CN116532658A - Metal three-dimensional structural member and method for regulating and controlling carbon content by photocuring additive manufacturing - Google Patents
Metal three-dimensional structural member and method for regulating and controlling carbon content by photocuring additive manufacturing Download PDFInfo
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- CN116532658A CN116532658A CN202310831112.0A CN202310831112A CN116532658A CN 116532658 A CN116532658 A CN 116532658A CN 202310831112 A CN202310831112 A CN 202310831112A CN 116532658 A CN116532658 A CN 116532658A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 94
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 84
- 239000002184 metal Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000000654 additive Substances 0.000 title claims abstract description 26
- 230000000996 additive effect Effects 0.000 title claims abstract description 26
- 230000001276 controlling effect Effects 0.000 title claims abstract description 12
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 59
- 239000000843 powder Substances 0.000 claims abstract description 55
- 238000007599 discharging Methods 0.000 claims abstract description 42
- 239000003292 glue Substances 0.000 claims abstract description 42
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims description 42
- 238000010146 3D printing Methods 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 12
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 9
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 8
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 8
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 7
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910021386 carbon form Inorganic materials 0.000 abstract description 3
- 230000003014 reinforcing effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 25
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 13
- 229910001021 Ferroalloy Inorganic materials 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- 229910000881 Cu alloy Inorganic materials 0.000 description 10
- 229910000604 Ferrochrome Inorganic materials 0.000 description 10
- 229910000990 Ni alloy Inorganic materials 0.000 description 10
- 229910000838 Al alloy Inorganic materials 0.000 description 9
- 229910001182 Mo alloy Inorganic materials 0.000 description 9
- 229910001080 W alloy Inorganic materials 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910000861 Mg alloy Inorganic materials 0.000 description 8
- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 description 8
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 8
- 229910000640 Fe alloy Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
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
- B22F10/12—Formation of a green body by photopolymerisation, e.g. stereolithography [SLA] or digital light processing [DLP]
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
-
- 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
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
-
- 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
- B22F3/1039—Sintering only by reaction
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a metal three-dimensional structural member and a method for regulating and controlling carbon content in photocuring additive manufacturing thereof, and relates to the technical field of additive manufacturing. The method comprises the steps of mixing photosensitive resin with corresponding carbide forming element metal powder, a photoinitiator and a dispersing agent to prepare slurry, and manufacturing a molded blank by photocuring additive; and then the green body is subjected to glue discharging, the organic photosensitive resin is decomposed, discharged and remains in the green body in a carbon form, and further sintered to obtain a compact metal three-dimensional structural member. According to the invention, carbide is added to form elemental metal powder and the residual carbon after thermal decomposition of the photosensitive resin is combined into metal carbide, so that free carbon in the metal part is completely removed, and the carbide exists in a second phase form to play a reinforcing role.
Description
Technical Field
The invention relates to the technical field of additive manufacturing, in particular to a metal three-dimensional structural member and a method for regulating and controlling carbon content in photocuring additive manufacturing of the metal three-dimensional structural member.
Background
Additive Manufacturing (AM), also known as 3D printing, is a rapid manufacturing technology developed at the end of the 80 s of the 20 th century. The basic principle of the technology is that raw materials are piled into target solid parts in a layer-by-layer lamination mode according to a designed 3D digital model. The additive manufacturing technique has unique advantages over traditional subtractive (e.g., machining, etc.), isogenic (e.g., die forging, etc.) manufacturing methods: (1) Alloy parts with extremely high complexity can be prepared, and the requirements of the modern high-end field on parts with complex structures are better met; (2) The material is wide in application range, and parts with any alloy composition can be prepared; (3) Improving the processability of difficult-to-process materials and expanding the engineering application field; (4) the preparation process is simplified, and the production efficiency is high; (5) The material utilization rate is high, the energy consumption is low, the pollutant emission is low, and the environment-friendly sustainable development concept is met.
The principle of the photo-curing additive manufacturing technology is that under the control of digital signals, ultraviolet light is utilized to selectively cure photosensitive resin, and the resin is piled layer by layer after curing until a complete three-dimensional structural part is formed. The photocuring 3D printing technology has the advantages of high speed, low energy consumption, high precision and the like, and can be used for preparing parts with complex structures which are difficult to obtain by the conventional additive manufacturing technology.
The metal parts are prepared by adopting a photocuring additive manufacturing technology, and organic photosensitive resin and the like can be completely removed in the glue discharging process in theory. However, the inventors have found during the course of experiments that organics are not practically totally excluded and often remain in free carbon form within the metal parts. It is found from scanning electron microscope observation that free carbon or solid solution carbon irregularly distributed in the metal matrix at the fracture position makes sintering necks among metal powder particles difficult to form in the sintering process, and the inter-crystal combination is not precise, so that the density of the metal part is reduced, and the strength of the metal part is further reduced. Meanwhile, other properties of the metal parts, such as corrosion resistance of corrosion resistant alloy stainless steel, electrical conductivity and thermal conductivity of the electrical and thermal conductive copper alloy, and the like, are seriously reduced by the increase of the carbon content.
Disclosure of Invention
The invention provides a metal three-dimensional structural member and a method for regulating and controlling carbon content in photo-curing additive manufacturing of the metal three-dimensional structural member, and aims to solve the problems in the prior art.
In order to achieve the above object, the embodiments of the present invention provide a method for controlling carbon content in a metal three-dimensional structural member and a photocuring additive manufacturing method thereof, which controls carbon content in a metal photocuring additive manufactured part by optimizing photosensitive resin, degreasing process, and adding carbide forming element metal powder. In particular, the photosensitive resin is optimized according to the carbon residue amount after the thermal decomposition of the photosensitive resin.
A method for regulating and controlling carbon content in photo-curing additive manufacturing of a metal three-dimensional structural member comprises the following steps:
s1: placing photosensitive resin into a mixer, sequentially adding a dispersing agent, a photoinitiator and carbide to form elemental metal powder, and performing ball milling and mixing to obtain slurry;
wherein the addition amount of the photosensitive resin is 23-58 vol%, the addition amount of the dispersing agent is 5-10 vol%, the addition amount of the photoinitiator is 0.01-2 vol%, and the addition amount of the carbide forming element metal powder is 0.1-70 vol%;
s2: filling the slurry into a photocuring 3D printer, and performing 3D printing to obtain a blank;
s3: discharging glue from the blank body, and sintering to obtain a metal three-dimensional structural member;
wherein the chemical formula of the photosensitive resin is C x H y O z ，1<x<20，2<y<30，1<z<15, the residual carbon content of the photosensitive resin after thermal decomposition is 0.001-10 wt percent.
Preferably, the photosensitive resin is any one of trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, lauryl methacrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, glycidyl methacrylate, hydroxyethyl methacrylate, and hydroxyethyl acrylate.
Preferably, the carbide-forming elemental metal powder is at least one of a Fe, ti, cr, V, W, mo, ta pure elemental metal, or an alloy thereof.
Preferably, the glue discharging condition is as follows: the glue discharging atmosphere is vacuum, nitrogen or hydrogen, the temperature is raised to 300-350 ℃ at 0.1-10 ℃/min, the temperature is kept for 0.1-10 h, and the temperature is raised to 550-600 ℃ at 0.01-5 ℃/min, and the temperature is kept for 0.1-10 h.
Preferably, the sintering conditions are: the sintering atmosphere is vacuum, nitrogen or hydrogen, and the temperature is raised to 500-2500 ℃ at 0.1-20 ℃/min, and the temperature is kept for 0.1-10 h. Wherein the sintering temperature depends on the target alloy.
Preferably, the dispersant is SP-710, KOS110 or KH560, and the photoinitiator is phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide or 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide.
Preferably, the ball milling speed is 100-400 rpm.
Based on one general inventive concept, the embodiment of the invention also provides the metal three-dimensional structural member obtained by the method.
Preferably, the three-dimensional metal structural member is composed of a metal grain-metal grain, metal grain-carbide structure.
Preferably, the carbon content in the metal three-dimensional structural member is 0.01-10 wt%.
Preferably the photosensitive resin has a residual carbon content from high to low after thermal decomposition in the order: trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, lauryl methacrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, glycidyl methacrylate, hydroxyethyl methacrylate and hydroxyethyl acrylate.
Preferably, the carbide-forming elemental metal powder is any one of Fe, ti, cr, V, W, mo, ta and alloys thereof, including but not limited to.
The carbide forming element metal powder selected by the invention is Fe, ti, cr, V, W, mo, ta metal and alloy thereof, and according to the carbon content of the target alloy (according to the industry conventional tool manual alloyBrand-name) and the amount of carbon residue after thermal decomposition of the photosensitive resin (depending on the carbon content after thermal decomposition of the pure photosensitive resin), the corresponding photosensitive resin is selected. Wherein the photosensitive resin is C x H y O z ，1<x<20，2<y<30，1<z<15, the residual carbon amount after thermal decomposition is 0.001-wt% to 10-wt%. The preferred photosensitive resin has a residual carbon content from high to low after thermal decomposition of: trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, lauryl methacrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, glycidyl methacrylate, hydroxyethyl methacrylate and hydroxyethyl acrylate.
Reaction mechanism:
the invention mixes photosensitive resin and carbide forming element metal powder which just forms carbide with corresponding residual carbon after thermal decomposition, photoinitiator and dispersing agent to prepare slurry, and adopts photo-curing additive to manufacture a formed blank. And then the green body is subjected to glue discharging, and the organic photosensitive resin is decomposed, discharged and remains in the green body in a carbon form. And in the high-temperature sintering stage, residual carbon generated in the glue discharging process and carbide forming element metal powder undergo carbonization reaction to obtain carbide. It should be noted that at room temperature of the slurry prepared by mixing and at low temperature of the green body discharging, there is no residual carbon in the green body or residual carbon is being formed and the temperature is low, so that carbide forming elemental metal powder does not substantially react to form carbide.
That is, free carbon in the metal part is completely removed by adding carbide-forming element metal powder to bond with the photosensitive resin thermal decomposition residual carbon into carbide. At the same time, the carbide exists in the form of a second phase, which plays a role in strengthening. The method comprises the following steps: when the prepared target alloy has low carbon content requirement and even contains no carbon, selecting photosensitive resin with less thermal decomposition residual carbon, adding carbide forming element metal powder capable of reacting with the thermal decomposition residual carbon to enable the carbide forming element metal powder to generate carbonization reaction in a high-temperature sintering stage after glue discharging, alloying the residual carbon, and further removing free carbon in the target alloy; when the carbon content of the prepared target alloy is allowed to be higher, a photosensitive resin with higher residual carbon content is selected, and carbide forming element metal powder can be added to carry out carbonization reaction with residual carbon in a glue discharging stage in a high-temperature sintering stage to form carbide, so that on one hand, the free carbon content in the target alloy is controlled, and on the other hand, the carbide serves as a reinforcing phase to play a second-phase reinforcing role, and the strength of the target alloy is increased.
The scheme of the invention has the following beneficial effects:
the invention can effectively regulate and control the carbon content of metal photocuring additive manufacturing, and solves the problem that the carbon content of the traditional metal photocuring additive manufacturing is uncontrolled so as to influence the performance, and has the following specific advantages:
1. the preparation method can effectively regulate and control the carbon content of the metal manufactured by photocuring additive, completely eliminate the existence of free carbon in the metal matrix, ensure that the microscopic distribution of the metal matrix only has two arrangements of metal grains-metal grains and metal grains-carbide, and improve the strength and corrosion resistance of the metal part.
2. The preparation method is simple and quick, and has few working procedures. The aim of effectively regulating and controlling the carbon content of the metal photocuring additive manufacturing can be achieved by optimizing photosensitive resin and adding carbide forming element metal powder.
3. The preparation method of the invention has lower cost, preferably the photosensitive resin and the carbide-added element metal powder are not added in essence, the production process is not increased, and the raw material purchasing cost used in the improvement process is lower, thus the preparation method can be better applied to actual industrial production.
4. The preparation method provided by the invention has a wide application range, and can be applied to metal photocuring additive manufacturing of iron alloy, copper alloy, aluminum alloy, tungsten alloy, nickel alloy and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a method for regulating and controlling carbon content in photo-curing additive manufacturing of a metal three-dimensional structural member according to an embodiment of the invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Aiming at the existing problems, the invention provides a method for regulating and controlling the carbon content in a metal three-dimensional structural member and a photocuring additive manufacturing method thereof.
As shown in fig. 1, an embodiment of the present invention provides a schematic flow chart of a method for regulating and controlling carbon content in photo-curing additive manufacturing of a metal three-dimensional structural member.
Example 1
Preparation of iron alloy (316) parts by preference of photosensitive resin with low residual carbon content and addition of carbide-forming elemental metal powder vanadium
The photosensitive resin of hydroxyethyl methacrylate and isobornyl acrylate, a dispersing agent KOS110, a photoinitiator 819, pure vanadium powder and ferroalloy 316 powder (D 50 =10μm, carbon content below 0.06%) was ball milled and mixed in a container to obtain a slurry. Wherein, the adding amount of the hydroxyethyl methacrylate is 31 parts by volume fraction; the addition amount of the isobornyl acrylate is 11 parts; KOS110 is added in an amount of 7 parts; 819 is added in an amount of 1.5 parts; the addition amount of vanadium is 3.5 parts; the adding amount of the ferroalloy 316 powder is 46 parts. The added carbide forming element metal powder vanadium combines with free carbon generated by decomposition of photosensitive resin to form second-phase vanadium carbide, thereby generating second-phase strengthening effect and improving ferroalloyStrength of the part.
And carrying out photocuring 3D printing on the slurry to obtain the ferroalloy blank structure.
And placing the ferroalloy blank into a furnace for glue discharging. The glue discharging atmosphere is hydrogen. The glue discharging process comprises the following steps: the temperature is raised to 350 ℃ at 3 ℃/min for 1h, and then is raised to 600 ℃ at 0.1 ℃/min for 1h.
And then placing the ferroalloy blank into a furnace for sintering. The sintering atmosphere is vacuum. The sintering process comprises the following steps: heating to 1360 ℃ at 7 ℃/min, and preserving heat for 6 hours.
Finally, the three-dimensional structural part of the iron alloy with the carbon content of the iron alloy 316 matrix of 0.06 percent, high corrosion resistance (the corrosion rate in natural water containing 100ppm of chloride ions is less than 0.4 mm/year) and 98 percent of compactness is obtained.
Example 2
Preparation of iron alloy (440) parts by adding carbide forming elemental metal powder chromium to photosensitive resins preferably having high residual carbon content
1, 6-hexanediol diacrylate as a photosensitive resin, KOS110 as a dispersing agent, 819 as a photoinitiator, pure chromium powder and 440 iron alloy powder (D 50 =15 μm, carbon content of 0.75%) was put into a container and ball-milled and mixed to obtain a slurry. Wherein, the adding amount of 1, 6-hexanediol diacrylate is 46 parts by volume fraction; KOS110 is added in an amount of 6 parts; 819 is added in an amount of 1.5 parts; the addition amount of chromium is 2.5 parts; the powder of ferroalloy 440 was added in an amount of 44 parts. The carbon content of the selected ferroalloy 440 powder is 0.75 percent, the requirement of the carbon content of the part cannot be met, the photosensitive resin with high residual carbon content is used for improving the carbon content, and meanwhile, the added carbide forming element metal powder chromium is combined with free carbon generated by decomposition of the photosensitive resin to form second-phase chromium carbide, so that the second-phase strengthening effect is generated to improve the strength of the ferroalloy part.
And carrying out photocuring 3D printing on the slurry to obtain the ferroalloy blank structure.
And placing the ferroalloy blank into a furnace for glue discharging. The glue discharging atmosphere is nitrogen. The glue discharging process comprises the following steps: the temperature is raised to 350 ℃ at 3 ℃/min for 1h, and then is raised to 600 ℃ at 0.5 ℃/min for 1h.
And then placing the ferroalloy blank into a furnace for sintering. The sintering atmosphere is vacuum. The sintering process comprises the following steps: heating to 1360 ℃ at 7 ℃/min, and preserving heat for 6 hours.
Finally, the ferroalloy 440 substrate carbon content is 1%, the intensity is 1900MPa, and the compactness is 98.4%.
Example 3
Preparation of pure copper parts from photosensitive resin with low carbon residue
Hydroxyethyl acrylate serving as a photosensitive resin, KH560 serving as a dispersing agent, TPO serving as a photoinitiator, and pure copper powder (D 50 =15 μm, carbon content less than 0.05%) was put into a container and ball-milled and mixed to obtain a slurry. Wherein, the adding amount of the hydroxyethyl acrylate is 41 parts by volume fraction; KH560 is added in an amount of 7 parts; TPO is added in an amount of 2 parts; the copper powder was added in an amount of 50 parts.
And carrying out photocuring 3D printing on the slurry to obtain a pure copper blank structure.
And placing the pure copper blank into a furnace for glue discharging. The glue discharging atmosphere is hydrogen. The glue discharging process comprises the following steps: heating to 300 ℃ at 3 ℃/min, preserving heat for 3 hours, and then heating to 600 ℃ at 0.1 ℃/min, preserving heat for 3 hours.
And then the pure copper blank is put into a furnace for sintering. The sintering atmosphere is vacuum. The sintering process comprises the following steps: heating to 1000 ℃ at 3 ℃/min, and preserving heat for 6 hours.
Finally, the pure copper three-dimensional structural part with the carbon content of 0.05 percent, the conductivity of 55IACS and the density of 98.9 percent is obtained.
Example 4
Preparation of nickel alloy (200) parts by preference of photosensitive resin with low residual carbon content and addition of carbide-forming elemental metal powder chromium
The photosensitive resin of hydroxyethyl methacrylate and isobornyl acrylate, a dispersing agent KOS110, a photoinitiator 819, pure chromium powder and nickel alloy 200 powder (D 50 =20 μm, carbon content of 0.1%) was put into a container and ball-milled and mixed to obtain a slurry. Wherein, the adding amount of the hydroxyethyl methacrylate is 36 parts by volume fraction; the addition amount of the isobornyl acrylate is 8 parts; KOS110 is added in an amount of 6 parts; 819 is added in an amount of 2 parts; the adding amount of the chromium powder is 3 parts; the addition amount of the nickel alloy powder is 45 parts.
And carrying out photocuring 3D printing on the slurry to obtain the nickel alloy blank structure.
And (5) placing the nickel alloy blank into a furnace for glue discharging. The glue discharging atmosphere is hydrogen. The glue discharging process comprises the following steps: the temperature is raised to 300 ℃ at 3 ℃/min for 1h, and then is raised to 600 ℃ at 0.1 ℃/min for 1h.
And then the nickel alloy blank is put into a furnace for sintering. The sintering atmosphere is vacuum. The sintering process comprises the following steps: heating to 1300 ℃ at 5 ℃/min, and preserving heat for 6 hours.
Finally, the nickel alloy 200 three-dimensional structural part with the carbon content of the matrix of the nickel alloy 200 of 0.08 percent, extremely high corrosion resistance (the corrosion rate of the nickel alloy 200 part in a solution with the hydrochloric acid concentration of 3 percent at the temperature of 100 ℃ is less than 0.04 mm/year) and the compactness of 97.8 percent is obtained.
Example 5
Aluminum alloy (2024) parts prepared by preferring photosensitive resin with low residual carbon content and adding carbide forming element metal powder molybdenum
Photosensitive resin 2-phenoxyethyl acrylate and lauryl methacrylate, dispersing agent KOS110, photoinitiator TPO, pure molybdenum powder and aluminum alloy 2024 powder (D 50 =15 μm, carbon content less than 0.05%) was put into a container and ball-milled and mixed to obtain a slurry. Wherein, the addition amount of the 2-phenoxyethyl acrylate is 30 parts by volume fraction; the adding amount of the lauryl methacrylate is 7 parts; KOS110 is added in an amount of 7 parts; TPO is added in an amount of 1 part; the adding amount of the molybdenum powder is 3 parts; the powder of aluminum alloy 2024 was added in an amount of 52 parts.
And carrying out photocuring 3D printing on the slurry to obtain the aluminum alloy blank structure.
And (5) placing the aluminum alloy blank into a furnace for glue discharging. The glue discharging atmosphere is hydrogen. The glue discharging process comprises the following steps: the temperature is raised to 300 ℃ at 2 ℃/min for 2 hours, and then is raised to 550 ℃ at 0.1 ℃/min for 3 hours.
And then the aluminum alloy blank is put into a furnace for sintering. The sintering atmosphere is vacuum. The sintering process comprises the following steps: heating to 600 ℃ at 1 ℃/min, and preserving heat for 3 hours.
Finally, the aluminum alloy three-dimensional structural part with the aluminum alloy 2024 matrix carbon content of 0.03% and the compactness of 98.8% is obtained.
Example 6
High-carbon ferrochrome part prepared by preferentially selecting photosensitive resin with high residual carbon and adding carbide-forming element metal powder vanadium
The photosensitive resin trimethylolpropane triacrylate and 1, 6-hexanediol diacrylate, dispersant SP-710, photoinitiator 819, pure vanadium powder and ferrochrome powder (D 50 =25 μm, carbon content of about 5%) was put into a container and ball-milled and mixed to obtain a slurry. Wherein, the adding amount of the trimethylolpropane triacrylate is 21 parts by volume fraction; the addition amount of the 1, 6-hexanediol diacrylate is 21 parts; the addition amount of SP-710 is 6.5 parts; 819 is added in an amount of 1.5 parts; the adding amount of the vanadium powder is 3 parts; the adding amount of ferrochrome powder is 47 parts. The carbon content of the ferrochrome powder is 5 percent, the requirement of the carbon content of a target part cannot be met, the carbon content of the part is improved by adopting photosensitive resin with high residual carbon content, and added carbide forming element metal powder vanadium is combined with carbon generated by decomposition of the photosensitive resin to form second-phase vanadium carbide, so that the second-phase strengthening effect is generated to improve the strength of the ferrochrome part.
And (3) carrying out photocuring 3D printing on the slurry to obtain the ferrochrome green body structure.
And (3) placing the ferrochrome blank into a furnace for glue discharging. The glue discharging atmosphere is nitrogen. The glue discharging process comprises the following steps: the temperature is raised to 300 ℃ at 1 ℃/min for 1h, and then the temperature is raised to 600 ℃ at 1 ℃/min for 1h.
And then placing the ferrochrome blank into a furnace for sintering. The sintering atmosphere is vacuum. The sintering process comprises the following steps: heating to 1500 ℃ at 5 ℃/min, and preserving heat for 6 hours.
Finally, the high-carbon ferrochrome three-dimensional structural part with the ferrochrome matrix carbon content of 7 percent, the strength of up to 2170MPa and the compactness of 98.5 percent is obtained.
Example 7
Preferably, photosensitive resin with low residual carbon content and carbide-forming element metal powder vanadium are added to prepare tungsten-copper alloy parts
Glycidyl methacrylate and hydroxyethyl methacrylate, KOS110, 819, pure vanadium powder and tungsten copper alloy powder (D) 50 =10μm, carbon content less than 0.07%) was put into a container and ball-milled and mixed to obtain a slurry. Wherein, by volumeThe added amount of the glycidyl methacrylate is 10 parts by weight; the adding amount of the hydroxyethyl methacrylate is 30 parts; KOS110 is added in an amount of 6 parts; 819 is added in an amount of 2 parts; the adding amount of the vanadium powder is 3 parts; the adding amount of the tungsten copper alloy powder is 49 parts.
And carrying out photocuring 3D printing on the slurry to obtain the tungsten-copper alloy blank structure.
And (3) placing the tungsten-copper alloy blank into a furnace for glue discharging. The glue discharging atmosphere is hydrogen. The glue discharging process comprises the following steps: the temperature is raised to 350 ℃ at 2 ℃/min for 2 hours, and then is raised to 600 ℃ at 0.1 ℃/min for 2 hours.
And then the tungsten-copper alloy blank is put into a furnace for sintering. The sintering atmosphere is vacuum. The sintering process comprises the following steps: heating to 1400 ℃ at 7 ℃/min, and preserving heat for 6 hours.
Finally, the three-dimensional structural part of the tungsten-copper alloy with the carbon content of 0.03 percent, good high-temperature performance, high-temperature strength of 200MPa, thermal conductivity of 170W/(m.K) and compactness of 98.4 percent is obtained under the high-temperature condition of 700 ℃.
Example 8
Preparation of nickel-tungsten alloy parts by preferring photosensitive resin with low residual carbon content and adding carbide forming element metal powder chromium
Glycidyl methacrylate and 2-phenoxyethyl acrylate as photosensitive resin, KOS110 as dispersing agent, 819 as photoinitiator, chromium powder and nickel tungsten alloy powder (D 50 =10μm, carbon content less than 0.05%) was put into a container and ball-milled and mixed to obtain a slurry. Wherein, the adding amount of the glycidyl methacrylate is 40 parts by volume fraction; the addition amount of the 2-phenoxyethyl acrylate is 5 parts; KOS110 is added in an amount of 6 parts; 819 is added in an amount of 2 parts; the adding amount of the chromium powder is 1 part; the adding amount of the nickel-tungsten alloy powder is 46 parts.
And carrying out photocuring 3D printing on the slurry to obtain the nickel-tungsten alloy blank structure.
And (3) placing the nickel-tungsten alloy blank into a furnace for glue discharging. The glue discharging atmosphere is hydrogen. The glue discharging process comprises the following steps: the temperature is raised to 350 ℃ at 3 ℃/min for 1h, and then is raised to 600 ℃ at 0.1 ℃/min for 2h.
And then the nickel-tungsten alloy blank is put into a furnace for sintering. The sintering atmosphere is vacuum. The sintering process comprises the following steps: heating to 1750 ℃ at a speed of 5 ℃/min, and preserving heat for 8 hours.
Finally, the nickel-tungsten alloy three-dimensional structural part with the carbon content of the nickel-tungsten alloy matrix of 0.01%, the strength of 1200MPa and the compactness of 98.6% is obtained.
Example 9
Molybdenum alloy parts prepared by preferably using photosensitive resin with low residual carbon content and adding carbide-forming element metal powder vanadium
The photosensitive resin hydroxyethyl methacrylate, a dispersing agent KOS110, a photoinitiator 819, pure vanadium powder and molybdenum alloy powder (D 50 =7μm, carbon content less than 0.05%) was put into a container and ball-milled and mixed to obtain a slurry. Wherein, the adding amount of the hydroxyethyl methacrylate is 39 parts by volume fraction; KOS110 is added in an amount of 5 parts; 819 is added in an amount of 2 parts; the adding amount of the vanadium powder is 3 parts; the molybdenum alloy powder is added in an amount of 51 parts. The added carbide forming element metal powder vanadium combines with free carbon generated by decomposition of the photosensitive resin to form second-phase vanadium carbide, and the second-phase strengthening effect is generated to improve the strength of the molybdenum alloy part.
And carrying out photocuring 3D printing on the slurry to obtain the molybdenum alloy blank structure.
And (5) placing the molybdenum alloy blank into a furnace for glue discharging. The glue discharging atmosphere is hydrogen. The glue discharging process comprises the following steps: heating to 350 ℃ at 3 ℃/min, preserving heat for 3 hours, and then heating to 600 ℃ at 0.1 ℃/min, preserving heat for 3 hours.
And then the molybdenum alloy blank is put into a furnace for sintering. The sintering atmosphere is vacuum. The sintering process comprises the following steps: heating to 2000 ℃ at 2 ℃/min, and preserving heat for 8 hours.
Finally, the molybdenum alloy three-dimensional structural part with the molybdenum alloy matrix carbon content of 0.02 percent and the strength of 1720MPa and the compactness of 97.9 percent is obtained.
Example 10
Preparation of magnesium alloy parts by preferring photosensitive resin with low residual carbon content
Glycidyl methacrylate and hydroxyethyl acrylate, KOS110 as dispersing agent, TPO as photoinitiator, and magnesium alloy powder (D) 50 =10μm, carbon content less than 0.04%) was put into a container and ball-milled and mixed to obtain a slurry. Wherein, the first is calculated according to the volume fractionThe added amount of the glycidyl acrylate is 5 parts; the adding amount of the hydroxyethyl acrylate is 35 parts; KOS110 is added in an amount of 6 parts; TPO is added in an amount of 1 part; the magnesium alloy powder is added in an amount of 53 parts.
And carrying out photocuring 3D printing on the slurry to obtain the magnesium alloy blank structure.
And placing the magnesium alloy blank into a furnace for glue discharging. The glue discharging atmosphere is hydrogen. The glue discharging process comprises the following steps: the temperature is raised to 300 ℃ at 1 ℃/min for 2 hours, and then is raised to 550 ℃ at 0.1 ℃/min for 2 hours.
And then the magnesium alloy blank is put into a furnace for sintering. The sintering atmosphere is vacuum. The sintering process comprises the following steps: heating to 600 ℃ at 1 ℃/min, and preserving heat for 3 hours.
Finally, the magnesium alloy matrix with the carbon content of 0.01 percent and the density of 1.8g/cm is obtained 3 And the density of the magnesium alloy three-dimensional structural part is 98.8 percent.
Comparative example 1
In comparison with example 1, the photosensitive resin used in comparative example 1 was trimethylolpropane triacrylate, and no carbide-forming elemental metal powder was added, the remainder being identical. The obtained iron alloy part has a matrix carbon content of 7% and low corrosion resistance (corrosion rate in natural water containing 100ppm chloride ions is greater than 3 mm/year).
Comparative example 2
In comparison with example 3, the photosensitive resin used in comparative example 2 was 1, 6-hexanediol diacrylate, the remainder being identical. The obtained pure copper part has 3% of matrix carbon content and 40IACS of conductivity.
Comparative example 3
In comparison with example 7, the photosensitive resin used in comparative example 3 was 1, 6-hexanediol diacrylate, and no carbide forming elemental metal powder was added, the remainder being identical. The obtained tungsten-copper alloy part has the matrix carbon content of 2.5 percent and the high-temperature performance is reduced, and the high-temperature strength is 100MPa under the high-temperature condition of 700 ℃.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The method for regulating and controlling the carbon content in the photo-curing additive manufacturing of the three-dimensional metal structural member is characterized by comprising the following steps of:
s1: placing photosensitive resin into a mixer, sequentially adding a dispersing agent, a photoinitiator and carbide to form elemental metal powder, and performing ball milling and mixing to obtain slurry;
wherein the addition amount of the photosensitive resin is 23-58 vol%, the addition amount of the dispersing agent is 5-10 vol%, the addition amount of the photoinitiator is 0.01-2 vol%, and the addition amount of the carbide forming element metal powder is 0.1-70 vol%;
s2: filling the slurry into a photocuring 3D printer, and performing 3D printing to obtain a blank;
s3: discharging glue from the blank body, and sintering to obtain a metal three-dimensional structural member;
wherein the chemical formula of the photosensitive resin is C x H y O z ，1<x<20，2<y<30，1<z<15, the residual carbon content of the photosensitive resin after thermal decomposition is 0.001-10 wt percent.
2. The method according to claim 1, wherein the photosensitive resin is any one of trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, lauryl methacrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, glycidyl methacrylate, hydroxyethyl methacrylate, and hydroxyethyl acrylate.
3. The method of claim 2, wherein the carbide-forming elemental metal powder is at least one of a Fe, ti, cr, V, W, mo, ta pure elemental metal, or an alloy thereof.
4. A method according to claim 3, wherein the glue removal conditions are: the glue discharging atmosphere is vacuum, nitrogen or hydrogen, the temperature is raised to 300-350 ℃ at 0.1-10 ℃/min, the temperature is kept for 0.1-10 h, and the temperature is raised to 550-600 ℃ at 0.01-5 ℃/min, and the temperature is kept for 0.1-10 h.
5. The method of claim 4, wherein the sintering conditions are: the sintering atmosphere is vacuum, nitrogen or hydrogen, and the temperature is raised to 500-2500 ℃ at 0.1-20 ℃/min, and the temperature is kept for 0.1-10 h.
6. The method of claim 5, wherein the dispersant is SP-710, KOS110, or KH560, and the photoinitiator is phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide or 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide.
7. The method of claim 6, wherein the ball milling rate is 100-400 rpm.
8. A metal three-dimensional structural member obtained by the method of any one of claims 1 to 7.
9. The metallic three-dimensional structural member of claim 8, wherein the metallic three-dimensional structural member is comprised of a metallic grain-to-metallic grain, metallic grain-to-carbide structure.
10. The three-dimensional metal structural member of claim 9, wherein the carbon content of the three-dimensional metal structural member is 0.01-10 wt%.
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