CN109014230B - Preparation method of molybdenum metal grid - Google Patents

Preparation method of molybdenum metal grid Download PDF

Info

Publication number
CN109014230B
CN109014230B CN201811011979.7A CN201811011979A CN109014230B CN 109014230 B CN109014230 B CN 109014230B CN 201811011979 A CN201811011979 A CN 201811011979A CN 109014230 B CN109014230 B CN 109014230B
Authority
CN
China
Prior art keywords
molybdenum
powder
metal grid
electron beam
rod
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811011979.7A
Other languages
Chinese (zh)
Other versions
CN109014230A (en
Inventor
韩强
王峰
何凯
李晶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jinduicheng Molybdenum Co Ltd
Original Assignee
Jinduicheng Molybdenum Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jinduicheng Molybdenum Co Ltd filed Critical Jinduicheng Molybdenum Co Ltd
Priority to CN201811011979.7A priority Critical patent/CN109014230B/en
Publication of CN109014230A publication Critical patent/CN109014230A/en
Application granted granted Critical
Publication of CN109014230B publication Critical patent/CN109014230B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
    • 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
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • 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
    • B22F10/20—Direct sintering or melting
    • B22F10/25—Direct deposition of metal particles, e.g. direct metal deposition [DMD] or laser engineered net shaping [LENS]
    • 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
    • B22F10/50—Treatment of workpieces or articles during build-up, e.g. treatments applied to fused layers during build-up
    • 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
    • B22F10/60—Treatment of workpieces or articles after build-up
    • B22F10/64—Treatment of workpieces or articles after build-up by thermal means
    • 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
    • B22F10/80—Data acquisition or data processing
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • 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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
    • 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
    • B33Y10/00—Processes of additive manufacturing
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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 invention discloses a preparation method of a molybdenum metal grid, which comprises the following steps: firstly, sequentially carrying out cold isostatic pressing, high-temperature sintering, hot precision forging and straightening treatment on molybdenum powder to obtain a molybdenum rod; secondly, processing the molybdenum rod into spherical molybdenum powder by adopting plasma rotating electrode powder-making equipment; and thirdly, preparing a molybdenum metal grid formed part by using spherical molybdenum powder as a raw material and adopting a powder bed electron beam 3D printer, and then sequentially carrying out annealing, hot isostatic pressing treatment and alkali washing to obtain the molybdenum metal grid. According to the invention, the molybdenum powder is prepared into spherical molybdenum powder, and then the molybdenum metal grid is prepared by adopting a powder bed electron beam 3D printer, so that the defects of high molybdenum metal strength, low plasticity, high possibility of oxidation, poor forming performance and difficulty in processing into complex structural parts and functional parts are overcome by utilizing the characteristics of good fluidity, compact and uniform particles, tight combination after rapid melting and high heat of an electron beam, the specification and the use performance of the molybdenum metal grid are improved, and the preparation cost is saved.

Description

Preparation method of molybdenum metal grid
Technical Field
The invention belongs to the field of processing of refractory metal materials, and particularly relates to a preparation method of a molybdenum metal grid.
Background
The melting point of the molybdenum is 2620 ℃, the boiling point is 5560 ℃, and the linear expansion coefficient is (5.8-6.2) multiplied by 10-6The percent of molybdenum metal has the advantages of high temperature resistance, corrosion resistance, small expansion coefficient, excellent electrical conductivity and thermal conductivity and the like, and simultaneously, the molybdenum metal has higher strength and hardness at normal temperature and high temperature due to the extremely strong bonding force among molybdenum atoms. Therefore, molybdenum metal is widely used as an additive in the steel smelting industry, an electrode and a packaging material in the power electronics industry, a high-temperature-resistant nozzle component in the aerospace field, a corrosion-resistant and temperature-resistant cladding material in the nuclear industry field, and high-temperature soaking molybdenum in the sapphire glass preparation fieldCrucible parts, flame sprayed molybdenum wire materials for piston rings and gears in the automobile industry, wire cut molybdenum wire materials for the precision die machining field, and high temperature resistant components such as heating bodies, shielding screens and the like in the vacuum furnace equipment field.
At present, the traditional production method of molybdenum metal products mainly comprises two modes, namely a vacuum melting method and a powder metallurgy method. The vacuum smelting method is characterized in that waste molybdenum metal blocks, rods or molybdenum powder are used as raw materials, the raw materials of molybdenum metal products are melted into liquid state in a vacuum condition in an electric arc or electron beam heating mode, the liquid state is solidified into molybdenum metal ingots in a cooling crystallizer, then the molybdenum metal ingots are subjected to processes of multi-pass extrusion, forging, rolling, annealing and the like to break and smelt as-cast crystal grains of the molybdenum ingots, the texture property of molybdenum metal is improved, and the molybdenum metal products are prepared into products such as molybdenum metal rods, plates, pipes, section bars and the like, and the molybdenum metal structural products with more complex points need to be subjected to stress-relief heating annealing and then are prepared according to different machining modes. The powder metallurgy method is characterized in that molybdenum metal powder is used as a raw material, the molybdenum metal powder is filled into a rubber sleeve die, the molybdenum metal powder is compacted and then integrally placed in a pressure-bearing cavity of isostatic pressing equipment to be pressed into a molybdenum metal biscuit, then the molybdenum metal biscuit is sintered into a sintered blank at high temperature in a vacuum or atmosphere furnace, and finally the sintered blank is processed into molybdenum rods, plates, pipes and simple special-shaped products in the modes of forging, rolling, extruding, annealing and the like.
The two processing modes can finish the preparation of simple geometric shapes (rods, plates, pipes and sections) of molybdenum metal products, but the two processing modes have long production processes and need more large-scale equipment, so that the quality control cost and the labor cost in the preparation process of the molybdenum products are increased; meanwhile, when the molybdenum product with a slightly complex shape is prepared, different machining modes are required to be adopted, so that the processing cost of the molybdenum product is increased, and the waste of rare and precious molybdenum metal raw materials is caused. For the molybdenum metal grid with the length, the width, the height and the thickness of each square through hole being (10 mm-100 mm) x (10 mm-100 mm), the size of each square through hole being (1 mm-10 mm) x (1 mm-10 mm) and the wall thickness of each partition fence being 0.1 mm-1 mm, no successful process of the vacuum melting method or the powder metallurgy method is reported in the prior art, and a new solution is required to be found for preparing the molybdenum grid product with the size so as to meet the application in the special field.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing a molybdenum metal grid aiming at the defects of the prior art. According to the method, molybdenum powder is prepared into spherical molybdenum powder, and then a molybdenum metal grid is prepared by a powder bed electron beam 3D printer, so that the defects that the molybdenum metal is high in strength, low in plasticity, easy to oxidize, poor in forming performance and difficult to process into complex structural parts and functional parts are overcome by utilizing the characteristics of good flowability, compact and uniform particles, tight combination after rapid melting and high heat of an electron beam, and the molybdenum metal grid with the size of (10 mm-100 mm) × (10 mm-100 mm) (length, width and height), the size of each square through hole (1 mm-10 mm) × (1 mm-10 mm) and the thickness of a barrier wall (0.1 mm-1 mm) is obtained, the service performance of the molybdenum metal grid is improved, and the preparation cost is saved.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for preparing a molybdenum metal grid is characterized by comprising the following steps:
step one, preparing a molybdenum rod:
step 101, loading molybdenum powder into a prefabricated rubber sleeve die, sealing the die with a rubber plug after compaction, then placing the die into a pressure-bearing cavity of a cold isostatic press for cold isostatic pressing, and demoulding to obtain a molybdenum rod biscuit; the granularity of the molybdenum powder is 2.0-4.5 mu m, the mass purity of the molybdenum powder is not less than 99.95 percent, the mass content of oxygen is not more than 1500ppm, and the tap density of the molybdenum powder is 2.0g/cm3～6.0g/cm3；
Step 102, finishing the outer surface of the molybdenum rod biscuit obtained in the step 101, and then placing the molybdenum rod biscuit in a vacuum furnace for high-temperature sintering treatment to obtain a molybdenum rod semi-finished product;
103, performing hot precision forging on the molybdenum rod semi-finished product obtained in the step 102 to obtain a forged molybdenum rod, straightening the forged molybdenum rod, and turning to remove surface scale to obtain the molybdenum rod; the cogging temperature of the hot precision forging is 1380-1500 ℃, and the forging system is one heating and three times;
step two, preparing spherical molybdenum powder:
step 201, clamping one end of the molybdenum rod prepared in the step 103 on a three-jaw chuck of plasma rotating electrode powder manufacturing equipment, extending the other end of the molybdenum rod into the center of a high-temperature cavity of the plasma rotating electrode powder manufacturing equipment, and generating a plasma arc in a space formed by the molybdenum rod and a plasma auxiliary electrode;
202, utilizing high temperature generated by a plasma arc to enable the end face of a molybdenum rod extending into the center of a high-temperature cavity to form molten liquid, enabling a three-grab chuck to drive the molybdenum rod to rotate at a high speed and to perform linear feeding motion towards the direction of the high-temperature cavity, condensing the molten liquid into spherical liquid drops under the action of centrifugal force of high-speed rotation, throwing the spherical liquid drops into a powder condensation collection bin, and condensing and sieving the spherical liquid drops to obtain spherical molybdenum powder; the micron-sized molybdenum metal spherical powder has the particle size of 60-120 mu m, the angle of repose of not more than 35 degrees, the sphericity of not less than 0.92 and the apparent density of not less than 5.5g/cm3Tap density of not less than 6.2g/cm3The mass content of oxygen is not more than 150ppm, and the mass content of H, C, N, Ca, Si, Mg, Al, Fe, Ni and Cu in the spherical molybdenum powder is less than 1 percent relative to the mass content increment of corresponding elements in the molybdenum rod;
step three, preparing a molybdenum metal grid:
301, loading the spherical molybdenum powder prepared in the step 202 into a bin of a powder bed electron beam 3D printer, inputting a CAD model of a molybdenum metal grid die into a control computer of the powder bed electron beam 3D printer, slicing the CAD model by using slicing software to obtain slicing data, preheating a forming substrate in a working cavity of the powder bed electron beam 3D printer by using an electron beam, laying the spherical molybdenum powder in the bin on the forming substrate according to the slicing data, heating by using the electron beam, melting the spherical molybdenum powder laid on the forming substrate into liquid metal in a surface exposure or point scanning manner, cooling to form single-layer solid sheet layers, and repeating the melting and cooling processes until the single-layer solid sheet layers are stacked layer by layer to obtain a molybdenum metal grid forming part; the thickness of the spreading layer is 80-120 mu m;
step 302, annealing the molybdenum metal grid formed part prepared in the step 301 in a hydrogen furnace, performing hot isostatic pressing treatment, and performing alkali washing to obtain a molybdenum metal grid; the size of the molybdenum metal grid is (10 mm-100 mm) × (10 mm-100 mm), the size of each square through hole is (1 mm-10 mm) × (1 mm-10 mm), and the wall thickness of the partition is 0.1 mm-1 mm.
According to the invention, molybdenum powder is subjected to cold isostatic pressing, sintering and forging to obtain a molybdenum rod with higher density, then the molybdenum rod is prepared into spherical molybdenum powder with higher sphericity by adopting plasma rotating electrode powder-making equipment, and then the spherical molybdenum powder is used as a raw material to prepare a molybdenum metal grid by adopting a powder bed electron beam 3D printer.
The preparation method of the molybdenum metal grid is characterized in that the pressure of the cold isostatic pressing treatment in the step 101 is 150 MPa-230 MPa, and the pressure maintaining time is 10 min-15 min. The molybdenum powder is pressed into the molybdenum rod biscuit by adopting cold isostatic pressing, and the pressure maintaining time of the cold isostatic pressing are controlled, so that the molybdenum powder is uniformly stressed, the molecular distance of the molybdenum powder is reduced, the density of the molybdenum rod biscuit is increased, and the pressing efficiency is improved.
The preparation method of the molybdenum metal grid is characterized in that the specific process of the high-temperature sintering treatment in the step 102 is as follows: firstly, the molybdenum rod biscuit is kept at the temperature of 500-800 ℃ for 3-6 h for first-stage heating and impurity removal, then kept at the temperature of 1100-1300 ℃ for 3-6 h for second-stage heating and impurity removal, and finally kept at the temperature of 1800-2100 ℃ for 4-8 h for third-stage high-temperature sintering to obtain a molybdenum rod semi-finished product. The semi-finished product of the molybdenum rod is obtained by adopting a method of removing impurities in sections and then sintering, the contents of water, steam, oil stains and low-melting-point metal impurities in high-temperature sintering equipment and on a molybdenum rod biscuit are effectively reduced by gradually increasing the temperature, and the quality of the semi-finished product of the molybdenum rod is improved.
The preparation method of the molybdenum metal grid is characterized in that the straightness of the forged molybdenum bar subjected to straightening treatment in the step 103 is not more than 0.5%; the diameter of the molybdenum rod is 50-85 mm, the length of the molybdenum rod is 200-300 mm, and the relative density of the molybdenum rod is more than 97%. The straightness of the forged molybdenum rod after straightening treatment is controlled to be not more than 0.5%, so that the precision of the molybdenum rod is improved, and the preparation difficulty of spherical molybdenum powder is reduced; the molybdenum rod with proper size is convenient to be arranged in the plasma rotating electrode powder making equipment, and the melting effect of the molybdenum rod is ensured; the relative density of the molybdenum rod is more than 97 percent, which is favorable for forming uniform and compact spherical molybdenum powder.
The preparation method of the molybdenum metal grid is characterized in that the high temperature generated by the plasma arc in the step 201 is 10000-15000 ℃, and the current generated by the plasma arc is 2000-3000A. The high current and high temperature generated by the plasma arc ensure the complete and rapid melting of the molybdenum rod, and improve the density and size uniformity of the micron-sized molybdenum metal spherical powder.
The preparation method of the molybdenum metal grid is characterized in that the linear feeding speed of the molybdenum rod in the step 202 is not more than 2.0mm/s, and the high-speed rotation speed is 13000 rpm-23000 rpm. The particle size of the spherical molybdenum powder is effectively controlled by adjusting the linear feeding speed and the high-speed rotating speed of the molybdenum rod, and the sphericity, the quality purity and the preparation efficiency of the spherical molybdenum powder are improved.
The method for preparing the molybdenum metal grid is characterized in that different electron beam beams are adopted in the electron beam heating process in the step 301 along the height direction formed by the single-layer entity sheet layer of the molybdenum metal grid forming member, wherein the electron beam beams of 50-60 mA are adopted when the height formed by the single-layer entity sheet layer of the molybdenum metal grid forming member is below 1/3, and the electron beam beams of 40-E are adopted when the height formed by the single-layer entity sheet layer of the molybdenum metal grid forming member is above 1/3The scanning speed of the electron beam is 12m/s in the process of heating the electron beam, and the vacuum degree of the working cavity is 10-2Pa. The molybdenum metal grid is prepared by 3D printing of the powder bed electron beams, so that the precision of the molybdenum metal grid is further improved, the preparation energy consumption is reduced, and the production cost is reduced.
The preparation method of the molybdenum metal grid is characterized in that the annealing temperature in the step 302 is 800-1000 ℃, and the time is 0.5-1 h. The molybdenum metal grid forming part is annealed under the process parameters, so that the residual stress in the forming process is eliminated, the tissue uniformity of the molybdenum metal grid forming part is improved, the cracking of the molybdenum metal grid forming part is avoided, and the quality of the metal grid forming part is improved.
The preparation method of the molybdenum metal grid is characterized in that the hot isostatic pressing treatment in the step 302 is carried out under the pressure of 180 MPa-250 MPa, the pressure maintaining time is 3 h-6 h, and the temperature is 1300 ℃ to 1500 ℃. The molybdenum metal grid formed part is subjected to hot isostatic pressing treatment, and the molybdenum metal grid formed part is densified under the action of high temperature and high pressure, so that the mechanical property of the final product molybdenum metal grid is greatly improved.
The preparation method of the molybdenum metal grid is characterized in that the mass concentration of alkali liquor used for alkali washing in the step 302 is not less than 99.5%, and the alkali washing time is 0.5 min-2.0 min. Grease and an oxide film on the surface of the molybdenum metal grid formed part subjected to the hot isostatic pressing treatment are removed through alkaline washing, so that the surface quality of the final product molybdenum metal grid is improved.
Compared with the prior art, the invention has the following advantages:
1. the invention carries out cold isostatic pressing, sintering and forging on molybdenum powder to obtain a molybdenum rod with higher density, then prepares the molybdenum rod into spherical molybdenum powder with higher sphericity by adopting plasma rotating electrode powder-making equipment, then uses the spherical molybdenum powder as a raw material to prepare a molybdenum metal grid by adopting a powder bed electron beam 3D printer, and because the spherical molybdenum powder has high sphericity, good fluidity, compact and uniform particles and higher heat of an electron beam, the molybdenum powder is rapidly melted and tightly combined to form a compact and uniform structure in the process of 3D printing of the powder bed electron beam, the defects of high molybdenum metal strength, low plasticity, easy oxidation, poor forming performance and difficult processing into complex structural parts and functional parts are overcome, and finally the molybdenum rod is obtained into (10 mm-100 mm) x (10 mm-100 mm) long x wide x high with the size of each square through hole of (1 mm-10 mm) x (1 mm-10 mm), the wall thickness of the partition is 0.1 mm-1 mm.
2. The particle size of the spherical molybdenum powder is controlled to be 60-120 mu m, so that the spherical molybdenum powder is completely melted by heating the electron beam in the 3D printing process of the electron beam of the powder bed, and the density of the molybdenum metal grid is increased, so that the preparation precision of the molybdenum metal grid is improved, and the molybdenum metal grid with smaller size and more complex structure is obtained.
3. According to the invention, the molybdenum powder is processed into spherical molybdenum powder as a raw material for preparing the molybdenum metal grid, the size specification of the molybdenum metal grid can be flexibly adjusted according to actual needs, the molybdenum metal is not required to be processed into other sectional materials such as wires, plates or pipes, the working procedures such as rolling, extruding, turning, drilling, polishing and the like are avoided, the specification and the service performance of the molybdenum metal grid are further improved, and the equipment, labor and quality control cost are saved.
4. According to the method, the molybdenum metal grid is formed in one step by adopting a powder bed electron beam 3D printing method, other machining steps are not needed, the process flow of preparing the molybdenum metal product with the complex structure by a vacuum smelting method and a powder metallurgy method in the prior art is shortened, the utilization rate of metal materials for manufacturing the molybdenum product with the complex structure is improved, and the cost of the molybdenum metal raw materials is further reduced.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a photograph of a molybdenum metal grid produced in example 3 of the present invention.
Detailed Description
Example 1
The preparation method of this example includes the following steps:
step one, preparing a molybdenum rod:
step 101, putting molybdenum powder into a prefabricated rubber sleeve die, sealing the die with a rubber plug after compaction treatment, then placing the die into a pressure-bearing cavity of a cold isostatic press, carrying out cold isostatic pressing treatment for 12min under the condition that the pressure is 180MPa, and demoulding to obtain a molybdenum rod biscuit; the particle size of the molybdenum powder is 3.6 mu m, the mass purity of the molybdenum powder is 99.97 percent, the mass content of oxygen is 1100ppm, and the tap density of the molybdenum powder is 3.5g/cm3；
Step 102, trimming the outer surface of the molybdenum rod biscuit obtained in the step 101 to remove edge burrs and surface defects, and then placing the molybdenum rod biscuit in a vacuum furnace for high-temperature sintering treatment to obtain a molybdenum rod semi-finished product; the specific process of the high-temperature sintering treatment comprises the following steps: firstly, heat preservation is carried out on a molybdenum rod biscuit for 3 hours at the temperature of 650 ℃, primary heating and impurity removal are carried out, then heat preservation is carried out for 4 hours at the temperature of 1250 ℃, secondary heating and impurity removal are carried out, and finally heat preservation is carried out for 6 hours at the temperature of 1950 ℃ for three-stage high-temperature sintering, so that a molybdenum rod semi-finished product is obtained; the diameter of the molybdenum rod semi-finished product is 150mm, and the length of the molybdenum rod semi-finished product is 850 mm;
103, performing hot precision forging on the molybdenum rod semi-finished product obtained in the step 102 to obtain a forged molybdenum rod, straightening the forged molybdenum rod until the straightness of the forged molybdenum rod is 0.3%, and then turning to remove surface oxide skin to obtain the molybdenum rod; the cogging temperature of the hot precision forging is 1380 ℃, and the forging system is one heating and three times; the diameter of the molybdenum rod is 70mm, the length of the molybdenum rod is 250mm, and the relative density of the molybdenum rod is 98%;
step two, preparing spherical molybdenum powder:
step 201, clamping one end of the molybdenum rod prepared in the step 103 on a three-jaw chuck of plasma rotating electrode powder manufacturing equipment, extending the other end of the molybdenum rod into the center of a high-temperature cavity of the plasma rotating electrode powder manufacturing equipment, and generating a plasma arc in a space formed by the molybdenum rod and a plasma auxiliary electrode; the high temperature generated by the plasma arc is 10000 ℃, and the current generated by the plasma arc is 2000A;
202, utilizing the high temperature generated by the plasma arc to make the end surface of the molybdenum rod extending into the center of the high-temperature cavity form melt, and simultaneously making the three-grab chuck drive the molybdenum rod to rotate at high speed and to face the direction of the high-temperature cavityMaking linear feeding motion, condensing the melt liquid into spherical liquid drops under the action of centrifugal force of high-speed rotation, throwing the spherical liquid drops into a powder condensation and collection bin, and condensing and sieving the spherical liquid drops to obtain spherical molybdenum powder; the particle diameter of the spherical molybdenum powder is 80 mu m, the angle of repose is 30 degrees, the sphericity is 0.92, and the apparent density is 6.0g/cm3Tap density of 7.5g/cm3The mass content of oxygen is 150ppm, and the mass content of H, C, N, Ca, Si, Mg, Al, Fe, Ni and Cu in the spherical molybdenum powder is not higher than 5ppm relative to the mass content increment of corresponding elements in the molybdenum rod; the linear feeding speed of the molybdenum rod is 1.2mm/s, and the high-speed rotation speed is 13000 rpm;
step three, preparing a molybdenum metal grid:
301, loading the spherical molybdenum powder prepared in the step 202 into a bin of a powder bed electron beam 3D printer, inputting a CAD model of a molybdenum metal grid die into a control computer of the powder bed electron beam 3D printer, slicing the CAD model by using slicing software Magics to obtain slicing data, preheating a forming substrate in a working cavity of the powder bed electron beam 3D printer by using an electron beam, laying the spherical molybdenum powder in the bin on the forming substrate according to the slicing data, heating by using the electron beam, melting the spherical molybdenum powder laid on the forming substrate into liquid metal in a surface exposure or point scanning manner, cooling to form a single-layer solid sheet layer, and repeating the melting and cooling processes until the single-layer solid sheet layers are stacked layer by layer to obtain a molybdenum metal grid forming part; the thickness of the paving layer is 100 mu m; different electron beam currents are adopted along the height direction formed by the single-layer entity sheet layer of the molybdenum metal grid forming part in the electron beam heating process, wherein 55mA electron beam current is adopted when the height formed by the single-layer entity sheet layer of the molybdenum metal grid forming part is below 1/3, 45mA electron beam current is adopted when the height formed by the single-layer entity sheet layer of the molybdenum metal grid forming part is above 1/3, the scanning speed of the electron beam current is 12m/s in the electron beam heating process, and the vacuum degree of the working cavity is 10-2Pa；
302, placing the molybdenum metal grid formed part prepared in the step 301 in a hydrogen furnace, annealing for 0.6h at the temperature of 900 ℃, hot isostatic pressing for 4h at the pressure of 220MPa and the temperature of 1350 ℃, and performing alkali washing for 1.0min by using alkali liquor with the mass concentration of 99.7% to obtain a molybdenum metal grid; the size of the molybdenum metal grid is 40mm multiplied by 50mm multiplied by 60mm (length multiplied by width multiplied by height), the size of each square through hole is 5mm multiplied by 5mm (length multiplied by width), and the wall thickness of the partition is 0.5 mm.
The density of the molybdenum metal grid prepared in the embodiment is detected to be 10.02g/cm3The mass content of oxygen is 130ppm, the Rockwell hardness HRA is 58, the tensile strength is 650MPa, and the elongation after fracture is 10%, which shows that the molybdenum metal grid prepared by the embodiment is compact and uniform, the impurity content is low, the hardness is high, and the mechanical property is excellent.
Example 2
The preparation method of this example includes the following steps:
step one, preparing a molybdenum rod:
step 101, putting molybdenum powder into a prefabricated rubber sleeve die, sealing the die with a rubber plug after compaction treatment, then placing the die into a pressure-bearing cavity of a cold isostatic press, carrying out cold isostatic pressing treatment for 10min under the condition that the pressure is 150MPa, and demoulding to obtain a molybdenum rod biscuit; the granularity of the molybdenum powder is 2.0 mu m, the mass purity of the molybdenum powder is 99.95 percent, the mass content of oxygen is 1500ppm, and the tap density of the molybdenum powder is 2.0g/cm3；
Step 102, trimming the outer surface of the molybdenum rod biscuit obtained in the step 101 to remove edge burrs and surface defects, and then placing the molybdenum rod biscuit in a vacuum furnace for high-temperature sintering treatment to obtain a molybdenum rod semi-finished product; the specific process of the high-temperature sintering treatment comprises the following steps: firstly, the molybdenum rod biscuit is subjected to heat preservation for 3.5h at the temperature of 500 ℃ for first-stage heating and impurity removal, then is subjected to heat preservation for 3h at the temperature of 1100 ℃ for second-stage heating and impurity removal, and finally is subjected to heat preservation for 4h at the temperature of 1800 ℃ for third-stage high-temperature sintering to obtain a molybdenum rod semi-finished product; the diameter of the molybdenum bar semi-finished product is 100mm, and the length of the molybdenum bar semi-finished product is 850 mm;
103, performing hot precision forging on the molybdenum rod semi-finished product obtained in the step 102 to obtain a forged molybdenum rod, straightening the forged molybdenum rod until the straightness of the forged molybdenum rod is 0.5%, and then turning to remove surface oxide skin to obtain the molybdenum rod; the cogging temperature of the hot precision forging is 1450 ℃, and the forging system is one-fire three-pass; the diameter of the molybdenum rod is 50mm, the length of the molybdenum rod is 200mm, and the relative density of the molybdenum rod is 98%;
step two, preparing spherical molybdenum powder:
step 201, clamping one end of the molybdenum rod prepared in the step 103 on a three-jaw chuck of plasma rotating electrode powder manufacturing equipment, extending the other end of the molybdenum rod into the center of a high-temperature cavity of the plasma rotating electrode powder manufacturing equipment, and generating a plasma arc in a space formed by the molybdenum rod and a plasma auxiliary electrode; the high temperature generated by the plasma arc is 12500 ℃, and the current generated by the plasma arc is 2500A;
202, utilizing high temperature generated by a plasma arc to enable the end face of a molybdenum rod extending into the center of a high-temperature cavity to form molten liquid, enabling a three-grab chuck to drive the molybdenum rod to rotate at a high speed and to perform linear feeding motion towards the direction of the high-temperature cavity, condensing the molten liquid into spherical liquid drops under the action of centrifugal force of high-speed rotation, throwing the spherical liquid drops into a powder condensation collection bin, and condensing and sieving the spherical liquid drops to obtain spherical molybdenum powder; the particle diameter of the spherical molybdenum powder is 60 mu m, the angle of repose is 35 degrees, the sphericity is 0.94, and the apparent density is 5.5g/cm3Tap density of 6.2g/cm3The mass content of oxygen is 130ppm, and the mass content of H, C, N, Ca, Si, Mg, Al, Fe, Ni and Cu in the spherical molybdenum powder is not higher than 10ppm relative to the mass content increment of corresponding elements in the molybdenum rod; the linear feeding speed of the molybdenum rod is 1.6mm/s, and the high-speed rotation speed is 18000 rpm;
step three, preparing a molybdenum metal grid:
301, loading the spherical molybdenum powder prepared in the step 202 into a bin of a powder bed electron beam 3D printer, inputting a CAD model of a molybdenum metal grid mold into a control computer of the powder bed electron beam 3D printer, slicing the CAD model by using slicing software Magics to obtain slicing data, preheating a forming substrate in a working cavity of the powder bed electron beam 3D printer by using an electron beam, and paving the spherical molybdenum powder in the bin on the forming substrate according to the slicing dataHeating by adopting an electron beam, melting the spherical molybdenum powder laid on the forming substrate into liquid metal in a surface exposure or point scanning mode, cooling to form single-layer solid sheets, and repeating the melting and cooling processes until the single-layer solid sheets are stacked layer by layer to obtain a molybdenum metal grid forming part; the thickness of the paving layer is 80 μm; different electron beam currents are adopted along the height direction formed by the single-layer entity sheet layer of the molybdenum metal grid forming part in the electron beam heating process, wherein 50mA electron beam current is adopted when the height formed by the single-layer entity sheet layer of the molybdenum metal grid forming part is below 1/3, 40mA electron beam current is adopted when the height formed by the single-layer entity sheet layer of the molybdenum metal grid forming part is above 1/3, the scanning speed of the electron beam current is 12m/s in the electron beam heating process, and the vacuum degree of the working cavity is 10-2Pa；
302, placing the molybdenum metal grid formed part prepared in the step 301 in a hydrogen furnace, annealing for 0.5h at the temperature of 800 ℃, hot isostatic pressing for 3h at the pressure of 180MPa and the temperature of 1300 ℃, and then performing alkali washing for 0.5min by using alkali liquor with the mass concentration of 99.5% to obtain a molybdenum metal grid; the size of the molybdenum metal grid is 10mm multiplied by 10mm (length multiplied by width multiplied by height), the size of each square through hole is 1mm multiplied by 1mm (length multiplied by width), and the wall thickness of the partition is 0.1 mm.
The density of the molybdenum metal grid prepared by the embodiment is 10.08g/cm through detection3The mass content of oxygen is 110ppm, the Rockwell hardness HRA is 60, the tensile strength is 680MPa, and the elongation after fracture is 11%, which shows that the molybdenum metal grid prepared by the embodiment is compact and uniform, low in impurity content, high in hardness and excellent in mechanical property.
Example 3
The preparation method of this example includes the following steps:
step one, preparing a molybdenum rod:
step 101, putting molybdenum powder into a prefabricated rubber sleeve die, sealing the die with a rubber plug after compaction, then placing the die into a pressure-bearing cavity of a cold isostatic press, carrying out cold isostatic pressing for 15min under the condition that the pressure is 230MPa, and demoulding to obtain molybdenumA bar biscuit; the particle size of the molybdenum powder is 4.5 mu m, the mass purity of the molybdenum powder is 99.97 percent, the mass content of oxygen is 1200ppm, and the tap density of the molybdenum powder is 6.0g/cm3；
Step 102, trimming the outer surface of the molybdenum rod biscuit obtained in the step 101 to remove edge burrs and surface defects, and then placing the molybdenum rod biscuit in a vacuum furnace for high-temperature sintering treatment to obtain a molybdenum rod semi-finished product; the specific process of the high-temperature sintering treatment comprises the following steps: firstly, heat preservation is carried out on a molybdenum rod biscuit for 6 hours at the temperature of 800 ℃ for first-stage heating and impurity removal, then heat preservation is carried out for 6 hours at the temperature of 1300 ℃ for second-stage heating and impurity removal, and finally heat preservation is carried out for 8 hours at the temperature of 2100 ℃ for third-stage high-temperature sintering to obtain a molybdenum rod semi-finished product; the diameter of the molybdenum bar semi-finished product is 180mm, and the length of the molybdenum bar semi-finished product is 850 mm;
103, performing hot precision forging on the molybdenum rod semi-finished product obtained in the step 102 to obtain a forged molybdenum rod, straightening the forged molybdenum rod until the straightness of the forged molybdenum rod is 0.5%, and then turning to remove surface oxide skin to obtain the molybdenum rod; the cogging temperature of the hot precision forging is 1500 ℃, and the forging system is one-fire three-pass; the diameter of the molybdenum rod is 85mm, the length of the molybdenum rod is 300mm, and the relative density of the molybdenum rod is 98%;
step two, preparing spherical molybdenum powder:
step 201, clamping one end of the molybdenum rod prepared in the step 103 on a three-jaw chuck of plasma rotating electrode powder manufacturing equipment, extending the other end of the molybdenum rod into the center of a high-temperature cavity of the plasma rotating electrode powder manufacturing equipment, and generating a plasma arc in a space formed by the molybdenum rod and a plasma auxiliary electrode; the high temperature generated by the plasma arc is 15000 ℃, and the current generated by the plasma arc is 3000A;
202, utilizing high temperature generated by a plasma arc to enable the end face of a molybdenum rod extending into the center of a high-temperature cavity to form molten liquid, enabling a three-grab chuck to drive the molybdenum rod to rotate at a high speed and to perform linear feeding motion towards the direction of the high-temperature cavity, condensing the molten liquid into spherical liquid drops under the action of centrifugal force of high-speed rotation, throwing the spherical liquid drops into a powder condensation collection bin, and condensing and sieving the spherical liquid drops to obtain spherical molybdenum powder; the particle diameter of the spherical molybdenum powder is 120 mu m, and the angle of repose35 degrees, the sphericity of 0.96 and the apparent density of 5.9g/cm3Tap density of 7.1g/cm3The mass content of oxygen is 100ppm, and the mass content of H, C, N, Ca, Si, Mg, Al, Fe, Ni and Cu in the spherical molybdenum powder is not higher than 2ppm relative to the mass content increment of corresponding elements in the molybdenum rod; the linear feeding speed of the molybdenum rod is 2.0mm/s, and the high-speed rotation speed is 23000 rpm;
step three, preparing a molybdenum metal grid:
301, loading the spherical molybdenum powder prepared in the step 202 into a bin of a powder bed electron beam 3D printer, inputting a CAD model of a molybdenum metal grid die into a control computer of the powder bed electron beam 3D printer, slicing the CAD model by using slicing software Magics to obtain slicing data, preheating a forming substrate in a working cavity of the powder bed electron beam 3D printer by using an electron beam, laying the spherical molybdenum powder in the bin on the forming substrate according to the slicing data, heating by using the electron beam, melting the spherical molybdenum powder laid on the forming substrate into liquid metal in a surface exposure or point scanning manner, cooling to form a single-layer solid sheet layer, and repeating the melting and cooling processes until the single-layer solid sheet layers are stacked layer by layer to obtain a molybdenum metal grid forming part; the thickness of the paving layer is 120 mu m; different electron beam currents are adopted along the height direction formed by the single-layer entity sheet layer of the molybdenum metal grid forming part in the electron beam heating process, wherein 60mA electron beam current is adopted when the height formed by the single-layer entity sheet layer of the molybdenum metal grid forming part is below 1/3, 50mA electron beam current is adopted when the height formed by the single-layer entity sheet layer of the molybdenum metal grid forming part is above 1/3, the scanning speed of the electron beam current is 12m/s in the electron beam heating process, and the vacuum degree of the working cavity is 10-2Pa。
302, placing the molybdenum metal grid formed part prepared in the step 301 in a hydrogen furnace, annealing for 1h at the temperature of 1000 ℃, hot isostatic pressing for 6h at the pressure of 250MPa and the temperature of 1500 ℃, and then performing alkali washing for 2.0min by using alkali liquor with the mass concentration of 99.6% to obtain the molybdenum metal grid shown in the figure 1; the size of the molybdenum metal grid is 100mm multiplied by 100mm (length multiplied by width multiplied by height), the size of each square through hole is 10mm multiplied by 10mm (length multiplied by width), and the thickness of the partition wall is 1 mm.
The density of the molybdenum metal grid prepared in the embodiment is detected to be 10.05g/cm3The mass content of oxygen is 90ppm, the Rockwell hardness HRA is 62, the tensile strength is 680MPa, and the elongation after fracture is 12%, which shows that the molybdenum metal grid prepared by the embodiment is compact and uniform, low in impurity content, high in hardness and excellent in mechanical property.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims (10)

1. A method for preparing a molybdenum metal grid is characterized by comprising the following steps:
step one, preparing a molybdenum rod:
step 101, loading molybdenum powder into a prefabricated rubber sleeve die, sealing the die with a rubber plug after compaction, then placing the die into a pressure-bearing cavity of a cold isostatic press for cold isostatic pressing, and demoulding to obtain a molybdenum rod biscuit; the granularity of the molybdenum powder is 2.0-4.5 mu m, the mass purity of the molybdenum powder is not less than 99.95 percent, the mass content of oxygen is not more than 1500ppm, and the tap density of the molybdenum powder is 2.0g/cm3～6.0g/cm3；
Step 102, finishing the outer surface of the molybdenum rod biscuit obtained in the step 101, and then placing the molybdenum rod biscuit in a vacuum furnace for high-temperature sintering treatment to obtain a molybdenum rod semi-finished product;
103, performing hot precision forging on the molybdenum rod semi-finished product obtained in the step 102 to obtain a forged molybdenum rod, straightening the forged molybdenum rod, and turning to remove surface scale to obtain the molybdenum rod; the cogging temperature of the hot precision forging is 1380-1500 ℃, and the forging system is one heating and three times;
step two, preparing spherical molybdenum powder:
step 201, clamping one end of the molybdenum rod prepared in the step 103 on a three-jaw chuck of plasma rotating electrode powder manufacturing equipment, extending the other end of the molybdenum rod into the center of a high-temperature cavity of the plasma rotating electrode powder manufacturing equipment, and generating a plasma arc in a space formed by the molybdenum rod and a plasma auxiliary electrode;
202, utilizing high temperature generated by a plasma arc to enable the end face of a molybdenum rod extending into the center of a high-temperature cavity to form molten liquid, enabling a three-jaw chuck to drive the molybdenum rod to rotate at a high speed and to perform linear feeding motion towards the direction of the high-temperature cavity, condensing the molten liquid into spherical liquid drops under the action of centrifugal force of high-speed rotation, throwing the spherical liquid drops into a powder condensation collection bin, and condensing and sieving the spherical liquid drops to obtain spherical molybdenum powder; the particle size of the spherical molybdenum powder is 60-120 mu m, the angle of repose is not more than 35 degrees, the sphericity is not less than 0.92, and the apparent density is not less than 5.5g/cm3Tap density of not less than 6.2g/cm3The mass content of oxygen is not more than 150ppm, and the mass content of H, C, N, Ca, Si, Mg, Al, Fe, Ni and Cu in the spherical molybdenum powder is less than 1 percent relative to the mass content increment of corresponding elements in the molybdenum rod;
step three, preparing a molybdenum metal grid:
301, loading the spherical molybdenum powder prepared in the step 202 into a bin of a powder bed electron beam 3D printer, inputting a CAD model of a molybdenum metal grid die into a control computer of the powder bed electron beam 3D printer, slicing the CAD model by using slicing software to obtain slicing data, preheating a forming substrate in a working cavity of the powder bed electron beam 3D printer by using an electron beam, laying the spherical molybdenum powder in the bin on the forming substrate according to the slicing data, heating by using the electron beam, melting the spherical molybdenum powder laid on the forming substrate into liquid metal in a surface exposure or point scanning manner, cooling to form single-layer solid sheet layers, and repeating the melting and cooling processes until the single-layer solid sheet layers are stacked layer by layer to obtain a molybdenum metal grid forming part; the thickness of the spreading layer is 80-120 mu m;
step 302, annealing the molybdenum metal grid formed part prepared in the step 301 in a hydrogen furnace, performing hot isostatic pressing treatment, and performing alkali washing to obtain a molybdenum metal grid; the size of the molybdenum metal grid is (10 mm-100 mm) × (10 mm-100 mm), the size of each square through hole is (1 mm-10 mm) × (1 mm-10 mm), and the wall thickness of the partition is 0.1 mm-1 mm.
2. The method of claim 1, wherein the cold isostatic pressing is performed at a pressure of 150MPa to 230MPa for a dwell time of 10min to 15min in step 101.
3. The method for preparing a molybdenum metal grid according to claim 1, wherein the specific process of the high-temperature sintering treatment in step 102 is as follows: firstly, the molybdenum rod biscuit is kept at the temperature of 500-800 ℃ for 3-6 h for first-stage heating and impurity removal, then kept at the temperature of 1100-1300 ℃ for 3-6 h for second-stage heating and impurity removal, and finally kept at the temperature of 1800-2100 ℃ for 4-8 h for third-stage high-temperature sintering to obtain a molybdenum rod semi-finished product.
4. The method for preparing a molybdenum metal grid according to claim 1, wherein the straightness of the forged molybdenum rod after the straightening treatment in the step 103 is not more than 0.5%; the diameter of the molybdenum rod is 50-85 mm, the length of the molybdenum rod is 200-300 mm, and the relative density of the molybdenum rod is more than 97%.
5. The method of claim 1, wherein the plasma arc generates 10000-15000 ℃ and 2000-3000A of current in step 201.
6. The method of claim 1, wherein the linear feeding speed of the molybdenum bar in step 202 is not more than 2.0mm/s, and the high-speed rotation speed is 13000rpm to 23000 rpm.
7. A molybdenum metal grid according to claim 1The preparation method is characterized in that different electron beam current is adopted along the height direction formed by the single-layer entity sheet layer of the molybdenum metal grid forming part in the electron beam heating process in the step 301, wherein the electron beam current of 50 mA-60 mA is adopted when the height formed by the single-layer entity sheet layer of the molybdenum metal grid forming part is below 1/3, the electron beam current of 40 mA-50 mA is adopted when the height formed by the single-layer entity sheet layer of the molybdenum metal grid forming part is above 1/3, the scanning speed of the electron beam current in the electron beam heating process is 12m/s, and the vacuum degree of the working cavity is 10-2Pa。
8. The method of claim 1, wherein the annealing in step 302 is performed at a temperature of 800 ℃ to 1000 ℃ for 0.5h to 1 h.
9. The method of claim 1, wherein the hot isostatic pressing treatment in step 302 is performed at a pressure of 180MPa to 250MPa, a dwell time of 3h to 6h, and a temperature of 1300 ℃ to 1500 ℃.
10. The method for preparing the molybdenum metal grid according to claim 1, wherein the mass concentration of the alkali liquor used in the alkali washing in the step 302 is not less than 99.5%, and the time of the alkali washing is 0.5min to 2.0 min.
CN201811011979.7A 2018-08-31 2018-08-31 Preparation method of molybdenum metal grid Active CN109014230B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811011979.7A CN109014230B (en) 2018-08-31 2018-08-31 Preparation method of molybdenum metal grid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811011979.7A CN109014230B (en) 2018-08-31 2018-08-31 Preparation method of molybdenum metal grid

Publications (2)

Publication Number Publication Date
CN109014230A CN109014230A (en) 2018-12-18
CN109014230B true CN109014230B (en) 2021-11-05

Family

ID=64622640

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811011979.7A Active CN109014230B (en) 2018-08-31 2018-08-31 Preparation method of molybdenum metal grid

Country Status (1)

Country Link
CN (1) CN109014230B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109550957B (en) * 2019-01-11 2020-01-21 中南大学 Method for preparing powder metallurgy stretching eutectic high-entropy alloy by 3D printing
CN110181048B (en) * 2019-05-24 2021-02-12 清华大学 Electron beam additive manufacturing method of molybdenum-based alloy powder
CN110453166B (en) * 2019-09-17 2020-10-09 厦门钨业股份有限公司 Preparation method for improving plasticity of pure molybdenum block
CN111644631B (en) * 2020-06-10 2023-04-18 重庆材料研究院有限公司 Preparation method of spherical vanadium powder
CN113134615B (en) * 2021-03-17 2023-06-16 圣航粉末冶金河北有限公司 Method for preparing antifriction and wear-resistant BN/CuSn10 powder by atomizing and pulverizing with plasma rotary electrode

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103203600A (en) * 2013-04-12 2013-07-17 金堆城钼业股份有限公司 Method for producing molybdenum electrode bar by means of precision forging
JP2017025392A (en) * 2015-07-24 2017-02-02 Ｊｘ金属株式会社 Surface treatment metal powder for electron beam type 3d printer and manufacturing method therefor
CN106853536A (en) * 2016-12-19 2017-06-16 西安欧中材料科技有限公司 The method for preparing 3D printing CoCrWMo alloy spherical powder
CN107234240A (en) * 2017-06-29 2017-10-10 西安欧中材料科技有限公司 A kind of electron beam powdering of use SS PREP Ti6Al4V spherical powders increases the manufacture method of material
CN107470623A (en) * 2017-08-30 2017-12-15 湖南顶立科技有限公司 A kind of increasing material manufacturing method
CN107876794A (en) * 2017-12-21 2018-04-06 西安欧中材料科技有限公司 The Mo powder of increasing material manufacturing, the preparation method of Mo alloy spherical powder
CN107999779A (en) * 2017-12-21 2018-05-08 西安欧中材料科技有限公司 The electron beam melting increasing material manufacturing method of CoCrMo powder based on PREP techniques
CN108247049A (en) * 2017-12-21 2018-07-06 西安欧中材料科技有限公司 A kind of selective laser increasing material manufacturing method using CoCrMo alloy powders

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9643361B2 (en) * 2014-05-27 2017-05-09 Jian Liu Method and apparatus for three-dimensional additive manufacturing with a high energy high power ultrafast laser
CN107695350B (en) * 2017-09-28 2019-08-30 西北有色金属研究院 Method based on electron beam 3D printing technique preparation TiAl alloy component
CN107914014B (en) * 2017-11-24 2019-07-12 西北有色金属研究院 A kind of electron beam selective melting manufacturing process of pure tungsten metal part

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103203600A (en) * 2013-04-12 2013-07-17 金堆城钼业股份有限公司 Method for producing molybdenum electrode bar by means of precision forging
JP2017025392A (en) * 2015-07-24 2017-02-02 Ｊｘ金属株式会社 Surface treatment metal powder for electron beam type 3d printer and manufacturing method therefor
CN106853536A (en) * 2016-12-19 2017-06-16 西安欧中材料科技有限公司 The method for preparing 3D printing CoCrWMo alloy spherical powder
CN107234240A (en) * 2017-06-29 2017-10-10 西安欧中材料科技有限公司 A kind of electron beam powdering of use SS PREP Ti6Al4V spherical powders increases the manufacture method of material
CN107470623A (en) * 2017-08-30 2017-12-15 湖南顶立科技有限公司 A kind of increasing material manufacturing method
CN107876794A (en) * 2017-12-21 2018-04-06 西安欧中材料科技有限公司 The Mo powder of increasing material manufacturing, the preparation method of Mo alloy spherical powder
CN107999779A (en) * 2017-12-21 2018-05-08 西安欧中材料科技有限公司 The electron beam melting increasing material manufacturing method of CoCrMo powder based on PREP techniques
CN108247049A (en) * 2017-12-21 2018-07-06 西安欧中材料科技有限公司 A kind of selective laser increasing material manufacturing method using CoCrMo alloy powders

Also Published As

Publication number Publication date
CN109014230A (en) 2018-12-18

Similar Documents

Publication Publication Date Title
CN109014230B (en) Preparation method of molybdenum metal grid
CN112935252B (en) Method for preparing high-toughness eutectic high-entropy alloy based on selective laser melting technology
CN106756434B (en) Oxide dispersion intensifying low activation ferrite/martensite steel and its smelting process
US11634333B2 (en) Boron-containing titanium-based composite powder for 3D printing and method of preparing same
CN104550960B (en) The metal increasing material manufacturing method of application cold hearth melting and metal parts and application
CN106994471A (en) A kind of 780MPa intensity levels electron beam fuse 3D printing component titanium alloy wire materials
CN112795828B (en) Tantalum-tungsten alloy for 3D printing and method for preparing tantalum-tungsten alloy thin-walled plate
CN102392147B (en) Preparation method of ultrafine grain nickel base powder high temperature alloy
CN109514067B (en) Preparation method of high-strength TA18 titanium alloy component based on electron beam fuse material increase
CN113319292B (en) Tantalum-tungsten alloy preparation process based on selective laser melting forming and tantalum-tungsten alloy
CN109277675B (en) Preparation method of high-strength TA18 titanium alloy component based on plasma fuse material increase
CN112281032B (en) Preparation method of aluminum alloy welding material
CN101259584A (en) Method for preparing high-density molybdenum tube
CN110340361B (en) Technological process for quickly and directly manufacturing hot working die
CN113134627B (en) Selective laser melting processing method and application of high-nickel-rich NiTi alloy
CN108796304A (en) A kind of γ-TiAl prealloys gas-atomized powder electrode bar and preparation method thereof
CN112792308B (en) Roller for continuous induction type rapid quenching furnace and manufacturing method thereof
CN107746280B (en) High-density TiB2Preparation method of ceramic target material
CN1081242C (en) Process for preparing TiNi-base marmem directly from elements powder
CN114273676B (en) Refractory tungsten tantalum alloy complex structural member and additive manufacturing and forming method thereof
CN114054773B (en) Preparation method of laminated heterogeneous aluminum alloy plate with unevenly distributed precipitated phases
CN105177304A (en) Method for producing TB6 plate slab by electron beam cold hearth melting
CN115106540A (en) Tantalum-tungsten alloy product and preparation method thereof
CN110257664B (en) Copper-based composite material and preparation method thereof
CN115229205B (en) Method for manufacturing double-lamellar structure beta titanium alloy by electron beam additive

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant