CN116372187A - Method for assisting metal 3D printing in reducing atmosphere - Google Patents
Method for assisting metal 3D printing in reducing atmosphere Download PDFInfo
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- CN116372187A CN116372187A CN202310376404.XA CN202310376404A CN116372187A CN 116372187 A CN116372187 A CN 116372187A CN 202310376404 A CN202310376404 A CN 202310376404A CN 116372187 A CN116372187 A CN 116372187A
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- metal
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- powder
- reducing atmosphere
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- 239000007789 gas Substances 0.000 claims description 36
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- 239000010941 cobalt Substances 0.000 claims description 2
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- 239000001307 helium Substances 0.000 claims description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000000441 X-ray spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 239000010963 304 stainless steel Substances 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
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- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
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- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/32—Process control of the atmosphere, e.g. composition or pressure in a building chamber
-
- 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
- B22F10/30—Process control
- B22F10/36—Process control of energy beam parameters
- B22F10/366—Scanning parameters, e.g. hatch distance or scanning strategy
-
- 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
- B22F10/80—Data acquisition or data processing
- B22F10/85—Data acquisition or data processing for controlling or regulating additive manufacturing processes
-
- 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
- B33Y50/00—Data acquisition or data processing for additive manufacturing
- B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
-
- 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 provides a method for assisting metal 3D printing in a reducing atmosphere, which reduces metal compound powder into metal by thermally driving reducing gas in the printing process, and non-metal elements are discharged from an exhaust port of a 3D printer in a gaseous form. The reducing atmosphere assisted metal 3D printing method has low temperature and low reflectivity to heat source energy, can realize printing of high-purity metal structural parts at the temperature lower than the melting point of metal, and widens the selection range of printing materials.
Description
Technical Field
The invention relates to the field of 3D printing manufacturing, in particular to the field of reducing atmosphere assisted metal 3D printing.
Background
The three-dimensional (3D) printing of metal is based on computer-aided three-dimensional design (CAD), and raw materials such as metal powder, metal wires or metal sheets are directly melted by laser or other heat sources to prepare a complex three-dimensional object, so that the three-dimensional printing method is suitable for directly manufacturing a complex metal structure with high flexibility. At present, the 3D printing preparation method of the metal structural part mainly comprises material spraying, thin material superposition, material extrusion, powder bed melting, direct energy deposition and electrochemical deposition manufacturing. Powder bed fusion 3D printing is the most mature and widely used technology, and metal powder raw materials are selectively fused and stacked layer by layer to build a three-dimensional structural member by using a heat source such as laser or electron beam, and protective gas is generally used for preventing oxidation of the metal materials due to high temperature in the printing process. However, powder bed molten metal 3D printing technology has some problems, mainly including:
1) The range of printable materials is narrow: the protective gas or the reducing gas used in the existing powder bed molten metal 3D printing technology only plays a role in protection, does not participate in the reaction process of metal printing, and powder materials are often limited to high-purity metal powder or metal alloy powder, so that the metal powder is few in variety and fixed in element composition, and the application universality is limited.
2) The metal powder has high cost: besides the cost of the price of the metal itself, the state of raw materials, the particle size screening of the metal powder, etc., the common powder-making methods such as atomization, rotary electrode, spheroidization are expensive, resulting in high cost of the metal powder finally used for printing; in addition, metal powders have poor oxidation resistance, tend to reduce the purity of the powder, and require special protection during storage and transportation, all of which increase the cost of the powder. The method for preparing refractory high-entropy alloy powder disclosed in patent CN112662929B comprises the steps of mixing all metal precursors together, and synchronously degreasing, reducing, dehydrogenating and presintering, so that the production efficiency is improved. However, the preparation process of the alloy powder involves the use of a sol system, which is easy to cause pollution; the alloy powder is subjected to multiple steps such as degreasing and reduction treatment, dehydrogenation and presintering treatment, thermal processing and forming, and the like, so that the preparation cost of the alloy powder is greatly increased.
3) The reflectivity of the metal powder material to heat source energy is high: for example, the reflectivity of aluminum and silver to laser is up to more than 90%, the reflectivity of metallic copper to near infrared laser is up to 95% at room temperature, and the reflectivity is up to 60% even if green laser which is easy to be absorbed by copper is adopted. High reflectivity on the one hand causes damage to the printing equipment itself and on the other hand results in higher energy waste.
The prior invention patent CN108500276B discloses a method for manufacturing parts from metal oxide, which mixes and grinds a raw material mixture of metal oxide and graphite powder, and the like, obtains a product green body by a mold or 3D printing, reduces and sinters the product green body in a sintering furnace in a reducing or protective atmosphere, and then prepares a finished product. However, when sintering the 3D printed green body, there are problems such as volume shrinkage, structural deformation, segregation, and the like, which seriously affect the product quality.
At present, no technology for directly printing a metal structural part by using metal compound powder as a powder bed to melt 3D printing raw material exists in the prior art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for assisting metal 3D printing in a reducing atmosphere.
The invention adopts the technical scheme that: a method for assisting metal 3D printing in reducing atmosphere comprises the following steps:
(1) Preparing a metal compound powder raw material for 3D printing, wherein the particle size of the powder is 1nm-100 mu m;
(2) After the metal compound powder is added into a powder barrel of a powder bed fusion 3D printer, continuously introducing mixed gas of reducing gas and protective gas into a forming cavity of the 3D printer;
(3) Three-dimensional modeling is carried out by adopting CAD software, then a three-dimensional structure is divided into a plurality of layers of two-dimensional graphs by using slicing software, and heat source power, scanning speed and scanning path are set;
(4) Printing the metal compound powder into a three-dimensional metal structural part by adopting a powder bed melting 3D printer;
(5) And cleaning the surface of the three-dimensional metal structural part to obtain a 3D printing product.
Preferably, the powder particle size of the metal compound is 5 μm to 20. Mu.m.
Preferably, the metal compound powder comprises one or more of copper, iron, cobalt, nickel, zinc, manganese, chromium, vanadium, titanium, molybdenum, tungsten, tantalum, aluminum, platinum, silver, and gold.
Preferably, the metal compound is one or a mixture of more of metal oxides, metal hydroxides, metal halides, metal oxysalts, metal sulfides, metal carbides, metal nitrides, metal coordination compounds and metal organic compounds containing the metal elements.
Preferably, the metal compound powder is spherical in shape.
Preferably, the volume ratio of the reducing gas to the protective gas is 0.1:0.9-0.7:0.3.
Preferably, the reducing gas is one or more of hydrogen, carbon monoxide, ammonia and methane.
Preferably, the protective gas is one or more of nitrogen, argon, helium and carbon dioxide.
Preferably, the surface cleaning mode in the step (5) is high-pressure air flow or water flow cleaning.
According to the method for assisting in 3D printing of metal in the reducing atmosphere, metal is generated through full reaction of metal compound powder under the reducing gas, the reducing gas is combined with nonmetallic components in the metal compound in the reaction process to form nonmetallic compounds, and the nonmetallic compounds are discharged from the exhaust port of the 3D printer in a gaseous form, so that the purity of a printed structural member is ensured.
In addition, as the reflectivity of the metal compound to the heat source is far lower than that of the metal to the heat source, the metal 3D printing can be realized by adopting a temperature lower than that required by the traditional powder bed fusion 3D printing, and the temperature control is realized by adjusting the power of the heat source.
Under the condition of scanning and heating by a heat source, the reducing gas reacts with the metal compound powder to quickly reduce the oxidized metal compound into metal. The flow rate of the reducing gas and the protective gas introduced into the printer cavity is controlled within the range of 0.5L/min-2L/min, and the purposes of controlling the flow rates of the reducing gas and the protective gas are as follows: on the one hand, sufficient reducing gas is provided to ensure that the oxidized metal in the scanning area of the heat source is completely reduced to metal, and on the other hand, gaseous nonmetallic compounds generated by the reaction are carried out.
The invention is provided with a burner and an adsorption tank at the exhaust port of the 3D printer, unreacted combustible gas is fully oxidized and combusted in the burner and finally is introduced into the adsorption tank, and active carbon is arranged in the adsorption tank for adsorbing harmful substances and particles.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the method for assisting in 3D printing of metal in the reducing atmosphere, provided by the invention, the material selection range is widened, and the metal compound powder is added as the printing raw material on the basis that the metal powder is used as the raw material in the traditional powder bed melting 3D printing.
2. The metal compound powder selected by the invention has low cost, can be prepared in a large scale by a mild physicochemical method with low cost and controllable particle size, and simultaneously reduces the preparation, storage, transportation and use costs of powder raw materials because the metal compound powder is stable to air and water.
3. The reducing atmosphere assisted metal 3D printing method has the advantages that the required temperature is low, the reflectivity to heat source energy is low, printing of high-purity metal structural parts can be realized at the temperature lower than the melting point of metal, the requirement can be met by using low-power heat source equipment, the energy waste is effectively reduced, and meanwhile, the damage of the heat source to the equipment can be reduced to a great extent.
Drawings
FIG. 1 is a schematic diagram of a reducing atmosphere assisted metal 3D printing system;
in the figure: 1: a laser heat source; 2: an optical fiber; 3: a heat source; 4: an X-Y axis displacement table; 5: a powder barrel; 6: forming a substrate; 7: a Z-axis displacement table; 8: forming a cavity; 9: a powder spreading device; 10: printed metal structural members; 11: a reducing gas; 12: a protective gas; 13: a gas flow meter; 14: a gas mixer; 15: an air inlet; 16: an exhaust port; 17: a burner; 18: an adsorption tank.
Detailed Description
In order that those skilled in the art will better understand the technical solutions provided by the present invention, the following description is made with reference to specific embodiments.
Example 1
Adding 1kg of commercial copper oxide powder with the average particle diameter of 10 mu m into a powder barrel of a laser melting 3D printer, and continuously introducing standard mixed gas with the volume ratio of hydrogen to argon of 0.1:0.9 into a forming cavity at the flow rate of 1L/min through an air inlet of the printer; drawing a cylinder with the diameter of 8mm and the height of 6mm by using CAD three-dimensional modeling software, slicing by using slicing software, setting the thickness of a powder spreading layer to be 60 mu m, setting the diameter of a used fiber laser spot to be 100 mu m, setting the laser power to be 80W, scanning in a laser scanning mode of S-shaped orthogonal stacking fault, and starting a printing process at the laser scanning speed of 300 mm/S; and finally, carrying out water flow surface cleaning on the printed blank, wherein the water is used for dissolving and removing unreacted cuprous chloride powder adhered to the surface of the printed part, so as to obtain the 3D printed copper structure.
The actual dimensions of the printed cylinder were tested: diameter is 8.10mm, height is 5.95mm; the X-ray spectroscopy analysis showed the printed copper to be 99.9% pure.
Example 2:
mixing and stirring copper chloride, sodium hydroxide and water in a mass ratio of 5:3:200, filtering and washing formed precipitate after one hour, and drying at 200 ℃ to obtain spherical copper oxide powder with a particle size range of 5-10 mu m and D50=7mu m; then adding the obtained copper oxide powder into a powder barrel of a laser melting 3D printer, and continuously introducing standard mixed gas with the volume ratio of hydrogen to argon of 0.1:0.9 into a forming cavity at the flow rate of 2L/min through an air inlet of the printer; drawing a cuboid with the length, the width and the height of 20mm, 20mm and 10mm respectively by using CAD three-dimensional modeling software, then performing slicing treatment by using slicing software, setting the thickness of a powder spreading layer to be 60 mu m, setting the diameter of a used optical fiber laser spot to be 100 mu m, setting the laser power to be 100W, scanning in an S-shaped orthogonal stacking fault mode at the laser scanning speed of 200mm/S, and then starting a printing process; and finally, carrying out high-pressure air flow surface cleaning on the printed blank to remove unreacted copper oxide powder, and obtaining the 3D printed copper structure.
Through testing, the actual dimensions of the printing piece are 20.10mm, 20.08mm and 9.90mm in length, width and height respectively; the X-ray spectroscopy analysis showed the printed copper to be 99.8% pure.
Example 3:
copper nitrate and zinc nitrate particles are dissolved according to a metal mass ratio of 65:35, freeze-dried and ball-milled for 20 minutes at a speed of 200r/min to obtain spherical bi-component metal salt powder with a particle size range of 5-10 mu m and D50=8mu m; then, 1kg of the obtained mixed metal salt powder is melted into a 3D printer powder barrel by laser, and standard mixed gas with the volume ratio of hydrogen to argon of 0.3:0.7 is continuously introduced into a forming cavity through a printer air inlet at the flow rate of 1L/min; drawing triangular columns with 5mm side length and 8mm column height by using CAD three-dimensional modeling software, slicing by using slicing software, setting the thickness of a powder spreading layer to be 60 mu m, setting the diameter of a used fiber laser spot to be 100 mu m, setting the laser power to be 100W, scanning by using an S-shaped orthogonal stacking fault scanning mode and the laser scanning speed to be 300mm/S, and then starting a printing process; and finally, carrying out water flow surface cleaning on the printed blank to obtain the 3D printed piece of the copper-zinc alloy.
The actual size of the printed triangular prism is tested: the side length of the triangle is 5.16mm, and the height is 7.90mm; the X-ray energy spectrum analysis result shows that the printing part comprises the components of copper and zinc in a mass ratio of 71:29.
Example 4:
mixing ferric trichloride, chromium trichloride, nickel dichloride and manganese dichloride according to a metal mass ratio of 70:18:10:2 through ball milling at a rotating speed of 200r/min for 20 minutes to obtain spherical three-component metal salt powder with a particle size range of 4-10 mu m and D50=6mu m; then adding 1kg of the obtained mixed metal salt powder into a powder barrel, and continuously introducing standard mixed gas of hydrogen, carbon monoxide and argon in the volume ratio of 0.4:0.1:0.5 into a forming cavity at the flow rate of 0.5L/min through an air inlet of a printer; drawing a cuboid with the length, the width and the height of 20mm, 20mm and 10mm respectively by using CAD three-dimensional modeling software, slicing by using slicing software, setting the thickness of a powder spreading layer to be 60 mu m, setting the diameter of a laser spot to be 100 mu m, setting the laser power to be 120W, scanning in an S-shaped orthogonal stacking fault mode at the laser scanning speed of 300mm/S, and then starting a printing process; and finally, cleaning the water flow surface of the printed structural member to obtain the 304 stainless steel component structural member.
Through testing, the actual dimensions of the printing piece are 20.10mm, 20.15mm and 9.92mm in length, width and height respectively; the X-ray energy spectrum analysis result shows that the printing part comprises the components of iron, chromium, nickel and manganese in the mass ratio of 69:19:10:2.
Example 5:
ball milling and mixing titanium tetrachloride and molybdenum pentachloride according to a metal mass ratio of 85:15 under the protection of nitrogen at a rotating speed of 200r/min for 20 minutes to obtain spherical bimetallic salt powder with a particle size ranging from 2 mu m to 6 mu m and D50=4mu m; adding 1kg of titanium molybdenum bimetallic salt powder into a laser melting 3D printer powder barrel, and continuously introducing standard mixed gas with the volume ratio of hydrogen to argon of 0.5:0.5 into a forming cavity at the flow rate of 2L/min through a printer air inlet; drawing a cuboid with the length, the width and the height of 20mm, 20mm and 10mm respectively by using CAD three-dimensional modeling software, then performing slicing treatment by using slicing software, setting the thickness of a powder spreading layer to be 60 mu m, setting the diameter of a used optical fiber laser spot to be 100 mu m, setting the laser power to be 150W, scanning in an S-shaped orthogonal stacking fault mode at the laser scanning speed of 200mm/S, and then starting a printing process; and finally, carrying out high-pressure air flow surface cleaning on the printed blank to remove unreacted metal salt powder, and obtaining the 3D printed Ti-15Mo titanium molybdenum alloy structural member.
Through testing, the actual dimensions of the printing piece are 20.20mm, 20.15mm and 9.97mm in length, width and height respectively; the X-ray energy spectrum analysis result shows that the components of the printing piece are titanium and the mass ratio of molybdenum is 85.5:14.5.
Example 6:
nickel nitrate, chromium nitrate, ferric nitrate and manganese nitrate particles are mixed according to the metal mass ratio of 74:15:10:1, stirring and dissolving, and then adding sodium hydroxide into the solution until precipitation is complete; filtering and cleaning the precipitate, and drying at 200 ℃; finally ball milling is carried out for 20 minutes at a rotating speed of 200r/min, and spherical metal oxide powder with the particle size ranging from 5 μm to 10 μm and D50=7μm is obtained; adding 1kg of the tetrametal oxide powder into a laser melting 3D printer powder barrel, and continuously introducing mixed gas of hydrogen, carbon monoxide and argon in the volume ratio of 0.4:0.1:0.5 into a forming cavity at the flow rate of 2L/min through a printer air inlet; drawing a cuboid with the length, the width and the height of 20mm, 20mm and 10mm respectively by using CAD three-dimensional modeling software, then performing slicing treatment by using slicing software, setting the thickness of a powder spreading layer to be 60 mu m, setting the diameter of a used optical fiber laser spot to be 100 mu m, setting the laser power to be 150W, scanning in an S-shaped orthogonal stacking fault mode at the laser scanning speed of 300mm/S, and then starting a printing process; and finally, carrying out high-pressure air flow surface cleaning on the printed blank to remove unreacted oxide powder, and obtaining the 3D printed hastelloy structural member.
Through testing, the actual dimensions of the printing piece are 20.15mm, 20.10mm and 9.93mm in length, width and height respectively; the X-ray energy spectrum analysis result shows that the components of the printing piece are nickel, chromium, iron and manganese with the mass ratio of 73:16:10:1.
Claims (8)
1. The method for assisting in 3D printing of metal in reducing atmosphere is characterized by comprising the following steps of:
(1) Preparing a metal compound powder raw material for 3D printing, wherein the particle size of the powder is 1nm-100 mu m;
(2) After the metal compound powder is added into a powder barrel of a powder bed fusion 3D printer, continuously introducing mixed gas of reducing gas and protective gas into a forming cavity of the 3D printer;
(3) Three-dimensional modeling is carried out by adopting CAD software, then a three-dimensional structure is divided into a plurality of layers of two-dimensional graphs by using slicing software, and heat source power, scanning speed and scanning path are set;
(4) Printing the metal compound powder into a three-dimensional metal structural part by adopting a powder bed melting 3D printer;
(5) And cleaning the surface of the three-dimensional metal structural part to obtain a 3D printing product.
2. A method of reducing atmosphere assisted metal 3D printing according to claim 1, characterized in that: the powder particle size of the metal compound is 5-20 mu m.
3. A method of reducing atmosphere assisted metal 3D printing according to claim 1, characterized in that: the metal compound powder comprises one or more of copper, iron, cobalt, nickel, zinc, manganese, chromium, vanadium, titanium, molybdenum, tungsten, tantalum, aluminum, platinum, silver and gold.
4. A method of reducing atmosphere assisted metal 3D printing according to claim 3, characterized in that: the metal compound is one or a mixture of more of metal oxides, metal hydroxides, metal halides, metal oxysalts, metal sulfides, metal carbides, metal nitrides, metal coordination compounds and metal organic compounds containing the metal elements.
5. A method of reducing atmosphere assisted metal 3D printing according to claim 1, characterized in that: the metal compound powder is spherical in shape.
6. A method of reducing atmosphere assisted metal 3D printing according to claim 1, characterized in that: the volume ratio of the reducing gas to the protective gas is 0.1:0.9-0.7:0.3.
7. A method of reducing atmosphere assisted metal 3D printing according to claim 1, characterized in that: the reducing gas is one or more of hydrogen, carbon monoxide, ammonia and methane, and the protective gas is one or more of nitrogen, argon, helium and carbon dioxide.
8. A method of reducing atmosphere assisted metal 3D printing according to claim 1, characterized in that: and (5) cleaning the surface in the step (5) by high-pressure air flow or water flow.
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