CN114606479B - Molybdenum vapor deposition molding integrated device and method - Google Patents
Molybdenum vapor deposition molding integrated device and method Download PDFInfo
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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Abstract
The invention discloses a molybdenum vapor deposition molding integrated device and a method, wherein the molding device comprises a molybdenum source gasification sublimation area, a reaction reduction area, a strengthening deposition area and an online consolidation molding area; the method takes gaseous molybdenum trioxide as a raw material, takes uniform gas phase reduction as a basis, and takes electric field reinforced directional deposition as a core, thereby realizing product shaping, efficient deposition and online consolidation forming. The invention prepares high-purity MoO by a physical sublimation method 3 The molybdenum-containing gas source breaks through the toxicity and the pollution of the deposition process of the traditional molybdenum vapor deposition method in the raw material preparation process of molybdenum fluoride and molybdenum carbonyl; the precise control of the molybdenum particle size is realized by uniform gas phase reduction; the directional effect of an electric field is provided to realize the efficient directional deposition of molybdenum particles, and the deposition efficiency is obviously improved; the method overcomes the defects of toxicity of raw materials, process gas pollution, low efficiency and high cost of the traditional molybdenum vapor deposition, realizes the short-flow, high-efficiency, continuous and green manufacturing of the molybdenum metal material, and has subversive influence on the development of the molybdenum metal material forming technology.
Description
Technical Field
The invention relates to a metal material preparation technology, in particular to a molybdenum vapor deposition molding integrated device and a method.
Background
The refractory metal molybdenum has a melting point as high as 2690 ℃, has excellent heat conduction, electric conduction and corrosion resistance, low thermal expansion coefficient, higher hardness and good high-temperature strength, and therefore has wide application in the fields of electronic industry, aerospace industry, energy industry and the like. The industrial molybdenum trioxide prepared by roasting the molybdenum concentrate usually contains high-content impurities such as iron, nickel, silicon, calcium and the like, so that the industrial molybdenum trioxide needs to be purified to high-purity molybdenum trioxide by a chemical wet method to be used as a molybdenum metal material processing raw material, the process involves the use of a large amount of chemical substances such as ammonium, acid and the like, and the environmental protection pressure is huge.
As shown in fig. 1, the conventional molybdenum metal preparation process mainly includes the following three processes:
first, bulk molybdenum metal materials are typically produced using powder metallurgy methods due to the high melting point characteristics of molybdenum metal. The method generally takes molybdenum oxide as a raw material and needs to pass through industrial MoO in sequence 3 Hydrometallurgy, ammonium molybdate, calcination and high-purity MoO 3 One-stage reduction-MoO 2 Two-stage reduction, molybdenum powder, compression, sintering, pressure processing, heat treatment, mechanical processing and other working procedures. The method takes industrial molybdenum oxide as a raw material, prepares high-purity molybdenum oxide through chemical purification, and then prepares high-purity metal molybdenum powder through hydrogen multi-stage reduction. Then placing the molybdenum powder in a sheath for cold isostatic pressing and then sintering at high temperature (above 1700 ℃), or sintering and forming by hot isostatic pressing. The block material after consolidation forming is finally subjected to hot pressure processing processes such as extrusion, forging and the like to improve the material density, and is finally manufactured into various different-shaped parts through machining. The preparation process has long flow, low yield, more involved equipment, typical characteristics of material reduction and manufacturing and lower yield.
Currently, this technique has some drawbacks and limitations, mainly reflected in:
1) From a high-purity powder raw material to a final block material, multiple processes such as multi-section powder reduction, powder screening, powder pressing, green body sintering, hot pressure processing and the like are required, the preparation process is complex, the processing period is long, and the yield is low.
2) Because of the high melting point and easy oxidation characteristic of the refractory metal molybdenum, a plurality of high-energy-consumption precision devices such as a high-temperature hydrogen gas uniform distribution reduction reaction tank, an isostatic pressing machine, a hydrogen high-temperature sintering furnace and the like are required in the preparation process, the device types are multiple, and the investment of fixed assets is large. And generally, the method cannot be used in a linkage manner, only can be used for batch production in an intermittent manner, and has high operation cost. Particularly, the uniformity of a heated area is remarkable, the equipment capacity is limited, and the preparation of large molybdenum metal billets is very difficult.
3) The impurity removal capability in the powder metallurgy preparation process is weaker, so that the purity requirement on the used molybdenum oxide powder raw material is higher, the high-purity molybdenum oxide is usually prepared by industrial molybdenum oxide through a complex chemical purification process, a large amount of ammonium and acid are used, and the treatment difficulty of ammonia gas and wastewater generated in the industrial production process is high.
Secondly, in order to shorten the process flow and improve the preparation efficiency of the molybdenum material, in the past century, with the development of 3D printing technology, materials such as refractory metal tungsten, molybdenum, tantalum, niobium and the like gradually become main material objects for the development of 3D printing technology, and positive progress has been made. Molybdenum metal is printed by a 3D printing technology, molybdenum wires or spherical molybdenum powder is generally used as a material, and in order to obtain higher printing material strength, spheroidized molybdenum powder with small granularity of less than 50-80 microns, good sphericity and narrow distribution is a key and development direction for improving the quality of a 3D printing body. The raw materials need to be subjected to plasma spheroidization or spray granulation treatment on the basis of high-purity molybdenum powder, and the method relates to high energy consumption and a complex process treatment process, and has high cost and low yield. Moreover, the efficiency of the existing laser printing or plasma beam printing technology itself is to be further improved. Finally, 3D printing of refractory metal components has not been able to meet the demands of more conditions due to the low strength. And the like, which causes the difficulty that the refractory metal 3D printing technology falls into short flow and high cost. The method is only suitable for preparing the components with complex structures, and has no advantage for the production of large-scale conventional components.
Thirdly, compared with the molybdenum metal 3D printing manufacturing technology, the Chemical Vapor Deposition (CVD) method has more advantages. Firstly, the vapor deposition technology directly prepares the molybdenum metal material by taking a gasified molybdenum source as a raw material through reaction deposition, so the process is short; the vapor deposition technology has good plating winding performance and can deposit in multiple dimensions simultaneously; thirdly, the vapor deposition structure is finer, the strength is higher, and the requirements of more high-strength special-shaped components can be met, so that the development potential is higher.
In the soviet union, which studied vapor deposition technology to produce tungsten-molybdenum metal components as early as 60 years in the world, ultramet in the united states performed a great deal of technological development and application. However, the existing molybdenum vapor deposition technology mainly uses molybdenum fluoride and molybdenum carbonyl as metal vapor, such vapor is very expensive, and during the use process of molybdenum fluoride, molybdenum fluoride is firstly heated and volatilized into gas at low temperature, and then the gas is deposited in a deposition area and H 2 The mixture is mixed to carry out gas phase reaction to produce Mo and HF gas. At present, the recycling of HF gas has been successfully solved. However, the strong corrosiveness and toxicity of both hydrofluoric acid and HF itself place stringent requirements on equipment and personnel handling. Similarly, the preparation process of molybdenum carbonyl needs to be carried out in a CO environment, and the requirement is harsh, and although nickel carbonyl has been studied successfully and related to iron carbonyl and molybdenum carbonyl, the strict preparation environment severely limits the popularization of the molybdenum carbonyl in the industry. Most importantly, the traditional vapor deposition technology generally performs the forming stacking in the atomic superposition mode, has very slow efficiency, can only reach the maximum speed of 0.1-1mm/h, and can only be used for preparing functional thin film materials. For the preparation of products with larger specifications, the efficiency is lower.
The following three conventional techniques show that molybdenum belongs to refractory metals, has high melting point and is difficult to prepare. The traditional molybdenum metal material is prepared by a powder metallurgy method, and has the advantages of long flow, low yield and high cost. The 3D printing additive manufacturing technology is used as a core preparation technology of materials in the 21 st century, molybdenum wires or high-fluidity molybdenum powder is used as a raw material, but 3D printing powder is high in requirement, narrow in distribution, low in yield and low in printing speed, has the characteristics of short flow and high cost, and is not suitable for large-scale batch production. Compared with the two methods, the vapor deposition method for preparing the molybdenum metal has the characteristics of short flow, high efficiency, simple shape, good manufacturability and the like, and has good industrial application potential. However, molybdenum fluoride and molybdenum carbonyl are used as raw materials, so that the gas cost is high, the toxicity in the preparation process is high, the deposition speed is slow, the corrosion of a reaction product HF to equipment is serious, and the like, and the molybdenum fluoride and the molybdenum carbonyl are still in a laboratory state at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a molybdenum vapor deposition molding integrated device and method, which shorten the preparation process of a molybdenum metal material, reduce the cost, and reduce the preparation energy consumption and pollution discharge.
In order to achieve the purpose, the invention adopts the following technical scheme:
a molybdenum vapor deposition molding integrated device comprises a molybdenum source vapor sublimation installation area, a vapor reduction area, a strengthening deposition area and an online consolidation molding area;
the molybdenum source gas phase sublimation packaging area comprises a molybdenum trioxide evaporation tank, the molybdenum trioxide evaporation tank is connected with an argon pressure maintaining tank, and a first pressure detection meter is mounted on the molybdenum trioxide evaporation tank; a gas outlet of the molybdenum trioxide evaporation tank is communicated with a gaseous uniformly-distributed reduction reaction tank of the reaction reduction zone through a heat-insulating pipeline, and a raw gas inlet of the gaseous uniformly-distributed reduction reaction tank is connected with a hydrogen heating tank through a pipeline;
the reinforced deposition area comprises a negatively charged metal wire mesh arranged at a product outlet of the gaseous uniformly-distributed reduction reaction tank and a plus-shaped electrodeposition area positioned below the negatively charged metal wire mesh; the wire consolidation forming area comprises a positively charged deposition platform and a sintering device, the positively charged deposition platform is arranged below the enhanced deposition area, the sintering device is arranged below the positively charged deposition platform, and the deposition shape is controlled by controlling the electric field distribution of the positively charged deposition platform.
Further, the gaseous uniformly-distributed reduction reaction tank is of a multilayer concentric tube structure, a multilayer concentric tube-shaped hydrogen distribution bin is arranged in the gaseous uniformly-distributed reduction reaction tank, the inner wall and the outer wall of the tube-shaped hydrogen distribution bin are porous metal plates, two ends of the tube-shaped hydrogen distribution bin are sealed by annular compact metal plates, each layer of tube-shaped hydrogen distribution bin is communicated with the hydrogen heating tank through an external metal tube, heating hydrogen enters the tube-shaped hydrogen distribution bin under the action of pressure, and then the hydrogen is blown out in the radial direction of the tube through the porous metal plates on the inner wall.
Furthermore, the holes on the porous metal plates on the inner wall and the outer wall of the tubular hydrogen distribution bin are uniformly distributed.
And the gas-solid circulation recovery area comprises a dust collecting device, a steam-water separating device and an argon/hydrogen separating device, and is communicated with the corresponding gaseous uniformly-distributed reduction reaction tank, the hydrogen heating tank and the argon pressure maintaining tank.
An integrated method for molybdenum vapor deposition molding comprises the following steps:
1) Molybdenum source vapor phase sublimation
Adding MoO 3 Placing into molybdenum trioxide evaporation tank, vacuum exhausting and gas replacing to replace air in the furnace, heating the furnace to 600-1000 deg.C, opening the gas outlet valve when the positive pressure in the furnace is greater than or equal to 0.021Mpa, and sublimating MoO 3 Entering a gas phase uniform distribution reduction reaction tank through a heat insulation pipeline;
2) Gas phase reduction of
MoO from molybdenum trioxide evaporation tank 3 The gas enters a gaseous uniformly-distributed reduction reaction tank through a heat-insulating pipeline, meets heating hydrogen blown in from the tubular hydrogen distribution bin in the radial direction through the flow division of a plurality of coaxial tubular hydrogen distribution bins, realizes homogeneous gas-phase reduction, and generates nanoscale molybdenum powder with uniform particle size;
3) Enhanced deposition of nano-sized molybdenum powder
Under the action of gas pressure, the formed nanoscale molybdenum powder flows out from the other side of the gaseous uniformly-distributed reduction reaction tank, touches the wire mesh when passing through the negatively-charged wire mesh or carries minus electricity under the action of a corona field of the negatively-charged wire mesh, and under the action of an electric field, the minus-charged nanoscale powder is directionally deposited to a deposition area with plus electricity, meanwhile, the gas-solid separation of water vapor and excessive hydrogen from nanoscale molybdenum powder particles is realized, and trace nanoscale molybdenum powder is discharged out of a strengthened deposition area under the action of gas pressure in the furnace;
4) On-line consolidation forming
The deposition shape is controlled by controlling the electric field distribution of the positively charged deposition platform to form a molybdenum metal shape with a specific shape, and the molybdenum metal shape is sintered at the online low temperature of 800-1300 ℃ to form the required shape and size of a product.
Further, in the manufacturing process, a gas-solid circulation recovery area is utilized, water vapor and solid powder which are not completely reacted are respectively collected by a dust collection device, a steam-water separation device and an argon/hydrogen separation device, and then the water vapor and the solid powder are returned to the corresponding raw material tank, the hydrogen tank and the argon tank for recycling.
The invention has the following beneficial effects:
1. short flow and high efficiency
The method of the invention is to convert the molybdenum raw material into gaseous molybdenum trioxide to be reduced, sintered and deposited to form a molybdenum metal structure with a specific shape, so that the molybdenum exists in an ultrafine particle state before being converted into a solid. The designed continuous reaction equipment fully utilizes the characteristics of air flow, and all the working procedures are connected through pipelines, so that the continuous operation of all the working procedures is realized, and the purposes of fully utilizing reaction heat energy of all the stages and saving intermediate storage working procedures are achieved. In one device, the functions of multiple devices of multi-section reduction, screening, compression molding and sintering in the prior art can be realized, and the purposes of fully utilizing energy and saving the investment of complex devices are achieved by matching with a recovery system of argon, hydrogen and dust. Take 10mm molybdenum metal plate as an example. The method eliminates the steps of first-stage reduction of high-purity molybdenum trioxide for 6h, second-stage reduction for 8h, screening, batch combination for 4h, compression for 2h, sintering for 30h and the like, and the total time is about 50h. The total time of the method is about 8-10h according to the speed of 2 mm/h. Compared with the traditional method, the time is shortened by 80%; for the product shape with larger deposition area, the efficiency is higher;
2. low energy consumption
The method has the highest heating temperature of 800-1300 ℃, wherein each process stage is continuous and flows in a gas form, and the excess heat energy can conveniently flow among the processes, thereby hardly causing heat waste. In the traditional process, the reduction temperature of the molybdenum powder is 500-1150 ℃, and the sintering temperature is even 1800-2100 ℃. And because the traditional method has more processes, frequent cooling processes are required to be carried out in each process flow to ensure that materials can be conveniently transferred in each process, so that the energy consumption of heat energy, hydrogen and the like is much higher.
3. Continuous scale manufacture
The preparation of molybdenum metal by the powder metallurgy method is influenced by the capability of pressing and sintering equipment, and large-scale components cannot be prepared, and continuous manufacturing cannot be realized. The invention realizes low-temperature sintering and continuous powder supply through continuous preparation, deposition and sintering of nano-scale powder, and lays the foundation of continuous and large-scale preparation.
4. Simple equipment and low investment
The traditional powder metallurgy method for preparing molybdenum metal has multiple working procedures and multiple devices, needs two sections of molybdenum powder reduction furnaces, sieving machines, cold isostatic presses, high-temperature sintering furnaces and a plurality of supporting facilities thereof, and has high investment on fixed assets. The invention reduces the investment of fixed assets by more than 70 percent because of low molding temperature and continuous integrated preparation.
5. Good raw material adaptability, safety and environmental protection
The method adopts the sublimation method to effectively separate high boiling point impurities from the main molybdenum element in the raw material, can improve the purity of the molybdenum source, and can also improve the adaptability of the molybdenum smelting raw material. For example, industrial oxide can be adopted, so that the problem of three wastes in hydrometallurgical purification is effectively solved, the preparation process is greatly shortened, and the preparation cost is reduced. In addition, defective products, recovered waste molybdenum metal and the like in the preparation link of the molybdenum industrial chain can be used as raw materials of the method, so that the application range of molybdenum smelting raw materials is greatly expanded. Compared with the toxicity and harsh preparation environment, conditions and high cost of fluoride and molybdenum carbonyl, the method only uses hydrogen, greatly improves the safety and has no pollution.
The invention combines the molybdenum metal vapor deposition method to prepare high-purity MoO by a physical sublimation method 3 The molybdenum-containing gas source replaces the traditional vapor deposition method for preparing molybdenum fluoride and molybdenum carbonyl by a chemical method, and has the problems of toxicity, environmental protection, corrosion and the like. High-efficiency deposition technology for integrated vapor deposition of molybdenum particlesForming vapor deposition forming molybdenum metal preparation technology. The method overcomes the defects of low efficiency and high cost of the traditional molybdenum vapor deposition method, and realizes the short-flow, high-efficiency and continuous manufacturing of the molybdenum metal material; the method can realize the integrated molding from industrial molybdenum trioxide to molybdenum metal components, greatly shorten the preparation process of the molybdenum metal material, reduce the equipment investment and the operation cost, reduce the preparation energy consumption and the pollution emission of the molybdenum metal material, widen the application range of the molybdenum raw material, and realize the short-flow, high-efficiency, low-cost, greening and continuous manufacturing of the molybdenum metal material.
Drawings
FIG. 1 is a comparative diagram of three preparation process flows of molybdenum metal
FIG. 2 is a schematic diagram of the invention
FIG. 3 is a general schematic view of the apparatus of the present invention
FIG. 4a is an axial sectional view of the gaseous equispaced reduction reaction tank of the present invention
FIG. 4b is a radial cross-sectional view of the reduction reaction tank of the present invention having a uniform gas distribution
Reference numerals: 1. a molybdenum source gasification sublimation area; 2. a reaction reduction zone; 3. strengthening the deposition area; 4. solidifying and forming the area on line; 5. a gas-solid circulation recovery zone; 6. an argon pressure maintaining tank; 7. a first connecting valve; 8. a second connecting valve; 9. a first pressure detection meter; 10. a second pressure detection meter; 11. a hydrogen heating tank; 12. a molybdenum trioxide evaporator; 13. sealing the tank; 14. a positively charged deposition platform; 15. a negatively charged wire mesh; 16. uniformly distributing a reduction reaction tank in a gaseous state; 17. molybdenum trioxide as a raw material; 18. a tubular hydrogen distribution bin; 19. sublimating molybdenum oxide; 20. ultrafine molybdenum powder particles.
Detailed Description
The following examples are given to illustrate the present invention in further detail, but are not intended to limit the scope of the present invention.
As shown in figure 3, the molybdenum vapor deposition and molding integrated device comprises a molybdenum source gasification and sublimation area 1, a reaction reduction area 2, a strengthening and deposition area 3, an online consolidation molding area 4 and a gas-solid circulation and recovery area 5.
The molybdenum source gasification sublimation area 1 comprises a molybdenum trioxide evaporation tank 12The molybdenum evaporation tank 12 is connected with the argon pressure maintaining tank 6, and the molybdenum trioxide evaporation tank 12 is further provided with a pressure detection meter I9. The reaction reduction zone 2 comprises a gaseous uniformly-distributed reduction reaction tank 16, a molybdenum trioxide evaporation tank 12 is communicated with the gaseous uniformly-distributed reduction reaction tank 16 through a heat-insulating pipeline, the gaseous uniformly-distributed reduction reaction tank 16 is provided with a reduction gas inlet, and a hydrogen heating tank 11 is communicated with the reduction gas inlet through a pipeline. Mixing high-purity MoO 3 Putting the mixture into a molybdenum trioxide evaporation tank 12, introducing argon through a vacuum exhaust or argon pressure maintaining tank 6 to replace the air in the molybdenum trioxide evaporation tank 12, and heating the furnace to 600-1000 ℃. When the positive pressure in the furnace is more than or equal to 50pa, the gas outlet valve is opened to sublimate MoO 3 And enters the gaseous uniformly distributed reduction reaction tank 16 through a heat insulation pipeline.
The strengthened deposition area 3 comprises a negatively charged metal wire mesh 15 arranged at the product outlet of the gaseous uniformly distributed reduction reaction tank 16 and a plus-shaped electrodeposition area below the negatively charged metal wire mesh 15, and the nano-scale molybdenum powder formed by reduction in the gaseous uniformly distributed reduction reaction tank 16 flows out from the product outlet at the other side of the gaseous uniformly distributed reduction reaction tank under the action of gas pressure. The outlet of the gaseous uniformly distributed reduction reaction tank is provided with a metal gauze with minus electricity, and the deposition zone is provided with plus electricity. When the nano-sized molybdenum powder passes through the metal gauze, the nano-sized molybdenum powder is touched with the gauze or takes up the minus electricity under the action of the corona field of the nano-sized molybdenum powder. Under the action of an electric field, the powder with the minus nanometer level is directionally deposited to a deposition area with the plus electricity; the vapor and the excessive hydrogen generated by the gas phase reduction are not influenced by the electric field, so that the gas-solid separation with the nano-grade molybdenum powder particles is realized, and the nano-grade molybdenum powder particles are discharged out of the strengthening deposition area 3 under the action of the gas pressure in the furnace.
The wire consolidation forming zone 4 comprises a positively charged deposition platform 14, the positively charged deposition platform 14 is arranged below the enhanced deposition zone 3, and the deposition shape is controlled according to the electric field distribution. The deposition flat plate is charged with a positive voltage to form a plate-shaped structure; the molybdenum rod or the molybdenum ribbon is electrified to form a rod-shaped structure. The thickness of the deposition is related to the deposition rate and time; the deposited nano-powder realizes the on-line sintering at low temperature of 800-1300 ℃ by means of higher sintering activity of the nano-powder under the action of residual heat and concurrent heating, and forms required shape and size.
The gas-solid circulation recovery area 5 is used for returning water vapor and solid powder which are not completely reacted in the reaction reduction area 2, the enhanced deposition area 3 and the online consolidation forming area 4 to the corresponding raw material tank, the hydrogen tank and the argon tank for recycling through dust collection, vapor-water separation and argon/hydrogen separation devices respectively.
As shown in fig. 4a and fig. 4b, the gaseous uniform reduction reaction tank 16 is a multilayer concentric tube structure, a multilayer concentric tube-shaped hydrogen distribution bin 18 is arranged in the gaseous uniform reduction reaction tank 16, the inner wall and the outer wall of the tube-shaped hydrogen distribution bin 18 are porous metal plates, the holes on the porous metal plates are uniformly distributed, two ends of the tube-shaped hydrogen distribution bin 18 are blocked by annular compact metal plates, each layer of tube-shaped hydrogen distribution bin is communicated with the hydrogen heating tank 11 through an external metal tube, heated hydrogen enters the tube-shaped hydrogen distribution bin under the pressure action, and then hydrogen is blown out in the radial direction of the tube through the porous metal plates on the inner wall.
Sublimed MoO 3 And the gas-state uniformly-distributed reduction reaction tank enters a gap between each layer of tubular hydrogen distribution bin along the axial direction of the concentric tube and meets with heating hydrogen blown in from the radial direction of the tubular hydrogen distribution bins, homogeneous gas-phase reduction is realized in the reduction tube, and nano-grade molybdenum powder with uniform particle size is generated through mean reduction. The sublimation of MoO is realized by a method of uniform distribution of gas 3 And hydrogen is uniformly distributed and reacted, so that the granularity and the uniformity of the nano-scale molybdenum powder are ensured.
As shown in FIG. 2, the invention also discloses a molybdenum vapor deposition molding integrated method, which comprises the following specific steps:
1) Molybdenum source vapor phase sublimation
Mixing high-purity MoO 3 Industrial MoO 3 Put into molybdenum trioxide evaporating pot, through vacuum exhaust and argon gas replacement mode replacement stove air to make the gas pressure in the sublimation pipe keep the pressure of a little positive pressure in order to prevent the hydrogen entering in the reduction jar. Then, the temperature of the furnace is raised to 600-1000 ℃, when the positive pressure in the sublimation furnace is more than or equal to 0.02Mpa, the air outlet valve is opened to sublimate MoO 3 Entering a gas phase reduction reaction tank through a heat insulation pipeline;
2) Gas phase reduction of
Gas phase MoO entering the gas phase reaction tank through the heat preservation pipe 3 The gas enters the gas phase reduction tube. Firstly, the gas is shunted by a plurality of layers of tubular hydrogen distribution bins with the same axle center, then the gas enters a gaseous uniformly-distributed reduction zone layer by layer along the axial direction of the plurality of layers of tubular hydrogen distribution bins, and meets with heating hydrogen blown in from the radial direction of the tubular hydrogen distribution bins, homogeneous gas-phase reduction is realized in a reduction tube, and nano-grade molybdenum powder with uniform particle size is generated;
3) Enhanced deposition of nano-sized molybdenum powder
Under the action of gas pressure, the formed nano-grade molybdenum powder flows out from the other side of the gaseous uniformly-distributed reduction reaction tank. A belt-shaped electric wire mesh is arranged at the outlet. When the nanoscale molybdenum powder penetrates through a negatively charged metal wire mesh, the nanoscale molybdenum powder touches the wire mesh or is charged under the action of a corona field. Under the action of an electric field, the charged nanoscale powder is directionally deposited to a deposition area with a plus electrode, meanwhile, the gas-solid separation of water vapor and excessive hydrogen from nanoscale molybdenum powder particles is realized, and trace nanoscale molybdenum powder is discharged out of the enhanced deposition area under the action of gas pressure in the furnace;
4) On-line consolidation forming
The deposition shape is controlled by controlling the electric field distribution of the positively charged deposition platform to form a molybdenum metal shape with a specific shape, and the molybdenum metal shape is sintered at the online low temperature of 800-1300 ℃ to form the required shape and size of a product.
Further, in the manufacturing process, a gas-solid circulation recovery area is utilized, water vapor and solid powder which are not completely reacted are respectively collected by a dust collection device, a steam-water separation device and an argon/hydrogen separation device, and then the water vapor and the solid powder are returned to the corresponding raw material tank, the hydrogen tank and the argon tank for recycling.
Claims (6)
1. The utility model provides a molybdenum vapor deposition shaping integrated device which characterized in that: comprises a molybdenum source gasification sublimation area (1), a reaction reduction area (2), a strengthening deposition area (3) and an online consolidation forming area (4);
the molybdenum source gasification sublimation area (1) comprises a molybdenum trioxide evaporating pot (12), the molybdenum trioxide evaporating pot (12) is connected with an argon pressure maintaining pot (6), and a first pressure detection meter (9) is installed on the molybdenum trioxide evaporating pot (12); a gas outlet of the molybdenum trioxide evaporating pot (12) is communicated with a gaseous uniformly distributed reduction reaction pot (16) of the reaction reduction zone (2) through a heat insulation pipeline, and a raw gas inlet of the gaseous uniformly distributed reduction reaction pot (16) is connected with a hydrogen heating pot (11) through a pipeline;
the intensified deposition area (3) comprises a negatively charged metal wire mesh (15) arranged at a product outlet of the gaseous uniformly-distributed reduction reaction tank (16) and a plus electrodeposition area positioned below the negatively charged metal wire mesh (15); the online consolidation forming area (4) comprises a positively charged deposition platform (14) and a sintering device, the positively charged deposition platform (14) is arranged below the enhanced deposition area (3), the sintering device is arranged below the positively charged deposition platform (14), and the deposition shape is controlled by controlling the electric field distribution of the positively charged deposition platform (14).
2. The integrated molybdenum vapor deposition molding apparatus as claimed in claim 1, wherein: the gas-state uniform distribution reduction reaction tank (16) is of a multilayer concentric tube structure, a multilayer concentric tube-shaped hydrogen distribution bin (18) is arranged in the gas-state uniform distribution reduction reaction tank (16), the inner wall and the outer wall of the tube-shaped hydrogen distribution bin (18) are made of porous metal plates, two ends of the tube-shaped hydrogen distribution bin (18) are plugged by annular compact metal plates, each layer of tube-shaped hydrogen distribution bin is communicated with the hydrogen heating tank (11) through an external metal tube, heating hydrogen enters the tube-shaped hydrogen distribution bin under the action of pressure, and then the hydrogen is blown out towards the radial direction of the tube through the multi-hollow metal plates on the inner wall.
3. The integrated molybdenum vapor deposition molding apparatus as claimed in claim 2, wherein: the holes on the porous metal plates on the inner wall and the outer wall of the tubular hydrogen distribution bin (18) are uniformly distributed.
4. The integrated molybdenum vapor deposition molding apparatus according to any one of claims 1 to 3, wherein: the device is characterized by further comprising a gas-solid circulation recovery area (5), wherein the gas-solid circulation recovery area (5) comprises a dust collecting device, a steam-water separating device and an argon/hydrogen separating device, and the gas-solid circulation recovery area (5) is communicated with the corresponding gas uniformly-distributed reduction reaction tank (16), the hydrogen heating tank (11) and the argon pressure maintaining tank (6).
5. An integrated method for molybdenum vapor deposition molding based on the device of claim 4, which is characterized by comprising the following steps:
1) Molybdenum source vapor phase sublimation
Adding MoO 3 Putting into a molybdenum trioxide evaporation tank (12), replacing the air in the furnace by vacuum exhaust and gas replacement, heating the furnace to 600-1000 deg.C, opening the gas outlet valve when the positive pressure in the furnace is not less than 0.021Mpa, and sublimating MoO 3 Feeding the mixture into a gaseous uniformly-distributed reduction reaction tank through a heat-insulating pipeline;
2) Gas phase reduction of
MoO from molybdenum trioxide evaporator (12) 3 Gas enters a gaseous uniformly-distributed reduction reaction tank (16) through a heat-insulating pipeline, meets heating hydrogen blown in from the tubular hydrogen distribution bins in the radial direction through the shunt of a plurality of coaxial tubular hydrogen distribution bins to realize homogeneous gas-phase reduction, and generates nanoscale molybdenum powder with uniform particle size;
3) Enhanced deposition of nano-sized molybdenum powder
Under the action of gas pressure, the generated nanoscale molybdenum powder flows out from the other side of the gaseous uniformly-distributed reduction reaction tank (16), touches the wire mesh when passing through a negatively-charged wire mesh (15) or is electrified under the action of a corona field of the wire mesh, and under the action of an electric field, the nanoscale powder electrified with the electricity is directionally deposited to a deposition area with the electricity, meanwhile, the gas-solid separation of water vapor and excessive hydrogen from nanoscale molybdenum powder particles is realized, and trace nanoscale molybdenum powder is discharged out of the strengthened deposition area (3) under the action of the gas pressure in the furnace;
4) On-line consolidation forming
The deposition shape is controlled by controlling the electric field distribution of the positively charged deposition platform (14), the molybdenum metal shape with a specific shape is formed, and the molybdenum metal is sintered at the online low temperature of 800-1300 ℃ to form the required shape and size of the product.
6. The integrated molybdenum vapor deposition molding method according to claim 5, wherein a gas-solid recycling zone (5) is utilized in the manufacturing process, and water vapor and solid powder which are not completely reacted are respectively collected by a dust collection device, a vapor-water separation device and an argon/hydrogen separation device and then returned to corresponding raw material tanks, hydrogen tanks and argon tanks for recycling.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235488A (en) * | 2007-01-29 | 2008-08-06 | 北京行者多媒体科技有限公司 | Technique for forming thin film on substrate equipped outside radio frequency plasma |
| CN101396741A (en) * | 2008-11-06 | 2009-04-01 | 洛阳开拓者投资管理有限公司 | Preparation method of high-purity superfine metal molybdenum powder |
| CN102632249A (en) * | 2012-03-29 | 2012-08-15 | 洛阳开拓者投资管理有限公司 | Method for preparing metal molybdenum powder |
| CN103203455A (en) * | 2013-04-12 | 2013-07-17 | 金堆城钼业股份有限公司 | Method for manufacturing molybdenum powder |
| CN104651637A (en) * | 2013-11-18 | 2015-05-27 | 徐丽萍 | High-purity molybdenum trioxide processing technology |
| CN105710390A (en) * | 2016-05-05 | 2016-06-29 | 北京科技大学 | Method for preparing nano-grade molybdenum powder by directly utilizing industrial-grade molybdenum trioxide |
| CN111421144A (en) * | 2020-03-27 | 2020-07-17 | 西安交通大学 | Water corrosion resistant refractory metal molybdenum surface treatment method |
| CN113477185A (en) * | 2021-07-27 | 2021-10-08 | 郑州大学 | Device and method for preparing molybdenum trioxide through efficient vaporization |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030028296A (en) * | 2001-09-28 | 2003-04-08 | 학교법인 한양학원 | Plasma enhanced chemical vapor deposition apparatus and method of producing a cabon nanotube using the same |
| US6626976B2 (en) * | 2001-11-06 | 2003-09-30 | Cyprus Amax Minerals Company | Method for producing molybdenum metal |
| US20090050058A1 (en) * | 2006-10-12 | 2009-02-26 | Ovshinsky Stanford R | Programmed high speed deposition of amorphous, nanocrystalline, microcrystalline, or polycrystalline materials having low intrinsic defect density |
| CN202655636U (en) * | 2012-06-29 | 2013-01-09 | 金堆城钼业股份有限公司 | Hydrogen recovery system for reduction of molybdenum powder |
| CN110976900A (en) * | 2019-11-21 | 2020-04-10 | 金堆城钼业股份有限公司 | Production method of composite alloy molybdenum powder |
-
2022
- 2022-03-11 CN CN202210241275.9A patent/CN114606479B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235488A (en) * | 2007-01-29 | 2008-08-06 | 北京行者多媒体科技有限公司 | Technique for forming thin film on substrate equipped outside radio frequency plasma |
| CN101396741A (en) * | 2008-11-06 | 2009-04-01 | 洛阳开拓者投资管理有限公司 | Preparation method of high-purity superfine metal molybdenum powder |
| CN102632249A (en) * | 2012-03-29 | 2012-08-15 | 洛阳开拓者投资管理有限公司 | Method for preparing metal molybdenum powder |
| CN103203455A (en) * | 2013-04-12 | 2013-07-17 | 金堆城钼业股份有限公司 | Method for manufacturing molybdenum powder |
| CN104651637A (en) * | 2013-11-18 | 2015-05-27 | 徐丽萍 | High-purity molybdenum trioxide processing technology |
| CN105710390A (en) * | 2016-05-05 | 2016-06-29 | 北京科技大学 | Method for preparing nano-grade molybdenum powder by directly utilizing industrial-grade molybdenum trioxide |
| CN111421144A (en) * | 2020-03-27 | 2020-07-17 | 西安交通大学 | Water corrosion resistant refractory metal molybdenum surface treatment method |
| CN113477185A (en) * | 2021-07-27 | 2021-10-08 | 郑州大学 | Device and method for preparing molybdenum trioxide through efficient vaporization |
Non-Patent Citations (3)
| Title |
|---|
| Preparation of ultrafine molybdenum powder by vapour phase reaction of the MoO3-H2 system;koji Shibata;《Journal of the Less-Common Metals》;20030611;第157卷(第1期);第L5-L10页1 * |
| 氢气还原蒸发态MoO_3制取超细钼粉的探索;赵新瑞等;《中国钼业》;20040630;第28卷(第03期);第34-36页 * |
| 钼及钼合金粉末冶金技术研究现状与发展;冯鹏发;《中国钼业》;20100630;第34卷(第3期);第39-45页 * |
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