CN113798507A - Low-temperature 3D printing forming method for refractory alloy - Google Patents
Low-temperature 3D printing forming method for refractory alloy Download PDFInfo
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- CN113798507A CN113798507A CN202110927463.2A CN202110927463A CN113798507A CN 113798507 A CN113798507 A CN 113798507A CN 202110927463 A CN202110927463 A CN 202110927463A CN 113798507 A CN113798507 A CN 113798507A
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000010146 3D printing Methods 0.000 title claims abstract description 37
- 229910000753 refractory alloy Inorganic materials 0.000 title claims abstract description 17
- 238000005238 degreasing Methods 0.000 claims abstract description 66
- 239000000843 powder Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000012298 atmosphere Substances 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 46
- 239000000853 adhesive Substances 0.000 claims description 16
- 230000001070 adhesive effect Effects 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000007639 printing Methods 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012188 paraffin wax Substances 0.000 claims description 8
- -1 polyethylene vinyl acetate Polymers 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 229920006351 engineering plastic Polymers 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000003870 refractory metal Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 15
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- B22F10/10—Formation of a green body
-
- 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
- B22F10/62—Treatment of workpieces or articles after build-up by chemical 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
- B22F10/60—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
- 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
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- 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
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
- B22F3/1025—Removal of binder or filler not by heating only
-
- 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
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a low-temperature 3D printing forming method of refractory alloy, which is characterized by comprising the following steps of: step 1, mixing two or more than two kinds of metal powder according to a certain proportion to obtain mixed metal powder; step 2, uniformly mixing the mixed metal powder obtained in the step 1 with a binder with a specific formula according to a certain proportion to prepare a feed; step 3, loading the feed obtained in the step 2 into a desktop melt extrusion printer for 3D printing to obtain a blank body; step 4, performing two-step degreasing on the blank obtained in the step 3, namely performing solution degreasing at first and then performing thermal degreasing; and 5, sintering the degreased blank obtained in the step 4 in a certain atmosphere to obtain a final sample. The method realizes the die-free 3D printing free forming of refractory metal products, and obviously improves the mechanical property of parts after 3D printing forming.
Description
Technical Field
The invention belongs to the technical field of additive manufacturing of composite materials, and particularly relates to a low-temperature 3D printing forming method of refractory alloy.
Background
Refractory alloys such as tungsten-copper alloy, tungsten-nickel alloy, tungsten-titanium alloy, molybdenum-copper alloy, molybdenum-tungsten alloy and the like are widely applied to military high-temperature-resistant materials, electric alloys for high-voltage switches, electric processing electrodes and microelectronic materials, and are widely applied to industries such as aerospace, aviation, electronics, electric power, metallurgy, machinery, sports equipment and the like as parts and components. With the continuous progress and development of the technology in the above fields, the performance of tungsten-copper alloy is currently subject to more severe use requirements. Moreover, most of the commercial refractory alloys at present are prepared by adopting a powder metallurgy process, such as hot-pressing sintering, infiltration and the like after cold pressing of a die into a blank, and have the defects of low productivity, high price of a hot-pressing furnace, need of the die, difficulty in large-scale production, high subsequent machining cost, long flow and the like.
Disclosure of Invention
The invention aims to provide a low-temperature 3D printing forming method for refractory alloy, which realizes the mould-free 3D printing free forming of refractory metal products and obviously improves the mechanical property of parts after 3D printing forming.
The invention adopts the technical scheme that a low-temperature 3D printing forming method of refractory alloy comprises the following steps:
Mixing two or more than two kinds of metal powder according to a certain proportion to obtain mixed metal powder;
Uniformly mixing the mixed metal powder obtained in the step 1 with a binder with a specific formula according to a certain proportion to prepare a feed;
Loading the feed obtained in the step 2 into a desktop melt extrusion printer for 3D printing to obtain a blank body;
Carrying out two-step degreasing on the blank obtained in the step 3, namely firstly carrying out solution degreasing and then carrying out thermal degreasing;
And (4) sintering the degreased blank obtained in the step (4) in a certain atmosphere to obtain a final sample.
The present invention is also characterized in that,
in the step 1, the mixed metal powder is composed of two or more of tungsten, molybdenum, niobium, tantalum, titanium, iron, cobalt, copper and nickel in any proportion, and the mixed metal powder is obtained by mixing in a mixer or a ball mill.
In the step 2, the adhesive comprises the following raw materials in percentage by mass: 10-95 wt.% of semi-refined paraffin, 1-50 wt.% of high-density polyethylene, 1-50 wt.% of stearic acid and 1-50 wt.% of polyethylene vinyl acetate, wherein the sum of the mass percentages of the components is 100%; the mass ratio of the mixed powder to the adhesive is 1: 99-99.9: 0.1.
In step 3, the specific printing forming parameters are as follows: substrate material: glass, engineering plastic or metal stools; the temperature of the substrate is 5-300 ℃, the diameter of the nozzle is 0.001-10 mm, and the temperature of the nozzle is 5-400 ℃.
In the step 4, the first degreasing process of the green body obtained in the step 3 is to heat the green body to 30-150 ℃ in a cyclohexane solution and keep the temperature for 1-60 h; the second step of the thermal degreasing process of the blank body is to execute the following thermal degreasing process scheme under the protection of nitrogen or argon inert gas atmosphere: heating the sample from room temperature to 120 ℃ at a heating rate of 4 ℃/min, and storing at 120 ℃ for 30 min; then, the temperature is increased from 120 ℃ to 260-360 ℃ at the heating rate of 1-20 ℃/min, and the temperature is kept for 30 min-2 h; heating from 260-360 ℃ to 400-440 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 30 min-2 h, heating to 450-500 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 30 min-2 h, heating to 510-590 ℃ at a rate of 1-20 ℃/min, and preserving heat for 30 min-2 h at the temperature; and finally, raising the temperature to 600-800 ℃ at the speed of 1-20 ℃/min, preserving the temperature for 30-2 h, and cooling to room temperature in a furnace cooling mode.
In the step 5, the sintering of the degreased blank obtained in the step 4 is protected by nitrogen or argon inert atmosphere or is carried out in hydrogen reducing atmosphere, the sintering temperature is 850-1800 ℃, and the sintering time is 0.1-50 h.
The invention has the beneficial effects that:
the low-temperature 3D printing forming method of the refractory alloy has the advantages that the mould-free 3D printing free forming of refractory metal products is realized, the complete removal of the adhesive is realized by the subsequent two-step degreasing scheme, a perfect and clean composite material interface is obtained, and the remarkable improvement of the mechanical property is ensured. The low-temperature forming method integrates the advantages of 3D printing, injection molding, adhesive injection technology and the like, has the characteristics of high printing speed, high forming precision, wide range of printable materials, good product performance consistency, low cost, capability of preparing parts with complex shapes and the like, overcomes the defects that the commercial refractory alloy is prepared by carrying out hot-pressing sintering, infiltration and the like after being subjected to die cold pressing and blank forming brought by a powder metallurgy process at present, has low production efficiency, high price of a hot-pressing furnace, needs a die, is difficult to produce in a large scale, has high subsequent machining cost, long flow and the like, and provides a brand-new solution for preparing the refractory material with a complex structure.
Drawings
FIG. 1 is an SEM photograph of commercially available gas atomized spherical copper powder obtained in example 4 of the present invention.
FIG. 2 is an SEM photograph of a commercially available ultrafine tungsten powder obtained in example 4 of the present invention.
FIG. 3 is an SEM image of W-30 wt.% Cu powder obtained in example 4 of the present invention after ball milling.
FIG. 4 is a metallographic photograph of an adhesive obtained in example 4 of the present invention.
FIG. 5 is a TG curve of a binder obtained in example 4 of the present invention;
FIG. 6 is a DTG curve of the binder obtained in example 4 of the present invention;
FIG. 7 is a metallographic picture of a feedstock obtained in example 4 of the present invention.
FIG. 8 is a photomicrograph of a feedstock obtained in example 4 of the present invention.
FIG. 9 is a first photograph of a desktop 3D printer according to embodiment 4 of the present invention;
fig. 10 is a second photograph of a desktop 3D printer in accordance with embodiment 4 of the present invention;
FIG. 11 is a 3D model of a thin-walled cylinder of example 4 of the present invention;
FIG. 12 is a photograph of a blank after printing in example 4 of the present invention;
FIG. 13 is a stress-strain curve of a prepared sample obtained in example 4 of the present invention;
FIG. 14 is an SEM image of the fracture morphology of the prepared sample obtained in example 4 of the invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a low-temperature 3D printing forming method of refractory alloy, which comprises the following steps:
Mixing two or more than two kinds of metal powder according to a certain proportion to obtain mixed metal powder;
in the step 1, the mixed metal powder is composed of two or more of tungsten, molybdenum, niobium, tantalum, titanium, iron, cobalt, copper and nickel in any proportion, and the mixed metal powder is obtained by mixing in a mixer or a ball mill.
Uniformly mixing the mixed metal powder obtained in the step 1 with a binder with a specific formula according to a certain proportion to prepare a feed;
in the step 2, the adhesive comprises the following raw materials in percentage by mass: 10-95 wt.% of semi-refined paraffin, 1-50 wt.% of high-density polyethylene, 1-50 wt.% of stearic acid and 1-50 wt.% of polyethylene vinyl acetate, wherein the sum of the mass percentages of the components is 100%; the mass ratio of the mixed powder to the adhesive is 1: 99-99.9: 0.1.
Loading the feed obtained in the step 2 into a desktop melt extrusion printer for 3D printing to obtain a blank body;
in step 3, the specific printing forming parameters are as follows: substrate material: the temperature of the glass (or engineering plastics or metal stools) and the substrate is 5-300 ℃, the diameter of the nozzle is 0.001-10 mm, and the temperature of the nozzle is 5-400 ℃.
Carrying out two-step degreasing on the blank obtained in the step 3, namely firstly carrying out solution degreasing, and then carrying out thermal degreasing according to a specific degreasing scheme;
in the step 4, the first degreasing process of the green body obtained in the step 3 is to heat the green body to 30-150 ℃ in a cyclohexane solution and keep the temperature for 1-60 h; the second step of the thermal degreasing process of the blank body is to execute the following thermal degreasing process scheme under the protection of nitrogen or argon inert gas atmosphere: heating the sample from room temperature to 120 ℃ at a heating rate of 4 ℃/min, and storing at 120 ℃ for 30 min; then, the temperature is increased from 120 ℃ to 260-360 ℃ at the heating rate of 1-20 ℃/min, and the temperature is kept for 30 min-2 h; heating from 260-360 ℃ to 400-440 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 30 min-2 h, heating to 450-500 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 30 min-2 h, heating to 510-590 ℃ at a rate of 1-20 ℃/min, and preserving heat for 30 min-2 h at the temperature; and finally, raising the temperature to 600-800 ℃ at the speed of 1-20 ℃/min, preserving the temperature for 30-2 h, and cooling to room temperature in a furnace cooling mode.
Sintering the degreased blank obtained in the step 4 in a certain atmosphere to obtain a final sample;
in the step 5, the sintering of the degreased blank obtained in the step 4 is protected by nitrogen or argon inert atmosphere or is carried out in hydrogen reducing atmosphere, the sintering temperature is 850-1800 ℃, and the sintering time is 0.1-50 h.
Example 1
Molybdenum powder and iron powder were mixed by a ball mill at a mass ratio of 1:9 to obtain Mo-90 wt.% Fe mixed powder.
Mixing the mixed metal powder obtained in the step 1 with a binder according to a mass ratio of 80: 20, preparing feed after uniformly mixing; the adhesive comprises the following raw materials in percentage by mass: 10 wt.% of semi-refined paraffin, 50 wt.% of high-density polyethylene, 30 wt.% of stearic acid and 10 wt.% of polyethylene vinyl acetate, wherein the sum of the mass percentages of the components is 100%.
And (3) loading the feed obtained in the step (2) into a desktop melt extrusion printer for 3D printing to obtain a blank body. The specific printing forming parameters are as follows: the substrate is made of an aluminum plate, the temperature of the substrate is 300 ℃, the diameter of the nozzle is 10mm, and the temperature of the nozzle is 5 ℃.
And (3) carrying out two-step degreasing on the blank obtained in the step (3), namely firstly carrying out solution degreasing, and then carrying out thermal degreasing according to a specific degreasing scheme. The first step degreasing process of the sample is to heat the sample to 30 ℃ in a cyclohexane solution and keep the temperature for 60 hours; the second step of the thermal degreasing process of the sample is to execute the following thermal degreasing process scheme under the protection of nitrogen atmosphere: the sample was heated from room temperature to 120 ℃ at a ramp rate of 4 ℃/min and stored at 120 ℃ for 30 min. Subsequently, the temperature was raised from 120 ℃ to 270 ℃ at a ramp rate of 1 ℃/min and maintained at that temperature for 2 h. Heating from 270 deg.C to 440 deg.C at a rate of 20 deg.C/min, maintaining for 30min, and heating to 450 deg.C at a rate of 1 deg.C/min. After 30min of heat preservation, the temperature is raised to 510 ℃ at the speed of 1 ℃/min, and heat preservation is carried out for 1h at the temperature. And finally, raising the temperature to 800 ℃ at the speed of 20 ℃/min, preserving the heat for 50min, and cooling to room temperature in a furnace cooling mode.
And (4) sintering the degreased blank obtained in the step (4) in a certain atmosphere to obtain a final sample. The sintering of the sample is carried out in a nitrogen atmosphere, the sintering temperature is 850 ℃, and the sintering time is 50 h.
Example 2
Mixing niobium powder and titanium powder in a mass ratio of 5:5 by a ball mill to obtain Nb-50 wt.% Ti mixed powder.
Mixing the mixed metal powder obtained in the step 1 with a binder according to a mass ratio of 99.9:0.1 percent of the mixture is uniformly mixed to prepare feed; the adhesive comprises the following raw materials in percentage by mass: 48 wt.% of semi-refined paraffin, 1 wt.% of high-density polyethylene, 50 wt.% of stearic acid and 1 wt.% of polyethylene vinyl acetate, wherein the sum of the mass percentages of the components is 100%.
And (3) loading the feed obtained in the step (2) into a desktop melt extrusion printer for 3D printing to obtain a blank body. The specific printing forming parameters are as follows: the substrate is made of stainless steel, the temperature of the substrate is 200 ℃, the diameter of the nozzle is 3mm, and the temperature of the nozzle is 200 ℃.
And (3) carrying out two-step degreasing on the blank obtained in the step (3), namely firstly carrying out solution degreasing, and then carrying out thermal degreasing according to a specific degreasing scheme. The first degreasing process of the sample comprises the steps of heating the sample to 100 ℃ in a cyclohexane solution, and keeping the temperature for 5 hours; the second step of the thermal degreasing process of the sample is to execute the following thermal degreasing process scheme under the protection of argon atmosphere: the sample was heated from room temperature to 120 ℃ at a ramp rate of 4 ℃/min and stored at 120 ℃ for 30 min. Subsequently, the temperature was raised from 120 ℃ to 360 ℃ at a ramp rate of 20 ℃/min and held at that temperature for 1 h. Then heating from 360 ℃ to 410 ℃ at the heating rate of 1 ℃/min, preserving the heat for 2h, and then heating to 500 ℃ at the heating rate of 20 ℃/min. After 2h of incubation, the temperature was raised to 590 ℃ at a rate of 20 ℃/min and incubated at that temperature for 2 h. And finally, raising the temperature to 650 ℃ at the speed of 1 ℃/min, preserving the heat for 2 hours, and cooling to room temperature in a furnace cooling mode.
And (4) sintering the degreased blank obtained in the step (4) in a certain atmosphere to obtain a final sample. The sample is sintered in a hydrogen atmosphere at 1000 ℃ for 10 h.
Example 3
Mixing tungsten powder and cobalt powder at a mass ratio of 9:1 by a ball mill to obtain W-70 wt.% Co mixed powder.
Mixing the mixed metal powder obtained in the step 1 with a binder according to a mass ratio of 1%: preparing a feed after uniformly mixing 99 percent of the mixture; the adhesive comprises the following raw materials in percentage by mass: 30 wt.% of semi-refined paraffin, 10 wt.% of high-density polyethylene, 10 wt.% of stearic acid and 50 wt.% of polyethylene vinyl acetate, wherein the sum of the mass percentages of the components is 100%.
And (3) loading the feed obtained in the step (2) into a desktop melt extrusion printer for 3D printing to obtain a blank body. The specific printing forming parameters are as follows: the substrate is made of a titanium alloy plate, the temperature of the substrate is 150 ℃, the diameter of a nozzle is 0.1mm, and the temperature of the nozzle is 300 ℃.
And (3) carrying out two-step degreasing on the blank obtained in the step (3), namely firstly carrying out solution degreasing, and then carrying out thermal degreasing according to a specific degreasing scheme. The first degreasing process of the sample comprises the steps of heating the sample to 120 ℃ in a cyclohexane solution, and keeping the temperature for 30 hours; the second step of the thermal degreasing process of the sample is to execute the following thermal degreasing process scheme under the protection of argon atmosphere: the sample was heated from room temperature to 120 ℃ at a ramp rate of 4 ℃/min and stored at 120 ℃ for 30 min. Subsequently, the temperature was raised from 120 ℃ to 300 ℃ at a temperature rising rate of 5 ℃/min and maintained at that temperature for 30 min. Then heating from 300 ℃ to 420 ℃ at the heating rate of 10 ℃/min, preserving the heat for 1h, and then heating to 480 ℃ at the heating rate of 5 ℃/min. After 1h of incubation, the temperature was raised to 520 ℃ at a rate of 5 ℃/min and incubated at that temperature for 1 h. And finally, raising the temperature to 700 ℃ at the speed of 8 ℃/min, preserving the temperature for 40min, and cooling to room temperature in a furnace cooling mode.
And (4) sintering the degreased blank obtained in the step (4) in a certain atmosphere to obtain a final sample. The sintering of the sample is carried out in an argon atmosphere, the sintering temperature is 1400 ℃, and the sintering time is 25 h.
Example 4
Tungsten powder and copper powder were mixed by a ball mill at a mass ratio of 7:3 to obtain W-30 wt.% Cu mixed powder.
Mixing the mixed metal powder obtained in the step 1 with a binder according to a mass ratio of 97%: preparing feed after 3 percent of the mixture is uniformly mixed; the adhesive comprises the following raw materials in percentage by mass: 65 wt.% of semi-refined paraffin, 5 wt.% of high-density polyethylene, 25 wt.% of stearic acid and 5 wt.% of polyethylene vinyl acetate, wherein the sum of the mass percentages of the components is 100%.
And (3) loading the feed obtained in the step (2) into a desktop melt extrusion printer for 3D printing to obtain a blank body. The specific printing forming parameters are as follows: the substrate is made of polyimide, the temperature of the substrate is 90 ℃, the diameter of a nozzle is 0.95mm, and the temperature of the nozzle is 150 ℃.
And (3) carrying out two-step degreasing on the blank obtained in the step (3), namely firstly carrying out solution degreasing, and then carrying out thermal degreasing according to a specific degreasing scheme. The first degreasing process of the sample comprises the steps of heating the sample to 50 ℃ in a cyclohexane solution, and keeping the temperature for 20 hours; the second step of the thermal degreasing process of the sample is to execute the following thermal degreasing process scheme under the protection of nitrogen atmosphere: the sample was heated from room temperature to 120 ℃ at a ramp rate of 4 ℃/min and stored at 120 ℃ for 30 min. Subsequently, the temperature was raised from 120 ℃ to 260 ℃ at a ramp rate of 3 ℃/min and maintained at 260 ℃ for 30 min. Then heating from 260 ℃ to 400 ℃ at the heating rate of 2 ℃/min, preserving the heat for 60min, and then heating to 450 ℃ at the heating rate of 2 ℃/min. After the temperature is kept for 30min, the temperature is raised to 550 ℃ at the speed of 2 ℃/min, and the temperature is kept at 550 ℃ for 30 min. Finally, the temperature is raised to 600 ℃ at the speed of 4 ℃/min, the temperature is kept for 30min, and then the temperature is cooled to room temperature in a furnace cooling mode, and the TG and DTG curves of the adhesive are shown in figures 5-6.
And (4) sintering the degreased blank obtained in the step (4) in a certain atmosphere to obtain a final sample. The sample is sintered in hydrogen atmosphere at 1350 ℃ for 2 h.
SEM of the metal powder raw materials copper powder and tungsten powder adopted in the example 4 are shown in figures 1 and 2, wherein the copper powder is micron-sized spherical powder, and the tungsten powder is nano-sized powder and is seriously agglomerated; an SEM (scanning electron microscope) of W-30 wt.% Cu powder obtained after mechanical ball milling and powder mixing is shown in figure 3, and can be seen that easily agglomerated nano-grade tungsten powder is uniformly dispersed on the surface of copper powder, and the copper powder deforms to a certain degree; FIG. 4 is a metallographic photograph of the adhesive showing that the components are mixed uniformly; FIG. 7 is a metallographic photograph of a feedstock after the binder was uniformly mixed with the mixed metal powder, again showing uniform mixing of all ingredients and no apparent porosity; FIG. 8 is a macro photograph of a feedstock; FIGS. 9-12 are photographs of a desktop 3D printer printing a sample, 3D model diagrams of a thin-walled cylinder, and a printed blank, showing good room temperature formability, high precision, complex and controllable shape, one-shot forming; fig. 13-14 are the stress-strain curves and fracture morphology of the finally obtained samples, the strength of which is up to 1.1GPa, and the strain amount of which is up to 30%, and the extremely excellent strength and plastic deformability are shown.
Example 5
Tantalum powder and nickel powder were mixed by a mixer in a mass ratio of 9:1 to obtain Ta-10 wt.% Ni mixed powder.
Mixing the mixed metal powder obtained in the step 1 with a binder in a mass ratio of 50: 50, preparing feed after uniformly mixing; the adhesive comprises the following raw materials in percentage by mass: 95 wt.% of semi-refined paraffin, 1 wt.% of high-density polyethylene, 1 wt.% of stearic acid and 3 wt.% of polyethylene vinyl acetate, wherein the sum of the mass percentages of the components is 100%.
And (3) loading the feed obtained in the step (2) into a desktop melt extrusion printer for 3D printing to obtain a blank body. The specific printing forming parameters are as follows: the substrate is made of glass, the temperature of the substrate is 5 ℃, the diameter of the nozzle is 0.001mm, and the temperature of the nozzle is 400 ℃.
And (3) carrying out two-step degreasing on the blank obtained in the step (3), namely firstly carrying out solution degreasing, and then carrying out thermal degreasing according to a specific degreasing scheme. The first degreasing process of the sample comprises the steps of heating the sample to 150 ℃ in a cyclohexane solution, and keeping the temperature for 1 hour; the second step of the thermal degreasing process of the sample is to execute the following thermal degreasing process scheme under the protection of argon atmosphere: the sample was heated from room temperature to 120 ℃ at a ramp rate of 4 ℃/min and stored at 120 ℃ for 30 min. Subsequently, the temperature was raised from 120 ℃ to 320 ℃ at a ramp rate of 10 ℃/min and maintained at that temperature for 30 min. Then heating from 320 ℃ to 430 ℃ at the heating rate of 5 ℃/min, preserving the heat for 30min, and then heating to 460 ℃ at the heating rate of 10 ℃/min. After the heat preservation is carried out for 1.5h, the temperature is raised to 550 ℃ at the speed of 10 ℃/min, and the heat preservation is carried out for 30min at the temperature. And finally, raising the temperature to 750 ℃ at the speed of 12 ℃/min, preserving the heat for 1h, and cooling to room temperature in a furnace cooling mode.
And (4) sintering the degreased blank obtained in the step (4) in a certain atmosphere to obtain a final sample. The sample is sintered in argon atmosphere at 1800 ℃ for 0.1 h.
Claims (6)
1. A low-temperature 3D printing forming method of refractory alloy is characterized by comprising the following steps:
step 1, homogeneous mixing of metal powder
Mixing two or more than two kinds of metal powder according to a certain proportion to obtain mixed metal powder;
step 2, preparation of feedstock
Uniformly mixing the mixed metal powder obtained in the step 1 with a binder with a specific formula according to a certain proportion to prepare a feed;
step 3, 3D printing and forming of the blank
Loading the feed obtained in the step 2 into a desktop melt extrusion printer for 3D printing to obtain a blank body;
step 4, two-step degreasing of the blank
Carrying out two-step degreasing on the blank obtained in the step 3, namely firstly carrying out solution degreasing and then carrying out thermal degreasing;
step 5, sintering
And (4) sintering the degreased blank obtained in the step (4) in a certain atmosphere to obtain a final sample.
2. The method for 3D printing and forming of refractory alloy according to claim 1, wherein in step 1, the mixed metal powder is composed of two or more of tungsten, molybdenum, niobium, tantalum, titanium, iron, cobalt, copper and nickel in any ratio, and the mixing method is obtained by mixing in a mixer or a ball mill.
3. The low-temperature 3D printing and forming method of the refractory alloy according to claim 1, wherein in the step 2, the adhesive is composed of the following raw materials in percentage by mass: 10-95 wt.% of semi-refined paraffin, 1-50 wt.% of high-density polyethylene, 1-50 wt.% of stearic acid and 1-50 wt.% of polyethylene vinyl acetate, wherein the sum of the mass percentages of the components is 100%; the mass ratio of the mixed powder to the adhesive is 1: 99-99.9: 0.1.
4. The low-temperature 3D printing forming method of the refractory alloy according to claim 1, wherein in the step 3, specific printing forming parameters are as follows: substrate material: glass, engineering plastic or metal stools; the temperature of the substrate is 5-300 ℃, the diameter of the nozzle is 0.001-10 mm, and the temperature of the nozzle is 5-400 ℃.
5. The low-temperature 3D printing and forming method of the refractory alloy according to claim 1, wherein in the step 4, the first degreasing process of the blank obtained in the step 3 is to heat the blank to 30-150 ℃ in a cyclohexane solution and keep the temperature for 1-60 h; the second step of the thermal degreasing process of the blank body is to execute the following thermal degreasing process scheme under the protection of nitrogen or argon inert gas atmosphere: heating the sample from room temperature to 120 ℃ at a heating rate of 4 ℃/min, and storing at 120 ℃ for 30 min; then, the temperature is increased from 120 ℃ to 260-360 ℃ at the heating rate of 1-20 ℃/min, and the temperature is kept for 30 min-2 h; heating from 260-360 ℃ to 400-440 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 30 min-2 h, heating to 450-500 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 30 min-2 h, heating to 510-590 ℃ at a rate of 1-20 ℃/min, and preserving heat for 30 min-2 h at the temperature; and finally, raising the temperature to 600-800 ℃ at the speed of 1-20 ℃/min, preserving the temperature for 30-2 h, and cooling to room temperature in a furnace cooling mode.
6. The low-temperature 3D printing and forming method of the refractory alloy according to claim 1, wherein in the step 5, the sintering of the degreased blank obtained in the step 4 is protected by nitrogen or argon inert atmosphere, or is performed under hydrogen reducing atmosphere, the sintering temperature is 850-1800 ℃, and the sintering time is 0.1-50 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114505491A (en) * | 2022-04-18 | 2022-05-17 | 天津大学 | Degreasing sintering method for manufacturing formed piece based on nano-particle additive |
| CN115584158A (en) * | 2022-10-21 | 2023-01-10 | 江南大学 | Photo-thermal synergistic curing-based metal ink and additive manufacturing method thereof |
| CN116275117A (en) * | 2023-03-30 | 2023-06-23 | 吉林大学 | Preparation method of porous artificial bone with adjustable pore structure and porous artificial bone |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1290652A (en) * | 2000-10-11 | 2001-04-11 | 苏占忠 | Method for producing silicon carbide |
| CN1669704A (en) * | 2005-04-22 | 2005-09-21 | 北京科技大学 | Process for preparing tungsten parts and components with complicated shape and high dimensional accuracy |
| CN103642253A (en) * | 2013-12-04 | 2014-03-19 | 湖南大学 | Wax-based binder for compacting process in powder metallurgy as well as preparation method and application thereof |
| CN103801695A (en) * | 2014-02-11 | 2014-05-21 | 北京科技大学 | 3D printing mould-free injection forming method through metal sizing agents |
| CN106216699A (en) * | 2016-09-29 | 2016-12-14 | 柳州增程材料科技有限公司 | A kind of 3D prints and uses metal dust preparation technology |
| CN106984819A (en) * | 2017-03-02 | 2017-07-28 | 东莞市依诺电子科技有限公司 | A kind of Ti6Al4V injection molding feedstocks 3D printing increasing material manufacturing method |
| WO2018066726A1 (en) * | 2016-10-06 | 2018-04-12 | 주식회사 쓰리디컨트롤즈 | Three-dimensional printing method using metal powder-containing composition as raw material |
| CN108889954A (en) * | 2018-06-29 | 2018-11-27 | 中国科学院兰州化学物理研究所 | A kind of preparation method of infusibility high-entropy alloy powder |
| CN111283184A (en) * | 2020-03-17 | 2020-06-16 | 丽水学院 | Titanium alloy extrusion type indirect 3D printing method |
| CN111360247A (en) * | 2020-03-18 | 2020-07-03 | 丽水学院 | Low-cost titanium-aluminum intermetallic compound indirect 3D printing method |
| CN211165354U (en) * | 2019-06-03 | 2020-08-04 | 安世亚太科技股份有限公司 | 3D printing substrate easy to peel off and 3D printing system |
| CN113102753A (en) * | 2020-01-13 | 2021-07-13 | 天津大学 | Indirect 3D printing tungsten-based alloy part degreasing sintering method |
-
2021
- 2021-08-10 CN CN202110927463.2A patent/CN113798507B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1290652A (en) * | 2000-10-11 | 2001-04-11 | 苏占忠 | Method for producing silicon carbide |
| CN1669704A (en) * | 2005-04-22 | 2005-09-21 | 北京科技大学 | Process for preparing tungsten parts and components with complicated shape and high dimensional accuracy |
| CN103642253A (en) * | 2013-12-04 | 2014-03-19 | 湖南大学 | Wax-based binder for compacting process in powder metallurgy as well as preparation method and application thereof |
| CN103801695A (en) * | 2014-02-11 | 2014-05-21 | 北京科技大学 | 3D printing mould-free injection forming method through metal sizing agents |
| CN106216699A (en) * | 2016-09-29 | 2016-12-14 | 柳州增程材料科技有限公司 | A kind of 3D prints and uses metal dust preparation technology |
| WO2018066726A1 (en) * | 2016-10-06 | 2018-04-12 | 주식회사 쓰리디컨트롤즈 | Three-dimensional printing method using metal powder-containing composition as raw material |
| CN106984819A (en) * | 2017-03-02 | 2017-07-28 | 东莞市依诺电子科技有限公司 | A kind of Ti6Al4V injection molding feedstocks 3D printing increasing material manufacturing method |
| CN108889954A (en) * | 2018-06-29 | 2018-11-27 | 中国科学院兰州化学物理研究所 | A kind of preparation method of infusibility high-entropy alloy powder |
| CN211165354U (en) * | 2019-06-03 | 2020-08-04 | 安世亚太科技股份有限公司 | 3D printing substrate easy to peel off and 3D printing system |
| CN113102753A (en) * | 2020-01-13 | 2021-07-13 | 天津大学 | Indirect 3D printing tungsten-based alloy part degreasing sintering method |
| CN111283184A (en) * | 2020-03-17 | 2020-06-16 | 丽水学院 | Titanium alloy extrusion type indirect 3D printing method |
| CN111360247A (en) * | 2020-03-18 | 2020-07-03 | 丽水学院 | Low-cost titanium-aluminum intermetallic compound indirect 3D printing method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114505491A (en) * | 2022-04-18 | 2022-05-17 | 天津大学 | Degreasing sintering method for manufacturing formed piece based on nano-particle additive |
| CN114505491B (en) * | 2022-04-18 | 2022-06-24 | 天津大学 | Degreasing sintering method for manufacturing formed piece based on nano-particle additive |
| CN115584158A (en) * | 2022-10-21 | 2023-01-10 | 江南大学 | Photo-thermal synergistic curing-based metal ink and additive manufacturing method thereof |
| CN116275117A (en) * | 2023-03-30 | 2023-06-23 | 吉林大学 | Preparation method of porous artificial bone with adjustable pore structure and porous artificial bone |
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|---|---|
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