotted in the quality control test of application example 2.
Fig. 4 is a graph showing an analysis operation curve obtained in the quality control test of application example 3.
The present invention will be explained in further detail with reference to examples.
Detailed Description
In the invention:
the content means mass content.
It is to be understood that all materials, tools and equipment disclosed herein, unless otherwise specified, are materials, tools and equipment known in the art.
The present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention.
Example 1:
the embodiment provides a preparation method of a low-potassium molybdenum substrate, which specifically comprises the following steps:
step one, preparing a low-potassium molybdenum rod;
pressing molybdenum powder into a molybdenum rod blank by adopting a proper rubber sleeve die, placing the pressed molybdenum rod blank into a medium-frequency sintering furnace, and sintering for 6 hours at the temperature of 1910 ℃ to obtain a sintered molybdenum rod; and then placing the sintered molybdenum rod in an electron beam melting furnace, and preparing the low-potassium molybdenum rod under the conditions that the melting power of an electron gun is 110Kw, the main high-voltage is 30Kv, the current of the electron beam is 3.5A, the filament voltage is 5V, and the speed of an electrode rod is 120 mm/min.
In the embodiment, the content of potassium in the molybdenum powder used for preparing the molybdenum bar billet is less than 0.0048%, and the particle size distribution is between 5 and 15 mu m.
In this example, the density of the sintered molybdenum rod was 9.79g/cm3The section grain density of the sintered molybdenum rod is more than 1000/mm2. The content of potassium in the low-potassium molybdenum rod is less than or equal to 0.0001 percent.
Step two, preparing molybdenum substrate raw material particles;
slowly cutting the low-potassium molybdenum rod prepared in the step one layer by adopting an alloy cutter to prepare scrap-shaped molybdenum metal particles; and then placing the crumb-shaped molybdenum metal particles into a plastic container, adding 100mL of nitric acid and 300mL of pure water to carry out chemical reaction cleaning for 1h, cleaning with pure water after cleaning until the pH value of the cleaning solution is 7.0, and drying or naturally airing to obtain the molybdenum matrix raw material particles.
In the present example, the density ρ of nitric acid is 1.42g/mL, and pure water is secondary water that meets the GB/T6682 standard.
Step three, preparing a low-potassium molybdenum substrate;
loading the molybdenum-based raw material particles prepared in the step two into a material boat, pushing the material boat into a reduction furnace, and controlling the hydrogen flow at 20m3Performing reduction reaction at the temperature of 850 ℃ in the reduction furnace to obtain reduced molybdenum matrix raw material particles; and then sieving the reduced molybdenum metal particles by adopting a standard sieve with the sieve pore size of 75 mu m, and taking undersize to obtain the low-potassium molybdenum matrix. The true bookIn the example, the boat was a pure molybdenum boat as known in the art to ensure that the molybdenum substrate feedstock particles were not contaminated.
In this example, the potassium content in the low-potassium molybdenum substrate was measured by flame atomic absorption spectrometry for potassium content determination, inductively coupled plasma mass spectrometry, and glow discharge mass spectrometry, which are national standards GB/T4325-2013, and the results are shown in table 1. It should be noted that, when the method with the national standard of GB/T4325-2013 is used to detect the potassium content in a low-potassium molybdenum substrate, a molybdenum substrate known in the prior art is used as a blank reference.
TABLE 1, results of measuring potassium content in the low-potassium molybdenum substrate of example 1
| Measurement method | GB/T4325.16-2013 method | Inductively coupled plasma mass spectrometry | Glow discharge mass spectrometry measurements |
| Potassium content | ＜0.0002％ | 0.000085％ | 0.000068％ |
As can be seen from Table 1, the low-K molybdenum substrate prepared in this example meets the analysis and detection requirement that the K content is less than 0.0002%.
Application example 1:
the low-potassium molybdenum substrate prepared in example 1 is used as a molybdenum substrate for quality control detection of molybdenum powder products and molybdenum trioxide products, and the quality control detection adopts flame atomic absorption spectrometry for potassium content determination in a molybdenum chemical analysis method with the national standard of GB/T4325-2013, and the results are shown in FIG. 2 and Table 2.
Table 2 quality control test results of molybdenum powder product and molybdenum trioxide product of application example 1
| Quality control sample | Measured value/%) | Theoretical value/%) | Absolute difference/%) | Method allowed difference/%) |
| Quality control sample of molybdenum powder product | 0.0083 | 0.0084 | 0.0001 | 0.0015 |
| Quality control sample of molybdenum trioxide product | 0.0038 | 0.0043 | 0.0005 | 0.0010 |
As can be seen from fig. 2 and table 2, the linear correlation coefficient of the analysis working curve drawn by using the low-potassium molybdenum matrix is 0.9999, and the detection requirement that the linear correlation coefficient of the analysis working curve is not less than 0.9995 can be satisfied. The low-potassium molybdenum matrix is used as a molybdenum matrix detection quality control sample, the method tolerance is 0.0010% and 0.0015%, and the requirement of the quality detection method tolerance can be met.
Example 2:
the embodiment provides a preparation method of a low-potassium molybdenum substrate, which specifically comprises the following steps:
step one, preparing a low-potassium molybdenum rod;
pressing molybdenum powder into a molybdenum rod blank by adopting a proper rubber sleeve die, placing the pressed molybdenum rod blank into a medium-frequency sintering furnace, and sintering at 1850 ℃ for 7 hours to prepare a sintered molybdenum rod; and then placing the sintered molybdenum rod in an electron beam melting furnace, and preparing the low-potassium molybdenum rod under the conditions that the melting power of an electron gun is 110Kw, the main high-voltage is 30Kv, the current of the electron beam is 3.5A, the filament voltage is 5V, and the speed of an electrode rod is 120 mm/min.
In the embodiment, the content of potassium in the molybdenum powder used for preparing the molybdenum bar billet is less than 0.0023 percent, and the particle size distribution is between 5 and 15 mu m.
In this example, the density of the sintered molybdenum rod was 9.83g/cm3The section grain density of the sintered molybdenum rod is more than 1000/mm2. The content of potassium in the low-potassium molybdenum rod is less than or equal to 0.0001 percent.
Step two, preparing molybdenum substrate raw material particles;
slowly cutting the low-potassium molybdenum rod prepared in the step one layer by adopting an alloy cutter to prepare crumb-shaped molybdenum metal particles; then placing the crumb-shaped molybdenum metal particles into a plastic container, adding 500mL of nitric acid and 1500mL of pure water to carry out chemical reaction cleaning for 1.5h, cleaning with pure water after cleaning until the pH value of cleaning liquid is 7.0, and drying or naturally airing to obtain the molybdenum matrix raw material particles.
In the present example, the density ρ of nitric acid is 1.42g/mL, and pure water is first-grade water meeting GB/T6682 standard.
Step three, preparing a low-potassium molybdenum substrate;
loading the molybdenum substrate raw material particles prepared in the step two into a material boat, and then pushing the material boat into a reduction furnaceAt a hydrogen flow rate of 15m3Performing reduction reaction at the temperature of 900 ℃ in the reduction furnace to obtain reduced molybdenum matrix raw material particles; then, a standard screen with the mesh size of 50 mu m is adopted to sieve the reduced molybdenum metal particles, and undersize products are taken to prepare the low-potassium molybdenum matrix. In this example, the material boat is a pure molybdenum material boat known in the art to ensure that the molybdenum substrate raw material particles are not contaminated.
In this example, the potassium content in the low-potassium molybdenum matrix was measured by using flame atomic absorption spectrometry, inductively coupled plasma mass spectrometry, and glow discharge mass spectrometry, which are "methods for chemical analysis of molybdenum" having a national standard of GB/T4325-2013, and the results are shown in table 3. It should be noted that, when the method with the national standard of GB/T4325-2013 is used to detect the potassium content in a low-potassium molybdenum substrate, a molybdenum substrate known in the prior art is used as a blank reference.
Table 3 results of measuring potassium content in low-potassium molybdenum substrate of example 2
| Measurement method | GB/T4325.16-2013 method | Inductively coupled plasma mass spectrometry | Glow discharge mass spectrometry measurements |
| Potassium content | ＜0.0002％ | 0.000057％ | 0.000055％ |
As can be seen from Table 1, the low-K molybdenum substrate prepared in this example meets the analysis and detection requirement that the K content is less than 0.0002%.
Application example 2:
the low-potassium molybdenum substrate prepared in example 2 is used as a molybdenum substrate for quality control detection of molybdenum powder products and molybdenum trioxide products, and the quality control detection adopts flame atomic absorption spectrometry for potassium content determination in a molybdenum chemical analysis method with the national standard of GB/T4325-2013, and the results are shown in FIG. 3 and Table 4.
Table 4 quality control test results of molybdenum powder product and molybdenum trioxide product of application example 2
| Quality control sample | Measured value/%) | Theoretical value/%) | Absolute difference/%) | Method allowed difference/%) |
| Quality control sample of molybdenum powder product | 0.0086 | 0.0084 | 0.0002 | 0.0015 |
| Quality control sample of molybdenum trioxide product | 0.0042 | 0.0043 | 0.0001 | 0.0010 |
As can be seen from fig. 3 and table 4, the linear correlation coefficient of the analysis working curve drawn by using the low-potassium molybdenum matrix is 0.9998, and the detection requirement that the linear correlation coefficient of the analysis working curve is not less than 0.9995 can be satisfied. The low-potassium molybdenum matrix is used as a molybdenum matrix detection quality control sample, the method tolerance is 0.0010% and 0.0015%, and the requirement of the quality detection method tolerance can be met.
Example 3:
the embodiment provides a preparation method of a low-potassium molybdenum substrate, which specifically comprises the following steps:
step one, preparing a low-potassium molybdenum rod;
pressing molybdenum powder into a molybdenum rod blank by adopting a proper rubber sleeve die, placing the pressed molybdenum rod blank into a medium-frequency sintering furnace, and sintering at the temperature of 1500 ℃ for 8 hours to obtain a sintered molybdenum rod; and then placing the sintered molybdenum rod in an electron beam melting furnace, and preparing the low-potassium molybdenum rod under the conditions that the melting power of an electron gun is 110Kw, the main high-voltage is 30Kv, the current of the electron beam is 3.5A, the filament voltage is 5V, and the speed of an electrode rod is 120 mm/min.
In the embodiment, the content of potassium in the molybdenum powder used for preparing the molybdenum bar billet is less than 0.0012%, and the particle size distribution is between 5 and 15 microns.
In this example, the density of the sintered molybdenum rod was 9.71g/cm3The section grain density of the sintered molybdenum rod is more than 1000/mm2. The content of potassium in the low-potassium molybdenum rod is less than or equal to 0.0001 percent.
Step two, preparing molybdenum substrate raw material particles;
slowly cutting the low-potassium molybdenum rod prepared in the step one layer by adopting an alloy cutter to prepare scrap-shaped molybdenum metal particles; and then placing the crumb-shaped molybdenum metal particles into a plastic container, adding 1000mL of nitric acid and 3000mL of pure water to carry out chemical reaction cleaning for 2h, cleaning with pure water after cleaning until the pH value of the cleaning solution is 7.0, and drying or naturally airing to obtain the molybdenum matrix raw material particles.
In the present example, the density ρ of nitric acid is 1.42g/mL, and pure water is secondary water that meets the GB/T6682 standard.
Step three, preparing a low-potassium molybdenum substrate;
loading the molybdenum-based raw material particles prepared in the step two into a material boat, then pushing the material boat into a reduction furnace, and carrying out reduction reaction under the conditions that the hydrogen flow is 10m & lt 3 & gt/h and the temperature of the reduction furnace is 950 ℃ to prepare reduced molybdenum-based raw material particles; then, a standard screen with the mesh size of 75 mu m is adopted to sieve the reduced molybdenum metal particles, and undersize products are taken to prepare the low-potassium molybdenum matrix. In this example, the material boat is a pure molybdenum material boat known in the art to ensure that the molybdenum substrate raw material particles are not contaminated.
In this example, the potassium content in the low-potassium molybdenum substrate was measured by flame atomic absorption spectrometry for potassium content determination, inductively coupled plasma mass spectrometry, and glow discharge mass spectrometry, which are national standards GB/T4325-2013, and the results are shown in table 5. It should be noted that, when the method with the national standard of GB/T4325-2013 is used to detect the potassium content in the low-potassium molybdenum matrix, the molybdenum matrix known in the prior art is used as a blank reference.
TABLE 5 results of measuring potassium content in low-potassium molybdenum substrates of example 3
| Measurement method | GB/T4325.16-2013 method | Inductively coupled plasma mass spectrometry | Glow discharge mass spectrometry measurements |
| Potassium content | ＜0.0002％ | 0.000087％ | 0.000091％ |
As can be seen from Table 5, the low-K molybdenum substrate prepared in this example meets the analysis and detection requirement of the K content being less than 0.0002%.
Application example 3:
the low-potassium molybdenum substrate prepared in example 3 was used as a molybdenum substrate in quality control detection of molybdenum powder products and molybdenum trioxide products, and the results of the quality control detection were shown in fig. 4 and table 6, where flame atomic absorption spectrometry for determination of potassium content by molybdenum chemical analysis method, which is a national standard GB/T4325-2013, was used.
Table 6 quality control test results of molybdenum powder product and molybdenum trioxide product of application example 3
| Quality control sample | Measured value/%) | Theoretical value/% | Absolute difference/%) | Method allowed difference/%) |
| Quality control sample of molybdenum powder product | 0.0081 | 0.0084 | 0.0003 | 0.0015 |
| Quality control sample of molybdenum trioxide product | 0.0039 | 0.0043 | 0.0004 | 0.0010 |
As can be seen from fig. 4 and table 6, the linear correlation coefficient of the analysis working curve drawn by using the low-potassium molybdenum matrix is 0.9998, and the detection requirement that the linear correlation coefficient of the analysis working curve is not less than 0.9995 can be satisfied. The low-potassium molybdenum matrix is used as a molybdenum matrix detection quality control sample, the method tolerance is 0.0010% and 0.0015%, and the requirement of the quality detection method tolerance can be met.
Claims (9)
1. The preparation method of the low-potassium molybdenum substrate is characterized by comprising the following steps:
step one, preparing a low-potassium molybdenum rod;
pressing molybdenum powder into molybdenum rod blanks, and sintering the pressed molybdenum rod blanks to obtain sintered molybdenum rods; then carrying out electron beam melting on the sintered molybdenum rod to obtain a low-potassium molybdenum rod;
step two, preparing molybdenum substrate raw material particles;
cutting the low-potassium molybdenum rod prepared in the step one to prepare scrap-shaped molybdenum metal particles; then, chemically cleaning the scrap-shaped molybdenum metal particles by using nitric acid and water, and drying after cleaning to prepare molybdenum matrix raw material particles;
step three, preparing a low-potassium molybdenum substrate;
carrying out reduction reaction on the molybdenum matrix raw material prepared in the step two to prepare reduced molybdenum matrix raw material particles; and sieving the reduced molybdenum matrix raw material particles to obtain the low-potassium molybdenum matrix.
2. The method of claim 1, wherein the low-potassium molybdenum substrate has a potassium content of less than 0.0002%.
3. The method for preparing the low-potassium molybdenum substrate according to claim 1, wherein in the step one, the sintering temperature of the sintering is 1500-1910 ℃, and the sintering time is 6-8 h.
4. The method for preparing the low-potassium molybdenum substrate as claimed in claim 1, wherein in the first step, the electron gun melting power of the vacuum electron beam melting is 100-120 Kw, the main high voltage is 25-35 Kv, the electron beam current is 2.0-4.0A, the filament voltage is 4-6V, and the electrode rod speed is 100-150 mm/min.
5. The method for preparing a low-potassium molybdenum substrate according to claim 1, wherein in the second step, the volume ratio of the nitric acid to the water is 1.
6. The method for preparing a low-potassium molybdenum substrate according to claim 1, wherein in the second step, the cleaning time is 1-2 hours.
7. The method for preparing the low-potassium molybdenum substrate according to claim 1, wherein the hydrogen flow rate of the reduction reaction in the third step is 10-20 m3The temperature of the reduction furnace is 850-950 ℃.
8. A low-potassium molybdenum substrate, wherein the low-potassium molybdenum substrate is prepared by the method of any one of claims 1 to 7.
9. The use of the low-potassium molybdenum substrate of claim 8 as a molybdenum substrate in quality control testing of molybdenum powder products and molybdenum trioxide products.
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