CN113798507B - Low-temperature 3D printing forming method of refractory alloy - Google Patents
Low-temperature 3D printing forming method of refractory alloy Download PDFInfo
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- CN113798507B CN113798507B CN202110927463.2A CN202110927463A CN113798507B CN 113798507 B CN113798507 B CN 113798507B CN 202110927463 A CN202110927463 A CN 202110927463A CN 113798507 B CN113798507 B CN 113798507B
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- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000010146 3D printing Methods 0.000 title claims abstract description 44
- 229910000753 refractory alloy Inorganic materials 0.000 title claims abstract description 17
- 238000005238 degreasing Methods 0.000 claims abstract description 110
- 238000002156 mixing Methods 0.000 claims abstract description 46
- 238000005245 sintering Methods 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000000853 adhesive Substances 0.000 claims abstract description 35
- 230000001070 adhesive effect Effects 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 238000001125 extrusion Methods 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims description 76
- 239000000758 substrate Substances 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 17
- 239000011812 mixed powder Substances 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 16
- 238000007639 printing Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 12
- 235000021355 Stearic acid Nutrition 0.000 claims description 12
- 229920001903 high density polyethylene Polymers 0.000 claims description 12
- 239000004700 high-density polyethylene Substances 0.000 claims description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012188 paraffin wax Substances 0.000 claims description 12
- -1 polyethylene vinyl acetate Polymers 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000008117 stearic acid Substances 0.000 claims description 12
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 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
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000003870 refractory metal Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 15
- 238000011534 incubation Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 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
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011261 inert gas Substances 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
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 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
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 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
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding 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
- 238000000465 moulding Methods 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
- 239000011819 refractory material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
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 metal powders according to a certain proportion to obtain mixed metal powder; step 2, uniformly mixing the mixed metal powder obtained in the step 1 with an adhesive 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; step 4, degreasing the blank obtained in the step 3 in two steps, namely degreasing in solution at first, and then degreasing in heat; and 5, sintering the degreased blank obtained in the step 4 under a certain atmosphere to obtain a final sample. The method realizes the free forming of the refractory metal product by the die-free 3D printing, and the mechanical property of the part after the 3D printing forming is obviously improved.
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, electrical alloys for high voltage switches, electrical 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 the tungsten-copper alloy is currently faced with more severe use requirements. In addition, the current commercial refractory alloy is mostly prepared by adopting a powder metallurgy process, such as hot-pressing sintering, infiltration and the like after cold pressing into a blank by a die, and the commercial refractory alloy has the defects of low productivity, high price of a hot pressing furnace, requirement of the die, difficulty in mass production, high subsequent machining cost, long process and the like.
Disclosure of Invention
The invention aims to provide a low-temperature 3D printing forming method of refractory alloy, which realizes the free forming of the refractory metal product by the die-free 3D printing and leads the mechanical property of the part to be obviously improved after the 3D printing forming.
The technical scheme adopted by the invention is that the low-temperature 3D printing forming method of refractory alloy comprises the following steps:
step 1, uniformly mixing metal powder
Mixing two or more metal powders according to a certain proportion to obtain mixed metal powder;
step 2, preparation of feed
Uniformly mixing the mixed metal powder obtained in the step 1 with an adhesive 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;
step 4, two-step degreasing of the blank
Degreasing the blank obtained in the step 3 in two steps, namely degreasing in solution firstly, and then degreasing in heat;
step 5, sintering
And (3) sintering the degreased blank obtained in the step (4) under 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 mixing method is obtained by mixing by a mixer or a ball mill.
In the step 2, the adhesive consists of the following raw materials in percentage by mass: 10 to 95wt.% of semi-refined paraffin wax, 1 to 50wt.% of high density polyethylene, 1 to 50wt.% of stearic acid, 1 to 50wt.% of polyethylene vinyl acetate, the sum of the mass percentages of the above components being 100%; the mass ratio of the mixed powder to the adhesive is 1:99-99.9:0.1.
In step 3, specific printing forming parameters are as follows: the 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 cyclohexane solution and keep the green body for 1-60 h; the second step of thermal degreasing process of the blank 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 preserving at 120 ℃ for 30min; then, the temperature is increased from 120 ℃ to 260-360 ℃ at a heating rate of 1-20 ℃/min, and the temperature is kept for 30-2 h; heating from 260-360 ℃ to 400-440 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 30-2 h, heating to 450-500 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 30-2 h, heating to 510-590 ℃ at a heating rate of 1-20 ℃/min, and preserving heat for 30-2 h; finally, the temperature is raised to 600-800 ℃ at a speed of 1-20 ℃/min, and after heat preservation is carried out for 30-2 h, the temperature is cooled to the room temperature in a furnace cooling mode.
In the step 5, sintering of the degreased blank obtained in the step 4 is under the protection of nitrogen or argon inert atmosphere or under the hydrogen reducing atmosphere, wherein the sintering temperature is 850-1800 ℃ and the sintering time is 0.1-50 h.
The beneficial effects of the invention are as follows:
the low-temperature 3D printing forming method of the refractory alloy has the advantages that the die-free 3D printing free forming of the refractory metal product is realized, the adhesive is completely removed 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 spraying technology and the like, has the characteristics of high printing speed, high molding precision, wide printable material range, good product performance consistency, low cost, capability of preparing parts with complex shapes and the like, overcomes the defects that the existing commercial refractory alloy is prepared by performing hot-pressing sintering, infiltration and the like after cold pressing into blanks by using a die brought by a powder metallurgy process, has low productivity, high price of a hot pressing furnace, needs the die, is difficult to produce on a large scale, has high subsequent machining cost, has long flow and the like, and provides a brand-new solution idea and scheme for preparing refractory materials with complex structures.
Drawings
FIG. 1 is an SEM image of a commercially available aerosolized spherical copper powder obtained in example 4 of the present invention.
FIG. 2 is an SEM image of a commercially available ultrafine tungsten powder obtained in example 4 of the present invention.
FIG. 3 is an SEM image of W-30wt.% Cu powder after ball-milling of the powder blend obtained in example 4 of the invention.
FIG. 4 is a metallographic photograph of the adhesive obtained in example 4 of the present invention.
FIG. 5 is a graph showing the TG curve of the adhesive obtained in example 4 of the present invention;
FIG. 6 is a DTG trace of the adhesive according to example 4 of the present invention;
FIG. 7 is a metallographic photograph of the feed obtained in example 4 of the present invention.
FIG. 8 is a macroscopic photograph of the feed obtained in example 4 of the present invention.
FIG. 9 is a photograph of a desktop 3D printer of example 4 of the present invention;
FIG. 10 is a photograph II of a desktop 3D printer according to 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 green body printed in example 4 of the present invention;
FIG. 13 is a stress-strain curve of the prepared sample obtained in example 4 of the present invention;
FIG. 14 is a SEM image of the fracture morphology of a prepared sample obtained in example 4 of the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention provides a low-temperature 3D printing forming method of refractory alloy, which comprises the following steps:
step 1, uniformly mixing metal powder
Mixing two or more metal powders 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 mixing method is obtained by mixing by a mixer or a ball mill.
Step 2, preparation of feed
Uniformly mixing the mixed metal powder obtained in the step 1 with an adhesive with a specific formula according to a certain proportion to prepare a feed;
in the step 2, the adhesive consists of the following raw materials in percentage by mass: 10 to 95wt.% of semi-refined paraffin wax, 1 to 50wt.% of high density polyethylene, 1 to 50wt.% of stearic acid, 1 to 50wt.% of polyethylene vinyl acetate, the sum of the mass percentages of the above components being 100%; the mass ratio of the mixed powder to the adhesive is 1:99-99.9:0.1.
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;
in step 3, specific printing forming parameters are as follows: the substrate material: glass (or engineering plastic, metal bench) and base plate at 5-300 deg.C, nozzle diameter of 0.001-10 mm and nozzle temperature of 5-400 deg.C.
Step 4, two-step degreasing of the blank
Performing two-step degreasing on the blank obtained in the step 3, namely performing solution degreasing firstly, and performing thermal degreasing secondly, wherein the degreasing is performed 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 cyclohexane solution and keep the green body for 1-60 h; the second step of thermal degreasing process of the blank 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 preserving at 120 ℃ for 30min; then, the temperature is increased from 120 ℃ to 260-360 ℃ at a heating rate of 1-20 ℃/min, and the temperature is kept for 30-2 h; heating from 260-360 ℃ to 400-440 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 30-2 h, heating to 450-500 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 30-2 h, heating to 510-590 ℃ at a heating rate of 1-20 ℃/min, and preserving heat for 30-2 h; finally, the temperature is raised to 600-800 ℃ at a speed of 1-20 ℃/min, and after heat preservation is carried out for 30-2 h, the temperature is cooled to the room temperature in a furnace cooling mode.
Step 5, sintering
Sintering the degreased blank obtained in the step 4 under a certain atmosphere to obtain a final sample;
in the step 5, sintering of the degreased blank obtained in the step 4 is under the protection of nitrogen or argon inert atmosphere or under the hydrogen reducing atmosphere, wherein the sintering temperature is 850-1800 ℃ and the sintering time is 0.1-50 h.
Example 1
Step 1, uniformly mixing metal powder
The molybdenum powder and the iron powder were mixed at a mass ratio of 1:9 by a ball mill to obtain a Mo-90wt.% Fe mixed powder.
Step 2, preparation of feed
Mixing the mixed metal powder obtained in the step 1 with an adhesive according to the mass ratio of 80:20, evenly mixing and preparing a feed; the adhesive consists of the following raw materials in percentage by mass: 10wt.% of semi-refined paraffin wax, 50wt.% of high density polyethylene, 30wt.% of stearic acid, 10wt.% of polyethylene vinyl acetate, the sum of the mass percentages of the above components being 100%.
Step 3, 3D printing and forming of the blank
And (3) loading the feed obtained in the step (2) into a desktop melt extrusion printer for 3D printing to obtain a blank. The specific printing forming parameters are as follows: the substrate is made of aluminum plate, the temperature of the substrate is 300 ℃, the diameter of the nozzle is 10mm, and the temperature of the nozzle is 5 ℃.
Step 4, two-step degreasing of the blank
And (3) degreasing the blank obtained in the step (3) in two steps, namely, degreasing in solution firstly, and then degreasing in heat, wherein the degreasing is carried out according to a specific degreasing scheme. The first degreasing process of the sample is to heat the sample to 30 ℃ in cyclohexane solution and keep the sample for 60 hours; the second step of 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 heating rate of 4℃per minute and stored at 120℃for 30min. Subsequently, the temperature was increased from 120℃to 270℃at a heating rate of 1℃per minute, and was maintained at that temperature for 2 hours. Then heating from 270 ℃ to 440 ℃ at a heating rate of 20 ℃/min, preserving heat for 30min, and heating to 450 ℃ at a heating rate of 1 ℃/min. After 30min incubation, the temperature was raised to 510℃at a rate of 1℃per min, and the incubation was carried out at this temperature for 1h. Finally, the temperature is raised to 800 ℃ at a speed of 20 ℃/min, and after heat preservation for 50min, the temperature is cooled to room temperature in a mode of cooling along with the furnace.
Step 5, sintering
And (3) sintering the degreased blank obtained in the step (4) under a certain atmosphere to obtain a final sample. The sample was sintered at 850℃under nitrogen atmosphere for 50 hours.
Example 2
Step 1, uniformly mixing metal powder
The niobium powder and the titanium powder were mixed at a mass ratio of 5:5 by a ball mill to obtain Nb-50wt.% Ti mixed powder.
Step 2, preparation of feed
Mixing the mixed metal powder obtained in the step 1 with an adhesive according to the mass ratio of 99.9:0.1% of the materials are evenly mixed to prepare a feed; the adhesive consists of the following raw materials in percentage by mass: 48wt.% of semi-refined paraffin wax, 1wt.% of high density polyethylene, 50wt.% of stearic acid, 1wt.% of polyethylene vinyl acetate, the sum of the mass percentages of the above components being 100%.
Step 3, 3D printing and forming of the blank
And (3) loading the feed obtained in the step (2) into a desktop melt extrusion printer for 3D printing to obtain a blank. 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 ℃.
Step 4, two-step degreasing of the blank
And (3) degreasing the blank obtained in the step (3) in two steps, namely, degreasing in solution firstly, and then degreasing in heat, wherein the degreasing is carried out according to a specific degreasing scheme. The first degreasing process of the sample is to heat the sample to 100 ℃ in cyclohexane solution and keep the sample for 5 hours; the second step of 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 heating rate of 4℃per minute and stored at 120℃for 30min. Subsequently, the temperature was increased from 120℃to 360℃at a heating rate of 20℃per minute, and maintained at that temperature for 1 hour. Then heating from 360 ℃ to 410 ℃ at a heating rate of 1 ℃/min, preserving heat for 2 hours, and heating to 500 ℃ at a heating rate of 20 ℃/min. After 2h incubation, the temperature was raised to 590℃at a rate of 20℃per minute, and the incubation was carried out at this temperature for 2h. Finally, the temperature is raised to 650 ℃ at a speed of 1 ℃/min, and after 2 hours of heat preservation, the temperature is cooled to room temperature in a mode of cooling along with the furnace.
Step 5, sintering
And (3) sintering the degreased blank obtained in the step (4) under a certain atmosphere to obtain a final sample. The sintering temperature of the sample is 1000 ℃ and the sintering time is 10 hours under the hydrogen atmosphere.
Example 3
Step 1, uniformly mixing metal powder
Tungsten powder and cobalt powder were mixed by a ball mill at a mass ratio of 9:1 to obtain a W-70wt.% Co mixed powder.
Step 2, preparation of feed
Mixing the mixed metal powder obtained in the step 1 with an adhesive according to the mass ratio of 1%: preparing a feed after 99% uniform mixing; the adhesive consists of the following raw materials in percentage by mass: 30wt.% of semi-refined paraffin wax, 10wt.% of high density polyethylene, 10wt.% of stearic acid, 50wt.% of polyethylene vinyl acetate, the sum of the mass percentages of the above components being 100%.
Step 3, 3D printing and forming of the blank
And (3) loading the feed obtained in the step (2) into a desktop melt extrusion printer for 3D printing to obtain a blank. The specific printing forming parameters are as follows: the substrate is made of titanium alloy plate, the temperature of the substrate is 150 ℃, the diameter of the nozzle is 0.1mm, and the temperature of the nozzle is 300 ℃.
Step 4, two-step degreasing of the blank
And (3) degreasing the blank obtained in the step (3) in two steps, namely, degreasing in solution firstly, and then degreasing in heat, wherein the degreasing is carried out according to a specific degreasing scheme. The first degreasing process of the sample is to heat the sample to 120 ℃ in cyclohexane solution and keep the sample for 30 hours; the second step of 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 heating rate of 4℃per minute and stored at 120℃for 30min. Subsequently, the temperature was raised from 120℃to 300℃at a heating rate of 5℃per minute, and was maintained at that temperature for 30 minutes. Heating from 300 ℃ to 420 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and heating to 480 ℃ at a heating rate of 5 ℃/min. After 1h incubation, the temperature was raised to 520℃at a rate of 5℃per minute, and the incubation was carried out at this temperature for 1h. Finally, the temperature is raised to 700 ℃ at a speed of 8 ℃/min, and after heat preservation for 40min, the temperature is cooled to room temperature in a mode of cooling along with the furnace.
Step 5, sintering
And (3) sintering the degreased blank obtained in the step (4) under a certain atmosphere to obtain a final sample. The sample was sintered under argon atmosphere at 1400℃for 25h.
Example 4
Step 1, uniformly mixing metal powder
Tungsten powder and copper powder were mixed in a mass ratio of 7:3 by a ball mill to obtain a W-30wt.% Cu mixed powder.
Step 2, preparation of feed
Mixing the mixed metal powder obtained in the step 1 with an adhesive according to the mass ratio of 97%:3% of the materials are evenly mixed to prepare a feed; the adhesive consists of the following raw materials in percentage by mass: 65wt.% of semi-refined paraffin wax, 5wt.% of high density polyethylene, 25wt.% of stearic acid, 5wt.% of polyethylene vinyl acetate, the sum of the above components being 100% by mass.
Step 3, 3D printing and forming of the blank
And (3) loading the feed obtained in the step (2) into a desktop melt extrusion printer for 3D printing to obtain a blank. The specific printing forming parameters are as follows: the substrate is polyimide, the temperature of the substrate is 90 ℃, the diameter of the nozzle is 0.95mm, and the temperature of the nozzle is 150 ℃.
Step 4, two-step degreasing of the blank
And (3) degreasing the blank obtained in the step (3) in two steps, namely, degreasing in solution firstly, and then degreasing in heat, wherein the degreasing is carried out according to a specific degreasing scheme. The first degreasing process of the sample is to heat the sample to 50 ℃ in cyclohexane solution and keep the sample for 20 hours; the second step of 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 heating rate of 4℃per minute and stored at 120℃for 30min. Subsequently, the temperature was raised from 120℃to 260℃at a heating rate of 3℃per minute, and was maintained at 260℃for 30 minutes. Then heating from 260 ℃ to 400 ℃ at a heating rate of 2 ℃/min, preserving heat for 60min, and heating to 450 ℃ at a heating rate of 2 ℃/min. After 30min incubation, the temperature was raised to 550℃at a rate of 2℃per min, and incubated at 550℃for 30min. Finally, the temperature was raised to 600℃at a rate of 4℃per minute, and after 30 minutes of incubation, the adhesive was cooled to room temperature with furnace cooling, and the TG and DTG curves of the adhesive were as shown in FIGS. 5-6.
Step 5, sintering
And (3) sintering the degreased blank obtained in the step (4) under a certain atmosphere to obtain a final sample. The sintering temperature of the sample is 1350 ℃ and the sintering time is 2 hours under the hydrogen atmosphere.
The SEM of the copper powder and tungsten powder used as the raw materials of the metal powder in example 4 is shown in fig. 1 and 2, wherein the copper powder is micron-sized spherical powder, and the tungsten powder is nano-sized powder and has serious agglomeration; SEM of the mixed powder obtained by mechanical ball milling and powder mixing is shown in figure 3, and it can be seen that the easily agglomerated nanoscale tungsten powder is uniformly dispersed on the surface of copper powder, and the copper powder is deformed to a certain extent; FIG. 4 is a metallographic photograph of the adhesive, and it can be seen that the components are uniformly mixed; FIG. 7 is a metallographic photograph of the feed obtained after the binder and mixed metal powder are uniformly mixed, as can be seen with all the ingredients uniformly mixed without significant voids; FIG. 8 is a macroscopic photograph of a feed; 9-12 are photographs of a desktop 3D printer when a sample is printed, a 3D model diagram of a thin-wall cylinder and a printed blank, and the printed blank has good room temperature formability, high precision and complex shape and can be formed in one step; fig. 13-14 are stress-strain curves and fracture morphology of the final obtained samples, with strength up to 1.1GPa and strain capacity up to 30%, showing very excellent strength and plastic deformability.
Example 5
Step 1, uniformly mixing metal powder
Tantalum powder and nickel powder were mixed by a mixer at a mass ratio of 9:1 to obtain Ta-10wt.% Ni mixed powder.
Step 2, preparation of feed
Mixing the mixed metal powder obtained in the step 1 with an adhesive in a mass ratio of 50:50, evenly mixing and preparing a feed; the adhesive consists of the following raw materials in percentage by mass: 95wt.% of semi-refined paraffin wax, 1wt.% of high density polyethylene, 1wt.% of stearic acid, 3wt.% of polyethylene vinyl acetate, the sum of the above components being 100% by mass.
Step 3, 3D printing and forming of the blank
And (3) loading the feed obtained in the step (2) into a desktop melt extrusion printer for 3D printing to obtain a blank. 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 ℃.
Step 4, two-step degreasing of the blank
And (3) degreasing the blank obtained in the step (3) in two steps, namely, degreasing in solution firstly, and then degreasing in heat, wherein the degreasing is carried out according to a specific degreasing scheme. The first degreasing process of the sample is to heat the sample to 150 ℃ in cyclohexane solution and keep the sample for 1h; the second step of 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 heating rate of 4℃per minute and stored at 120℃for 30min. Subsequently, the temperature was raised from 120℃to 320℃at a heating rate of 10℃per minute, and was maintained at that temperature for 30 minutes. Then heating from 320 ℃ to 430 ℃ at a heating rate of 5 ℃/min, preserving heat for 30min, and heating to 460 ℃ at a heating rate of 10 ℃/min. After 1.5h incubation, the temperature was raised to 550℃at a rate of 10℃per minute, and the incubation was carried out at this temperature for 30min. Finally, the temperature is raised to 750 ℃ at a speed of 12 ℃/min, and after heat preservation for 1h, the temperature is cooled to room temperature in a mode of cooling along with the furnace.
Step 5, sintering
And (3) sintering the degreased blank obtained in the step (4) under a certain atmosphere to obtain a final sample. The sample was sintered under argon atmosphere at 1800 c for 0.1h.
Claims (5)
1. A low-temperature 3D printing forming method of refractory alloy is characterized in that,
step 1, uniformly mixing metal powder
Mixing molybdenum powder and iron powder in a mass ratio of 1:9 by a ball mill to obtain Mo-90wt.% Fe mixed powder;
step 2, preparation of feed
Mixing the mixed powder obtained in the step 1 with an adhesive according to a mass ratio of 80:20, evenly mixing and preparing a feed; the adhesive consists of the following raw materials in percentage by mass: 10wt.% of semi-refined paraffin wax, 50wt.% of high density polyethylene, 30wt.% of stearic acid, 10wt.% of polyethylene vinyl acetate, the sum of the mass percentages of the above components being 100%;
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; the specific printing forming parameters are as follows: the substrate material is aluminum plate, and the substrate temperature is 300 o C, nozzle diameter 10mm, nozzle temperature 5 o C；
Step 4, two-step degreasing of the blank
And (3) degreasing the blank obtained in the step (3) in two steps, namely, degreasing in solution firstly, and then degreasing in heat, wherein the degreasing steps are carried out according to a specific degreasing scheme: the first degreasing process of the blank body is to heat the blank body to 30 ℃ in cyclohexane solution o C, and hold 60h; the second step of thermal degreasing process of the blank is to execute the following thermal degreasing process scheme under the protection of nitrogen atmosphere: at 4 o Heating the blank from room temperature to 120 at a heating rate of C/min o C, and at 120 o C, preserving for 30min; subsequently, the temperature was set at 1 o The temperature rise rate of C/min is increased from 120 ℃ to 270 DEG C o C, and maintaining at the temperature for 2 hours;and then use 20 o The heating rate of C/min is from 270 o C heating to 440 o C, preserving heat for 30min, and then adding 1 o Heating to 450 deg.C/min o C, performing operation; after 30min of heat preservation, 1 o Heating to 510 at a rate of C/min o C, preserving heat for 1h at the temperature; finally, the temperature is 20 o The C/min speed rises to 800 o C, after heat preservation for 50min, cooling to room temperature in a furnace cooling mode;
step 5, sintering
Sintering the degreased blank obtained in the step 4 in nitrogen atmosphere at a sintering temperature of 850 DEG C o And C, sintering time is 50h, and a final sample is obtained.
2. A low-temperature 3D printing forming method of refractory alloy is characterized in that,
step 1, uniformly mixing metal powder
Mixing niobium powder and titanium powder in a mass ratio of 5:5 by a ball mill to obtain Nb-50wt.% Ti mixed powder;
step 2, preparation of feed
Mixing the mixed powder obtained in the step 1 with an adhesive according to the mass ratio of 99.9:0.1, evenly mixing and preparing a feed; the adhesive consists of the following raw materials in percentage by mass: 48wt.% of semi-refined paraffin wax, 1wt wt.% of high-density polyethylene, 50wt.% of stearic acid, 1wt.% of polyethylene vinyl acetate, the sum of the mass percentages of the above components being 100%;
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; the specific printing forming parameters are as follows: the substrate is made of stainless steel, and the substrate temperature is 200 DEG C o C, nozzle diameter 3mm, nozzle temperature 200 o C；
Step 4, two-step degreasing of the blank
And (3) degreasing the blank obtained in the step (3) in two steps, namely, degreasing in solution firstly, and then degreasing in heat, wherein the degreasing steps are carried out according to a specific degreasing scheme: the first degreasing process of the blank body is to heat the blank body to 100 in cyclohexane solution o C, and protectHold 5h; the second step of thermal degreasing process of the blank is to execute the following thermal degreasing process scheme under the protection of argon atmosphere: at 4 o Heating the blank from room temperature to 120 at a heating rate of C/min o C, and at 120 o C, preserving for 30min; subsequently, the temperature is 20 o The temperature rise rate of C/min is increased from 120 ℃ to 360 DEG o C, and maintaining at the temperature for 1h; then 1 is used o The heating rate of C/min is 360 o C heating to 410 o C, preserving heat for 2 hours, and then adding 20 o Heating to 500 deg.C/min o C, performing operation; after 2h of heat preservation, the mixture is treated by 20 o The C/min rate is raised to 590 o C, preserving heat for 2 hours at the temperature; finally, the temperature is 1 o The C/min speed rises to 650 o C, after heat preservation for 2 hours, cooling to room temperature in a furnace cooling mode;
step 5, sintering
Sintering the degreased blank obtained in the step 4 in hydrogen atmosphere at a sintering temperature of 1000 DEG C o And C, sintering time is 10h, and a final sample is obtained.
3. A low-temperature 3D printing forming method of refractory alloy is characterized in that,
step 1, uniformly mixing metal powder
Mixing tungsten powder and cobalt powder in a mass ratio of 9:1 by a ball mill to obtain W-10wt.% Co mixed powder;
step 2, preparation of feed
Mixing the mixed powder obtained in the step 1 with an adhesive according to a mass ratio of 1:99, evenly mixing and preparing a feed; the adhesive consists of the following raw materials in percentage by mass: 30wt.% of semi-refined paraffin wax, 10wt.% of high density polyethylene, 10wt.% of stearic acid, 50wt.% of polyethylene vinyl acetate, the sum of the mass percentages of the above components being 100%;
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; the specific printing forming parameters are as follows: the substrate is made of titanium alloy plate with a substrate temperature of 150 DEG C o C, nozzle diameter 0.1mm, nozzle temperature 300 o C；
Step 4, two-step degreasing of the blank
And (3) degreasing the blank obtained in the step (3) in two steps, namely, degreasing in solution firstly, and then degreasing in heat, wherein the degreasing steps are carried out according to a specific degreasing scheme: the first degreasing process of the blank body is to heat the blank body to 120 ℃ in cyclohexane solution o C, and hold 30h; the second step of thermal degreasing process of the blank is to execute the following thermal degreasing process scheme under the protection of argon atmosphere: at 4 o Heating the blank from room temperature to 120 at a heating rate of C/min o C, and at 120 o C, preserving for 30min; subsequently, the temperature was set at 5 o The temperature rise rate of C/min is increased from 120 ℃ to 300 o C, maintaining at the temperature for 30min; and then 10 o The heating rate of C/min is from 300 o C heating to 420 o C, preserving heat for 1h, then adding 5 o Heating to 480 deg.C/min o C, performing operation; after 1h of heat preservation, the temperature is kept at 5 o Heating to 520 at a rate of C/min o C, preserving heat for 1h at the temperature; finally, the temperature is 8 o The C/min speed rises to 700 o C, after heat preservation for 40min, cooling to room temperature in a furnace cooling mode;
step 5, sintering
Sintering the degreased blank obtained in the step 4 in an argon atmosphere at a sintering temperature of 1400 DEG C o And C, sintering time is 25h, and a final sample is obtained.
4. A low-temperature 3D printing forming method of refractory alloy is characterized in that,
step 1, uniformly mixing metal powder
Mixing tungsten powder and copper powder in a mass ratio of 7:3 by a ball mill to obtain W-30wt.% Cu mixed powder;
step 2, preparation of feed
Mixing the mixed powder obtained in the step 1 with an adhesive according to a mass ratio of 97: 3. evenly mixing and preparing a feed; the adhesive consists of the following raw materials in percentage by mass: 65wt.% of semi-refined paraffin wax, 5wt wt.% of high density polyethylene, 25wt wt.% of stearic acid, 5wt.% of polyethylene vinyl acetate, the sum of the mass percentages of the above components being 100%;
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; the specific printing forming parameters are as follows: the substrate material is polyimide, the substrate temperature is 90 DEG o C, nozzle diameter 0.95. 0.95mm, nozzle temperature 150 o C；
Step 4, two-step degreasing of the blank
And (3) degreasing the blank obtained in the step (3) in two steps, namely, degreasing in solution firstly, and then degreasing in heat, wherein the degreasing steps are carried out according to a specific degreasing scheme: the first degreasing process of the blank body is to heat the blank body to 50 ℃ in cyclohexane solution o C, and hold 20h; the second step of thermal degreasing process of the blank is to execute the following thermal degreasing process scheme under the protection of nitrogen atmosphere: heating the blank from room temperature to 120 ℃ at a heating rate of 4 ℃/min, and at 120 DEG C o C, preserving for 30min; subsequently, the temperature was 3 o The temperature rise rate of C/min is increased from 120 ℃ to 260 ℃ and at 260 DEG C o C, keeping for 30min; then use 2 o Heating from 260 ℃ to 400 at the heating rate of C/min o C, preserving heat for 60min, and then adding 2 o Heating to 450 deg.C/min o C, performing operation; after 30min of heat preservation, the temperature is increased by 2 o The C/min rate is raised to 550 o C, preserving heat for 30min at 550 ℃; finally, the temperature is 4 o The C/min speed rises to 600 o C, after heat preservation for 30min, cooling to room temperature in a furnace cooling mode;
step 5, sintering
Sintering the degreased blank obtained in the step 4 in hydrogen atmosphere at 1350 DEG C o And C, sintering time is 2h, and a final sample is obtained.
5. A low-temperature 3D printing forming method of refractory alloy is characterized in that,
step 1, uniformly mixing metal powder
Mixing tantalum powder and nickel powder in a mass ratio of 9:1 by a mixer to obtain Ta-10wt.% Ni mixed powder;
step 2, preparation of feed
Mixing powder obtained in the step 1 and adhesive in a mass ratio of 50:50, evenly mixing and preparing a feed; the adhesive consists of the following raw materials in percentage by mass: 95wt.% of semi-refined paraffin wax, 1wt wt.% of high-density polyethylene, 1wt.% of stearic acid, 3wt.% of polyethylene vinyl acetate, the sum of the mass percentages of the above components being 100%;
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; the specific printing forming parameters are as follows: the substrate material is glass, the substrate temperature is 5 o C, nozzle diameter 0.001mm, nozzle temperature 400 o C；
Step 4, two-step degreasing of the blank
And (3) degreasing the blank obtained in the step (3) in two steps, namely, degreasing in solution firstly, and then degreasing in heat, wherein the degreasing steps are carried out according to a specific degreasing scheme: the first degreasing process of the blank body is to heat the blank body to 150 ℃ in cyclohexane solution o C and hold 1h; the second step of thermal degreasing process of the blank is to execute the following thermal degreasing process scheme under the protection of argon atmosphere: at 4 o Heating the blank from room temperature to 120 at a heating rate of C/min o C, and at 120 o C, preserving for 30min; subsequently, the temperature was 10 o The temperature rise rate of C/min is increased from 120 ℃ to 320 o C, maintaining at the temperature for 30min; then by 5 o The heating rate of C/min is from 320 o C heating to 430 o C, preserving heat for 30min, and then adding 10 o Heating at a heating rate of C/min to 460 o C, performing operation; after 1.5h of heat preservation, 10 percent o The C/min rate is raised to 550 o C, preserving the temperature for 30min; finally, the temperature is 12 o The C/min speed rises to 750 o C, after heat preservation for 1h, cooling to room temperature in a furnace cooling mode;
step 5, sintering
Sintering the degreased blank obtained in the step 4 in argon atmosphere at a sintering temperature of 1800 DEG C o C, sintering time is 0.1h, and a final sample is obtained.
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| 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 |
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