CN104476653B - The 3D of a kind of porous niobium product prints manufacture method - Google Patents
The 3D of a kind of porous niobium product prints manufacture method Download PDFInfo
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- CN104476653B CN104476653B CN201410701050.2A CN201410701050A CN104476653B CN 104476653 B CN104476653 B CN 104476653B CN 201410701050 A CN201410701050 A CN 201410701050A CN 104476653 B CN104476653 B CN 104476653B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
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Abstract
The 3D of a kind of porous niobium product prints manufacture method, and the present invention first passes through the selective laser sintering (Selective Laser Sintering, SLS) of niobium oxide powder, shapes complicated shape oxide product；Then carry out molten-salt electrolysis deoxidation as negative electrode, make niobium oxide product be reduced to niobium product, retain original shape simultaneously, thus obtain complicated shape porous niobium product, it is achieved " metallurgical material device " integration manufactures.The present invention provides through cheap niobium oxide powder, the manufacture method of complicated shape porous metals niobium product can be produced, it is not necessary to mould, have that technical process is simple, complex-shaped, low cost, the advantage of green manufacturing.
Description
Technical field
The invention belongs to 3D printing technique and molten-salt electrolysis combined shaping field, a kind of complicated shape porous niobium and the low-cost manufacture method of alloyed components.
Background technology
Porous material is a kind of material being made up of niobium skeleton and hole.Compared with dense material, the typical feature of porous material is internal containing substantial amounts of hole.Therefore, porous niobium has following premium properties, as little in density, that specific surface area is big, thermal conductivity is low, heat-sinking capability is high, permeability is strong, energy-absorbing inhales ripple acoustical absorptivity is strong, good biocompatibility etc..In recent years, porous material product has been obtained for application widely, as being used as biomaterial medical devices, amortisseur, buffer, filter, energy absorber, fluid through device, heat exchanger, fire extinguisher, engine exhaust muffler etc..
Prior powder metallurgy (Powder Metallurgy, PM) is the manufacturing process of a kind of common porous product.Its detailed process is niobium powder pine to be loaded on mould be pressed, and is then sintered, and in sintering process, powder particle mutually bonds, thus forms porous sintered body.This manufacturing process can produce the porous niobium product that porosity is 20% ~ 60%.
When but tradition shapes various porous niobium materials and parts, there is problems in that
(1) prior powder metallurgy prepares porous niobium needs by mould molding, so that its shape is restricted, it is difficult to direct forming goes out the product of any complicated shape.
(2) prior powder metallurgy needs the niobium powder used, and it needs to smelt from its corresponding mineral and extract, and forming process technique is loaded down with trivial details, pollution environment, relatively costly.
(3) tradition niobium powder metallurgy is prepared about the smelting of metal dust, material, and figuration manufacture is carried out separately, it is difficult to realizes " metallurgy-material-device " integration and manufactures.
Summary of the invention
The simple shape that exists for conventional porous niobium product powder metallurgically manufacturing method, niobium powder smelt pollute, deficiency that cost is high, the present invention provides the low-cost manufacture method of a kind of complicated shape porous niobium parts, the method, without mould, has that technical process is simple, complex-shaped, low cost, the feature of green manufacturing.The method be selective laser sintering by niobium oxide powder (Selective Laser Sintering,
SLS) shape complicated shape oxide product, then carry out molten-salt electrolysis deoxidation (referred to as FFC method), and then shape complicated shape porous niobium product.
The invention provides porous product near-net-shape method, the steps include:
(1) preparation of niobium oxide composite powder and 3D printing-forming: with one or more niobium oxide powders as raw material, add high polymer binder powder, or niobium oxide powder surface is covered adhensive membrane, thus prepare oxide/binding agent composite powder that applicable SLS shapes；Use 3D sculpting software to design the three-dimensional CAD model of product, after being then processed as by Slice Software, save as stl file, the data message of stl file is transported to SLS quick shaping equipment；Tile on metallic substrates the niobium oxide powder that certain thickness, certain particle diameter be to powder feeding mechanism；Use small-power CO2Laser instrument oxide/adhesive powder scanning to break area, and then make this layer and preceding layer strong bonded；Above procedure moves in circles, and carries out multilamellar manufacture, until whole oxide product shapes complete.
(2) above-mentioned oxidation niobio product is connected with a wherein electrode of molten-salt electrolysis, it addition, also meet two coated graphite rod electrrode, CaCl2-NaCl is electrolyte, and nickel crucible is electrolysis bath, and electrolysis bath is placed in resistance-heated furnace；In electrolysis bath, it is passed through the noble gases such as argon, is passed through argon, rise high-temperature and make fused salt melt, two graphite are fallen and contacts with fused salt, connect negative electrode and the anode of DC source respectively；And oxide product is not fallen, do not contact with fused salt；Carrying out preelectrolysis, during this, oxide product realizes defat and agglomeration under high temperature action, after preelectrolysis terminates, is risen to above fused salt by negative electrode graphite rod；
(3) being connected with the negative electrode of molten-salt electrolysis by above-mentioned niobium oxide product, with graphite as anode, with calcium chloride as electrolyte, carry out molten-salt electrolysis, electrolytic process is carried out at a certain temperature, and uses argon shield.First carry out high-temperature heating, make niobium oxide product defat and presintering.Then being electrolysed, after electrolysis certain time, niobium oxide negative electrode product then becomes metal niobium product, is drawn off after cooling.
Described high polymer binder powder is epoxy resin powder.
SLS forming technique is combined by the present invention with molten-salt electrolysis deoxy technology, and this complex method has the advantage that (1) uses the oxide product prototype that SLS manufactures, and when molten-salt electrolysis deoxidation becomes niobium product, still can retain its complicated shape.(2) technical process is simple, it is to avoid the techniques such as the smelting of niobium powder and powder process, directly becomes niobium parts from oxide, it is to avoid environmental pollution, cost are relatively low.
Detailed description of the invention
Detailed process to the present invention makees further details of elaboration below:
(1) according to final required niobium and alloy product composition, choosing niobium oxide powder or niobium oxide with other oxide mixed-powders is raw material, add high polymer binder powder, or niobium oxide powder surface is covered adhensive membrane, thus prepare oxide/binding agent composite powder that applicable SLS shapes；Use 3D sculpting software to design the three-dimensional CAD model of product, after being then processed as by Slice Software, save as stl file, the data message of stl file is transported to SLS quick shaping equipment；Powder feeding mechanism is tiled on metallic substrates one layer and be about the niobium oxide powder that 0.1 ~ 0.3mm thickness, particle diameter are 10-100 μm.Use the laser power CO less than or equal to 50W2Laser instrument oxide/adhesive powder scanning to break area, and then make this layer and preceding layer strong bonded；Above procedure moves in circles, and carries out multilamellar manufacture, until whole niobium oxide product shapes complete；
(2) above-mentioned oxidation niobio product is connected with a wherein electrode of molten-salt electrolysis.It addition, also meet two coated graphite rod electrrode, CaCl2-NaCl is electrolyte, and nickel crucible is electrolysis bath, and electrolysis bath is placed in resistance-heated furnace；Being passed through the noble gases such as argon in electrolysis bath, the argon flow speed control being passed through is at 1.5-3.5L/min, and temperature rises to 800 ~ 1000 DEG C, is fallen by two graphite and contacts with fused salt, connects negative electrode and the anode of DC source respectively.And oxide product is not fallen, do not contact with fused salt.Carrying out preelectrolysis 5 ~ 30 hours under 2.0V, during this, oxide product realizes defat and agglomeration under high temperature action.After preelectrolysis terminates, negative electrode graphite rod is risen to above fused salt；
(3) oxide product is connect negative electrode, and declined immersion fused salt, at 3.1V(less than fused salt CaCl2Decomposition voltage 3.214V) be electrolysed under voltage, after being electrolysed 20 ~ 150 hours, oxide-coated cathode product then becomes niobium product, is drawn off, cleans surface fused salt and can obtain complicated porous niobium product after cooling.
Below in conjunction with example, the invention will be further described.
Embodiment
1
(1) for manufacturing pure niobium porous metals product, with the niobium oxide powder of mean diameter 20 μm as raw material, it is mixed into the epoxy powder of mean diameter 20 μm, wherein epoxy powder mass fraction 10%, ball milling mixes 5 hours, prepares niobium oxide/epoxy resin composite powder that applicable SLS shapes；Use 3D sculpting software to design the three-dimensional CAD model of product, after being then processed as by Slice Software, save as stl file, the data message of stl file is transported to SLS quick shaping equipment；Powder feeding mechanism is tiled on metallic substrates one layer and be about the niobium oxide composite powder that 0.1mm thickness, particle diameter are 20 μm.Use the laser power CO equal to 50W2Laser instrument niobium oxide/epoxy resin composite powder scanning to break area, and then make this layer and preceding layer strong bonded；Repeat monolayer manufacture process, until whole niobium oxide/epoxy resin product SLS shapes complete；
(2) above-mentioned niobium oxide/epoxy resin product is connected with a wherein electrode of molten-salt electrolysis.It addition, also meet two coated graphite rod electrrode, CaCl2For electrolyte, nickel crucible is electrolysis bath, and electrolysis bath is placed in resistance-heated furnace；Being passed through the noble gases such as argon in electrolysis bath, the argon flow speed control being passed through is at 2L/min, and temperature rises to 900 DEG C, is fallen by two graphite and contacts with fused salt, connects negative electrode and the anode of DC source respectively.And oxide product is not fallen, do not contact with fused salt.Carrying out preelectrolysis 15 hours under 2.0V, during this, niobium oxide/epoxy resin product realizes defat and agglomeration under high temperature action, forms pure zirconia niobium product.After preelectrolysis terminates, negative electrode graphite rod is risen to above fused salt；
(3) niobium oxide product is connect negative electrode, and declined immersion fused salt, it is electrolysed under 3.1V voltage, after being electrolysed 100 hours, niobium oxide negative electrode product then becomes simple metal niobium product, is drawn off, cleans surface fused salt and can obtain complicated porous metals niobium product after cooling.
Embodiment
2
(1) for manufacturing Nb-20Ta alloy porous product, with the niobium oxide of mean diameter 10 μm, tantalum oxide powder as raw material, the most above-mentioned oxide powder ratio is added according to Nb-20Ta metering ratio, and it is mixed into the epoxy powder of mean diameter 10 μm, wherein epoxy powder mass fraction 10%, ball milling mixes 5 hours, prepares the Nb-20Ta/ epoxy resin composite powder that applicable SLS shapes；Use 3D sculpting software to design the three-dimensional CAD model of product, after being then processed as by Slice Software, save as stl file, the data message of stl file is transported to SLS quick shaping equipment；Powder feeding mechanism is tiled on metallic substrates one layer and be about the oxide composite metal powder that 0.05mm thickness, particle diameter are 10 μm.Use the CO of laser power 50W2The Nb-20Ta/ epoxy resin composite powder of break area is scanned by laser instrument, and then makes this layer and preceding layer strong bonded；Circular monolayer manufacture process, until whole Nb-20Ta/ epoxy resin product SLS shapes complete；
(2) above-mentioned Nb-20Ta/ epoxy resin product is connected with a wherein electrode of molten-salt electrolysis.It addition, also meet two coated graphite rod electrrode, CaCl2For electrolyte, nickel crucible is electrolysis bath, and electrolysis bath is placed in resistance-heated furnace；Being passed through the noble gases such as argon in electrolysis bath, the argon flow speed control being passed through is at 2L/min, and temperature rises to 950 DEG C, is fallen by two graphite and contacts with fused salt, connects negative electrode and the anode of DC source respectively.And oxide product is not fallen, do not contact with fused salt.Carrying out preelectrolysis 15 hours under 2.0V, during this, Nb-20Ta/ epoxy resin product realizes defat and agglomeration under high temperature action, forms pure zirconia niobium-Al2O3-ZrO2Product.After preelectrolysis terminates, negative electrode graphite rod is risen to above fused salt；
(3) niobium oxide product is connect negative electrode, and declined immersion fused salt, it is electrolysed under 3.2V voltage, after being electrolysed 80 hours, niobium oxide negative electrode product then becomes simple metal niobium product, is drawn off, cleans surface fused salt and can obtain complicated porous Nb-20Ta alloy product after cooling.
Claims (2)
1. the 3D of a porous niobium product prints manufacture method, it is characterised in that comprise the steps:
(1) according to final required niobium and alloy product composition, niobium oxide powder or niobium oxide and other oxide mixed powders are chosen
End is raw material, adds high polymer binder powder, or niobium oxide powder surface is covered adhensive membrane, thus prepare applicable SLS
Oxide/binding agent the composite powder shaped, SLS is the abbreviation of selective laser sintering；Employing 3D sculpting software designs
Go out the three-dimensional CAD model of product, be transported to SLS quick shaping equipment；Powder feeding mechanism is tiled on metallic substrates one layer 0.1 ~
0.3mm thickness, particle diameter are the niobium oxide powder of 10-100 μm；Use the laser power CO less than or equal to 50W2Laser instrument is to cutting
The oxide of panel region/adhesive powder scanning, and then make this layer and preceding layer strong bonded；Above procedure moves in circles, and enters
Row multilamellar manufactures, until whole niobium oxide product shapes complete；
(2) above-mentioned niobium oxide product is connected with a wherein electrode of molten-salt electrolysis, it addition, also connect two coated graphite rod electrrode,
CaCl2-NaCl is electrolyte, and nickel crucible is electrolysis bath, and electrolysis bath is placed in resistance-heated furnace；It is passed through argon in electrolysis bath,
The argon flow speed control being passed through is at 1.5-3L/min, and temperature rises to 800 ~ 1000 DEG C, is fallen by two graphite and contacts with fused salt, point
Do not connect negative electrode and the anode of DC source；And niobium oxide product is not fallen, do not contact with fused salt；Carry out under 2.0V preelectrolysis 5 ~
30 hours, during this, niobium oxide product realized defat and agglomeration under high temperature action, after preelectrolysis terminates, by negative electrode
Graphite rod rises to above fused salt；
(3) niobium oxide product is connect negative electrode, and declined immersion fused salt, be electrolysed under 3.1V voltage, be electrolysed 20 ~ 150
After hour, niobium oxide product then becomes niobium product, is drawn off, cleans surface fused salt, i.e. obtain complicated porous niobium system after cooling
Part.
2. the 3D of porous niobium product as claimed in claim 1 prints manufacture method, it is characterised in that: described macromolecule bonding
Agent powder is epoxy resin powder.
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| CN107973607B (en) * | 2016-10-21 | 2020-02-07 | 南京理工大学 | Selective laser melting/sintering forming method for ceramic slurry without binder |
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| CN201809445U (en) * | 2010-08-06 | 2011-04-27 | 昆明理工大学 | Fused salt electrolyzing device for reducing SiO2 into Si |
| CN102505128A (en) * | 2011-12-23 | 2012-06-20 | 西北有色金属研究院 | Method for directly preparing porous metal product by molten salt electrolysis |
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Inventor after: Yuan Tiechui Inventor after: Li Ruidi Inventor after: Liu Xiaojun Inventor after: Fan Wenbo Inventor after: Zhou Libo Inventor before: Li Ruidi Inventor before: Yuan Tiechui Inventor before: Liu Xiaojun Inventor before: Fan Wenbo Inventor before: Zhou Libo |
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