CN108788129B - Refractory metal powder, preparation method thereof and metal product - Google Patents
Refractory metal powder, preparation method thereof and metal product Download PDFInfo
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- CN108788129B CN108788129B CN201810695000.6A CN201810695000A CN108788129B CN 108788129 B CN108788129 B CN 108788129B CN 201810695000 A CN201810695000 A CN 201810695000A CN 108788129 B CN108788129 B CN 108788129B
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- 239000000843 powder Substances 0.000 title claims abstract description 146
- 239000003870 refractory metal Substances 0.000 title claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000002245 particle Substances 0.000 claims abstract description 67
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000001301 oxygen Substances 0.000 claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 37
- 238000007493 shaping process Methods 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 30
- 238000009826 distribution Methods 0.000 claims abstract description 30
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 25
- 230000009467 reduction Effects 0.000 claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 18
- 238000010146 3D printing Methods 0.000 claims abstract description 13
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001362 Ta alloys Inorganic materials 0.000 claims abstract description 9
- 229910001257 Nb alloy Inorganic materials 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000007873 sieving Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 8
- 238000005554 pickling Methods 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000007599 discharging Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
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- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
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- 238000013461 design Methods 0.000 description 2
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- 150000002431 hydrogen Chemical class 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 229910001069 Ti alloy Inorganic materials 0.000 description 1
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- -1 niobium metals Chemical class 0.000 description 1
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- 150000003481 tantalum Chemical class 0.000 description 1
Images
Classifications
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- B22F1/0003—
-
- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
-
- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
-
- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/34—Process control of powder characteristics, e.g. density, oxidation or flowability
-
- 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
- B22F9/023—Hydrogen absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The application provides refractory metal powder which is spherical and/or spheroidal, wherein the particle size distribution concentration coefficient M of the refractory metal powder is 1.0-2.0; the refractory metal powder is pure niobium powder, pure tantalum powder, niobium alloy powder or tantalum alloy powder. The invention also provides a preparation method of the refractory metal powder, which sequentially carries out a series of steps of hydrogenation, ball milling and crushing, dehydrogenation, airflow shaping, acid cleaning, vacuum heat treatment, oxygen reduction and acid cleaning to finally obtain the spherical/spheroidal refractory metal powder. The application also provides a metal product which is obtained by 3D printing the refractory metal powder.
Description
Technical Field
The invention relates to the technical field of metal powder, in particular to refractory metal powder, a preparation method thereof and a metal product.
Background
Laser additive manufacturing, also known as laser 3D printing technology, has developed rapidly in recent years. Laser additive manufacturing is a technology for directly manufacturing a solid part from a digital model in a layer-by-layer stacking mode. The basic idea of the laser additive manufacturing technology is to adopt an integral idea in mathematics, namely that any three-dimensional entity can be formed by overlapping infinite two-dimensional planes; firstly, CAD modeling is carried out on solid parts to be processed, a layered two-dimensional plane is cut, powder synchronously fed in is melted by laser or preset powder is selectively sintered to form a two-dimensional cladding layer, and the two-dimensional cladding layer is gradually and sequentially stacked into three-dimensional solid parts.
Compared with the traditional manufacturing technology, the laser additive manufacturing has the following characteristics: 1) saving materials, and realizing 'net forming' or 'near net forming' without or with a small amount of subsequent processing; 2) large forging and pressing equipment, a die and a special clamp are not needed; 3) the material with complex shape and difficult processing can be manufactured; 4) personalized design and flexible production; 5) the time from design to manufacture is shortened, and the manufacturing cost and risk are reduced; 6) can be used for repairing parts. The technology is a brand-new manufacturing technology with short period and low cost, and has important application prospect in the fields of aviation, aerospace, biomedicine and the like.
As powder-fed laser additive manufacturing is becoming more mature in titanium alloy application, various additive manufacturing companies begin to pay attention to application research of powder-fed laser additive manufacturing in the field of high-temperature refractory metals. The requirement of the powder feeding type laser additive manufacturing technology on tantalum powder is that the particle size is uniformly dispersed, preferably in a spherical or spheroidal shape, and the lower the oxygen content is, the better the oxygen content is; the powder with dispersed particle size distribution, especially single particles with larger or smaller particle size, can affect the powder spreading effect, or secondary agglomerated particles obtained after high-temperature treatment can cause uneven powder spreading, or the requirement of powder mechanical spreading uniformity in a printing cavity can not be met, so that the 3D printing effect is affected; particles with complex particle shapes (such as coral-shaped porous structures) can cause poor powder flowability and uneven powder laying; non-spherical or sphere-like solid particles (such as stone-like single particles) are sharp in edges and corners, which easily cause bridging among particles in the 3D printing process, and the particle structures of the two shapes can cause the generation of hollow and bubble phenomena in the product, thereby causing the performance of the product to be reduced; too high oxygen content can cause oxide in manufactured metal equipment to form defects, and the requirements of the 3D printing powder cannot be met. Therefore, research into spherical powder for 3D printing and a method of preparing the same has been increasing in recent years.
Plasma powder processing technology is one of the main methods for producing spherical powder. However, the plasma powder processing technology has large equipment investment, high technical requirements, complex process and high powder processing cost, and is difficult to produce on a large scale.
Spray granulation techniques also yield spherical metal powders. Chinese patents of application nos. cn201310470047.x and cn201410693232.x both disclose a method for preparing metal powder for 3D printing, which can only prepare metals or alloys having a melting point below 2000 ℃, but cannot prepare metals having a melting point above 2000 ℃, such as tantalum, niobium, etc.; chinese patent application No. CN201510044848.9 discloses a method and apparatus for preparing ultrafine spherical metal powder for 3D printing, which are also incapable of preparing metals with high melting point, such as tantalum and niobium metals.
The method comprises the steps of adding the tantalum powder which is coarsely crushed after hydrogenation into a cyclone type crushing classifier, introducing compressed air impact into the cyclone type crushing classifier to perform crushing classification, wherein the tantalum powder which is coarsely crushed after the coarse crushing contains a large amount of hydrogen, according to the characteristic of hydrogen brittleness of the tantalum powder, the tantalum powder which is coarsely crushed after the hydrogenation directly enters an air flow crusher to be crushed and classified, the grinding and shaping effects on the metal powder cannot be achieved, spherical or nearly spherical powder is difficult to obtain in the mode, and the edge angle of the finally obtained tantalum powder particle is sharp. Chinese patent application No. CN201410449771.9 discloses a tantalum powder with spherical or spheroidal particle shape, rounded corners and uniform particle size distribution, but from the drawings provided by the patent, the tantalum powder particle is polyhedral; the tantalum powder is prepared by subjecting tantalum ingots to hydrogenation, crushing, dehydrogenation and airflow impact, and then carrying out processes of first low-temperature heat treatment, second high-temperature heat treatment, high-temperature oxygen reduction, third high-temperature heat treatment and the like, so that the obtained tantalum powder particles are bonded, agglomerated and sintered to form secondary particles under the high-temperature treatment condition, the agglomeration is formed, the high-temperature treatment is favorable for forming a porous structure during later-stage capacitor preparation, and the tantalum powder particles do not exist in an independent and single particle form any more. According to the patent documents, the tantalum powder obtained by the hydrogenation crushing technology is not spherical/spheroidal in shape and has wide particle size distribution.
Disclosure of Invention
The invention aims to provide refractory metal powder and a preparation method thereof, and the refractory metal powder prepared by the method is spherical/spheroidal particles and has centralized particle size distribution.
In view of the above, the present application provides a refractory metal powder, which is spherical and/or spheroidal, and has a particle size distribution concentration coefficient M of 1.0 to 2.0; the refractory metal powder is pure niobium powder, pure tantalum powder, niobium alloy powder or tantalum alloy powder.
Preferably, the refractory metal powder consists of separate, unitary powder particles, and has a D90 ≦ 65 μm and an oxygen content ≦ 400 ppm.
The application also provides a preparation method of the refractory metal powder, which comprises the following steps:
A) carrying out hydrogenation treatment on a refractory metal ingot blank, wherein the refractory metal ingot blank is a pure niobium ingot, a niobium alloy ingot, a pure tantalum ingot or a tantalum alloy ingot;
B) ball-milling and crushing the refractory metal ingot blank subjected to hydrogenation treatment;
C) carrying out dehydrogenation treatment on the powder subjected to ball milling and crushing;
D) shaping the powder subjected to dehydrogenation through airflow;
E) pickling the powder obtained in the step D);
F) and E) carrying out vacuum heat treatment on the powder obtained in the step E), carrying out oxygen reduction on the powder subjected to the vacuum heat treatment, and finally carrying out acid pickling to obtain refractory metal powder.
Preferably, the air flow shaping device further comprises: and classifying the powder after the airflow shaping.
Preferably, the pickling further comprises the following steps: and (4) grading the powder after the acid washing.
Preferably, the particle size of the powder after ball milling and crushing is-325 meshes or-400 meshes.
Preferably, the dehydrogenation treatment temperature is 700-900 ℃, and the time is 2-5 h.
Preferably, the temperature of the vacuum heat treatment is 800-1300 ℃, and the time is 30-120 min.
Preferably, the temperature of the oxygen reduction is 650-850 ℃, and the time is 2-4 h; the amount of the magnesium powder in the oxygen reduction is 0.2-2.0 wt% of the powder after the vacuum heat treatment.
The application also provides a metal product, which is obtained by 3D printing of the refractory metal powder prepared by the preparation method in the scheme or the preparation method in the scheme.
The application provides refractory metal powder, which is spherical and/or spheroidal in shape, and the particle size distribution concentration coefficient M is 1.0-2.0; the refractory metal powder has concentrated particle size distribution, spherical and/or quasi-spherical shape and smooth edges and corners.
Further, the application also provides a preparation method of the refractory metal powder, which comprises the steps of hydrogenation treatment, ball milling and crushing, dehydrogenation treatment, gas flow shaping, acid cleaning, vacuum heat treatment, oxygen reduction and acid cleaning are sequentially carried out on a refractory metal ingot blank to prepare spherical/spheroidal powder, and the refractory metal powder consists of independent and single powder particles, is smooth in edges and corners, narrow in particle size distribution and good in spreadability and fluidity, is particularly suitable for 3D printing raw materials, and enables the prepared metal product to be high in quality.
Drawings
FIG. 1 is a graph showing the particle size distribution of tantalum powder prepared in example 1 of the present invention;
FIG. 2 is an SEM photograph of tantalum powder prepared in example 1 of the present invention;
FIG. 3 is an SEM photograph of tantalum powder prepared in example 2 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Aiming at the problems that the tantalum powder is not spherical or quasi-spherical in shape and has wider particle size distribution in the prior art, the refractory metal powder provided by the invention is spherical and/or quasi-spherical, has smooth edges and corners of powder particles and has centralized particle size distribution. Specifically, the refractory metal powder is spherical and/or spheroidal, and the particle size distribution concentration coefficient M of the refractory metal powder is 1.0-2.0; the refractory metal powder is pure niobium powder, pure tantalum powder, niobium alloy powder or tantalum alloy powder.
In the invention, the concentration of the particle size distribution of the powder is characterized by a particle size distribution concentration coefficient M, and the more concentrated the particle size distribution is, the smaller the value of M is. M ═ D4, 3/D3, 2, where D4, 3 is the volume average particle diameter of the powder and D3, 2 is the surface area average particle diameter of the powder; the closer the values of D4, 3 and D3, 2 are, the more regular the shape of the sample particles is, the more concentrated the particle size distribution is; the larger the difference, the broader the particle size distribution. M of the refractory metal powder is 1.0-2.0, in a specific embodiment, M is 1.0-1.5, and in a specific embodiment, M is 1.0-1.3; d90 ≦ 65 μm, in a specific embodiment, D90 ≦ 50 μm, and in a specific embodiment, D90 ≦ 40 μm. The oxygen content of the refractory metal powder is less than or equal to 400ppm, in a specific embodiment, the oxygen content of the refractory metal powder is less than or equal to 300ppm, and in a specific embodiment, the oxygen content of the refractory metal powder is less than or equal to 100 ppm.
The invention also discloses a preparation method of the refractory metal powder, which comprises the following steps:
A) carrying out hydrogenation treatment on a refractory metal ingot blank, wherein the refractory metal ingot blank is a pure niobium ingot, a niobium alloy ingot, a pure tantalum ingot or a tantalum alloy ingot;
B) ball-milling and crushing the refractory metal ingot blank subjected to hydrogenation treatment;
C) carrying out dehydrogenation treatment on the powder subjected to ball milling and crushing;
D) shaping the powder subjected to dehydrogenation through airflow;
E) pickling the powder obtained in the step D);
F) and E) carrying out vacuum heat treatment on the powder obtained in the step E), carrying out oxygen reduction on the powder subjected to the vacuum heat treatment, and finally carrying out acid pickling to obtain refractory metal powder.
In the above process of preparing refractory metal powder, the present application first performs a hydrogenation treatment on a refractory metal ingot blank to primarily crush the refractory metal ingot blank to obtain refractory metal chips. In the present application, the refractory metal ingot blank is specifically a pure niobium ingot, niobiumAn alloy ingot, a pure tantalum ingot or a tantalum alloy ingot. The hydrogenation treatment process comprises the following steps: hydrogen atmosphere, maintaining hydrogen pressure at 1.0 × 105Pa～1.2×105Heating to 700-900 ℃ under Pa, preserving heat for 2-4 h, cooling after heat preservation, and hydrogenating until the refractory metal ingot blank does not absorb hydrogen any more; more specifically, a refractory metal ingot blank is loaded into a clean stainless steel crucible, hung into a reaction bomb and vacuumized to 1 × 102Pa below, and hydrogen gas is charged to 1.0X 105Pa～1.2×105Pa, heating, and keeping the bomb internal pressure closely to not exceed 2.0 × 105Pa, preventing the rubber tube from being cracked due to overlarge pressure to cause hydrogen leakage, preserving heat for 2-4 h when the temperature is raised to 700-900 ℃, cutting off power and reducing the temperature for hydrogenation after the heat preservation is finished, and replenishing hydrogen in time in the temperature reduction process until the tantalum ingot does not absorb hydrogen any more.
According to the invention, the hydrotreated refractory metal ingot is then ball milled and crushed to obtain refractory metal powder. The ball milling is a well known technique to those skilled in the art, and the specific operation thereof is not particularly limited in this application. The materials after ball milling and crushing are sieved by different meshes, and the particle size distribution of the obtained hydrogenated materials is different, so that the particle size distribution of the subsequent obtained final product can be influenced. In the invention, the material after ball milling and crushing is preferably sieved by a 325-mesh or 400-mesh screen to obtain minus 325-mesh or minus 400-mesh undersize, so as to ensure that the final product has centralized particle size distribution, small D90 and good spheroidizing effect. If the subsequent treatment is carried out by using the oversize powder with the particle size of +325 meshes or coarser, the particle size distribution of the final product is wider, the D90 is larger, and the spheroidization effect of the particles is poor.
After ball milling, the powder obtained is subjected to dehydrogenation treatment, the specific flow of the dehydrogenation treatment is not particularly limited, and the hydrogenated material is heated by adopting a dehydrogenation treatment technical scheme well known to those skilled in the art. In the invention, the dehydrogenation treatment is preferably carried out under the protection of inert gas, and the temperature of the dehydrogenation treatment is 700-900 ℃, in certain embodiments 700-800 ℃, in certain embodiments 720 ℃, 750 ℃ or 780 ℃; the time of the dehydrogenation treatment is 2-5 h, in some embodiments, the time of the dehydrogenation treatment is 2-4 h, and in some embodiments, the time of the dehydrogenation treatment is 2-3 h. In the present invention, the dehydrogenation treatment makes the hydrogen content in the metal particles as low as possible while not allowing the ultrafine metal particles to adhere to the surface of the large particles, thereby ensuring the dispersibility of the metal particles. In the present invention, the finer the metal particles, the lower the dehydrogenation temperature should be. In the present invention, it is preferable that the metal particles after the heat preservation by heating are cooled, tapped and sieved to obtain the dehydrogenated refractory metal particles.
And shaping the gas flow after the dehydrogenation treatment so as to obtain powder with good spherical/spheroidal shaping effect. The air flow shaping is carried out in an air flow mill, in the air flow shaping process, the working pressure is 5.0-7.0 kg, the primary working frequency and the secondary working frequency are 20-50 HZ, the air flow shaping time is controlled to be 5-30 h, the appearance of powder is changed by controlling the parameters in the air flow shaping process, and ultrafine powder is collected in secondary powder in a centralized manner, so that the particle size distribution of the obtained primary powder is more concentrated and the ultrafine powder is basically absent. The method and the device can repeatedly carry out air flow shaping on the material according to the shape of the material after the air flow shaping so as to obtain powder with better spherical/quasi-spherical effect. According to the method, the gas flow shaping is carried out after the dehydrogenation treatment, otherwise, the refractory powder after ball milling and crushing contains a large amount of hydrogen, the powder after hydrogenation is directly subjected to gas flow milling treatment after ball milling, the grinding and shaping effects on metal powder particles cannot be achieved, spherical or nearly spherical powder is difficult to obtain in the mode, and the edges and corners of the obtained powder particles are sharp.
According to the invention, the powder after the gas flow shaping is subjected to acid washing to remove chemical impurities in the ball milling crushing and gas flow shaping processes, and the purification effect is achieved. In the present application, the acid solution for acid cleaning is preferably a mixed acid of nitric acid and hydrofluoric acid.
And after acid washing, performing vacuum heat treatment on the powder after acid washing, and removing H, F and other impurities brought in the acid washing process while ensuring that the metal powder is not sintered and does not grow. In the present application, it is preferable to perform vacuum heat treatment on the metal powder at a low temperature to remove impurities such as H, F introduced by acid washing and to ensure that the metal powder is not sintered and does not grow large. In the present invention, the temperature of the vacuum heat treatment is 800 to 1300 ℃, in some embodiments 1000 to 1250 ℃, and in some embodiments 1100 ℃. The method of vacuum heat treatment is not particularly limited in the present invention, and a heat treatment scheme known to those skilled in the art may be adopted. In the present invention, the heat treatment time is 30 to 120min, in some embodiments, 60 to 90min, and in some embodiments, 60 min. The invention preferably carries out cooling, passivation, furnace discharging and sieving on the product obtained after heat treatment.
After the vacuum heat treatment, the oxygen content of the powder after the vacuum heat treatment is reduced, so that the metal powder is prevented from being sintered and growing while the oxygen content is reduced; if the oxygen reduction is performed without vacuum heat treatment, it is not preferable to reduce the oxygen content in the powder. The powder after vacuum heat treatment is preferably subjected to oxygen reduction at a low temperature, wherein the temperature of the oxygen reduction is 650-850 ℃, in specific embodiments, the temperature of the oxygen reduction is 700-800 ℃, and in certain specific embodiments, the temperature of the oxygen reduction is 750 ℃. The method for reducing oxygen at low temperature is not particularly limited, and the technical scheme of reducing oxygen, which is well known to those skilled in the art, can be adopted. In the invention, the time for oxygen reduction is 2-4 h, in a specific embodiment, the time for oxygen reduction is 2.5-3.5 h, and in a specific embodiment, the time for oxygen reduction is 3 h. Magnesium powder is added in the oxygen reduction process, and the using amount of the magnesium powder is 0.2-2.0% of the mass of the metal powder after vacuum heat treatment, more preferably 0.5-1.5%, more preferably 0.8-1.2%, and most preferably 1.0%. The invention preferably carries out cooling, passivation, furnace discharging and sieving on the product obtained after the oxygen reduction treatment.
The powder after oxygen reduction is finally subjected to acid cleaning to remove chemical impurities such as magnesium, magnesium oxide and the like remained in the oxygen reduction process. The acid solution for acid cleaning is a mixed acid of nitric acid and hydrofluoric acid.
During the process of preparing the refractory metal powder, a grading treatment process is also included, and the grading treatment process can be used or not used, and is preferably used, so that a small amount of ultrafine powder in the metal powder can be removed. The grading treatment is carried out before the vacuum heat treatment, and the grading treatment and the pickling operation are not in sequence and can be interchanged. The classification is carried out in the examples by means of hydraulic classification.
The application also provides the refractory metal powder prepared by the method, wherein the refractory metal powder is pure tantalum powder, tantalum alloy powder, pure niobium powder or niobium alloy powder.
The application also provides a metal product which is obtained by 3D printing the refractory metal powder in the scheme. Since the refractory metal powder is spherical/spheroidal powder, the particle size distribution is concentrated, and the oxygen content is low, the quality of the metal product is higher.
The refractory metal powder provided by the invention is spherical/spheroidal powder, is composed of independent and single powder particles, has smooth edges and corners, narrow particle size distribution and good spreadability and fluidity, is particularly suitable for 3D printing raw materials, and the prepared metal product has higher quality and is beneficial to controlling defects such as hollowness, bubbles and the like. The preparation method of the refractory metal powder provided by the invention has the advantages of small equipment investment, low production cost, high working efficiency and short process route.
For further understanding of the present invention, the method for preparing the refractory metal powder according to the present invention is described in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
Selecting tantalum ingots with the tantalum content of more than 99.995%, and carrying out hydrogenation crushing on the tantalum ingots; ball-milling and crushing the tantalum chips obtained after hydrogenation, sieving the materials subjected to ball-milling and crushing by a 325-mesh sieve, and taking tantalum powder below the 325-mesh sieve to obtain 20kg of tantalum particles with the size of-325 meshes; then loading the tantalum particles into a reaction bomb, heating under vacuum condition, keeping the temperature at 800 ℃ for about 120min, and then carrying outCooling, discharging and sieving by a 100-mesh sieve to obtain 19.92kg of dehydrogenated tantalum powder; loading the tantalum powder after dehydrogenation into an airflow mill for airflow shaping, wherein the working pressure is 6.0kg, and the primary and secondary working frequencies are respectively 30HZ and 30HZ, and shaping for 10h to obtain 15.34kg of primary tantalum powder and 3.84kg of secondary tantalum powder; using HNO to the primary tantalum powder after the gas flow shaping3Mixed acid with HF (HNO)3The volume ratio of HF to water is 4:1:20), removing metal impurities by acid washing, drying and sieving to obtain 14.86kg of tantalum powder after acid washing;
then the tantalum powder after acid washing is added in 10-1Heat treatment under Pa vacuum condition, keeping the temperature at 1200 ℃ for 60min, and finally cooling, passivating and discharging; mixing the tantalum powder after heat treatment with magnesium powder accounting for 1.0% of the weight of the tantalum powder, heating to 800 ℃ under the protection of inert gas, preserving heat for 2 hours, evacuating and discharging magnesium for 3 hours, cooling, passivating, discharging, washing with nitric acid to remove redundant magnesium and magnesium oxide, washing with deionized water to be neutral, drying and sieving the tantalum powder to obtain 14.27kg of tantalum powder.
The tantalum powder prepared in this example was subjected to composition measurement according to GB/T15076 "chemical analysis method for tantalum and niobium", the test results are shown in Table 1, the performance test results of the tantalum powder prepared in the examples of the present invention are shown in Table 2, and the flowability was tested by using a Hall flow meter. The particle size distribution of the tantalum powder prepared in example 1 of the present invention was measured using a Mastersizer 2000 with a malvern instrument, and the results are shown in fig. 1, where fig. 1 is a particle size distribution diagram of the tantalum powder prepared in example 1 of the present invention; the tantalum powder prepared in the embodiment is SEM-detected by a JSM-5610LV high-low resolution scanning electron microscope, and the detection result is shown in fig. 2, and fig. 2 is an SEM photograph of 200 times of the tantalum powder prepared in embodiment 1 of the present invention.
Example 2
Selecting tantalum ingots with the tantalum content of more than 99.995%, and carrying out hydrogenation crushing on the tantalum ingots; ball-milling and crushing the hydrogenated tantalum chips, sieving the ball-milled and crushed materials with a 400-mesh sieve, and taking tantalum powder below the 400-mesh sieve to obtain 20kg of tantalum particles with the granularity of-400 meshes; then loading the tantalum particles into a reaction bomb, heating under vacuum condition, and keeping the temperature at 750 ℃ for about 120min, thenThen cooling, discharging and sieving by a 100-mesh sieve to obtain 19.87kg of dehydrogenated tantalum powder; loading the tantalum powder after dehydrogenation into an airflow mill for airflow shaping, wherein the working pressure is 6.5kg, and the primary and secondary working frequencies are 40HZ and 40HZ respectively, and shaping for 15h to obtain 14.62kg of primary tantalum powder and 3.20kg of secondary tantalum powder; the first-stage tantalum powder after air flow shaping uses HNO3Mixed acid with HF (HNO)3The volume ratio of HF to water is 4:1:20), removing metal impurities by acid washing, drying and sieving to obtain 13.46kg of tantalum powder after acid washing;
then the tantalum powder after acid washing is added in 10-1Heat treatment under Pa vacuum condition, heat preservation at 1100 ℃ for 60 minutes, and finally cooling, passivating and discharging; mixing the tantalum powder after heat treatment with magnesium powder accounting for 1.3% of the weight of the tantalum powder, heating to 750 ℃ under the protection of inert gas, preserving heat for 2 hours, evacuating and discharging magnesium for 3 hours, cooling, passivating, discharging, washing with nitric acid to remove redundant magnesium and magnesium oxide, washing with deionized water to be neutral, drying and sieving the tantalum powder to obtain 12.74kg of tantalum powder.
The tantalum powder prepared in this example was subjected to a performance test according to the method described in example 1, and the test results are shown in tables 1 and 2;
TABLE 1 compositional data for tantalum powders prepared in examples 1 and 2
| O(ppm) | N(ppm) | Fe(ppm) | Ni(ppm) | Cr(ppm) | |
| Example 1 | 86 | 20 | 9 | 3 | 3 |
| Example 2 | 180 | 20 | 10 | 3 | 3 |
TABLE 2 Table of Properties of tantalum powders prepared in examples 1 and 2
As can be seen from tables 1 and 2 and the accompanying drawings, the tantalum powder prepared by the method provided by the invention is spherical/spheroidal, the particle size distribution range is concentrated, the particle size distribution concentration coefficient is small, D90 is small, and the oxygen content is low.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. The refractory metal powder is characterized in that the refractory metal powder is spherical and/or spheroidal, and the particle size distribution concentration coefficient M of the refractory metal powder is 1.0-2.0; the refractory metal powder is pure niobium powder, pure tantalum powder, niobium alloy powder or tantalum alloy powder;
the preparation method of the refractory metal powder comprises the following steps:
A) carrying out hydrogenation treatment on a refractory metal ingot blank, wherein the refractory metal ingot blank is a pure niobium ingot, a niobium alloy ingot, a pure tantalum ingot or a tantalum alloy ingot;
B) ball-milling and crushing the refractory metal ingot blank subjected to hydrogenation treatment; sieving the ball-milled and crushed material by using a 325-mesh or 400-mesh sieve;
C) carrying out dehydrogenation treatment on the powder obtained in the step B);
D) shaping the powder subjected to dehydrogenation through airflow;
E) pickling the powder obtained in the step D);
F) carrying out vacuum heat treatment on the powder obtained in the step E), carrying out oxygen reduction on the powder subjected to vacuum heat treatment, and finally carrying out acid pickling to obtain refractory metal powder;
the dehydrogenation treatment temperature is 700-900 ℃, and the time is 2-5 h;
the temperature of the vacuum heat treatment is 800-1300 ℃, and the time is 30-120 min;
the air flow shaping is carried out in an air flow mill, in the air flow shaping process, the working pressure is 5.0-7.0 kg, the primary and secondary working frequencies are both 20-50 HZ, and the air flow shaping time is controlled to be 5-30 h;
the temperature of the oxygen reduction is 650-850 ℃, and the time is 2-4 h; the amount of the magnesium powder in the oxygen reduction is 0.2-2.0 wt% of the powder after the vacuum heat treatment.
2. The refractory metal powder as claimed in claim 1, wherein the refractory metal powder consists of separate, unitary powder particles and has a D90 ≤ 65 μ ι η and an oxygen content ≤ 400 ppm.
3. The refractory metal powder of claim 1, further comprising, after shaping the gas flow: and classifying the powder after the airflow shaping.
4. The refractory metal powder of claim 1, further comprising, after the acid washing: and (4) grading the powder after the acid washing.
5. The refractory metal powder as claimed in any one of claims 1 to 4, wherein the particle size of the ball-milled and crushed powder is-325 mesh or-400 mesh.
6. A metal product obtained by 3D printing the refractory metal powder according to any one of claims 1 to 5.
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