CN114669746B - Preparation method of porous metal microspheres for 3D printing - Google Patents
Preparation method of porous metal microspheres for 3D printing Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 105
- 239000002184 metal Substances 0.000 title claims abstract description 105
- 239000004005 microsphere Substances 0.000 title claims abstract description 104
- 238000010146 3D printing Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 46
- 239000000725 suspension Substances 0.000 claims abstract description 34
- 238000005516 engineering process Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 229920002545 silicone oil Polymers 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000005238 degreasing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000012530 fluid Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 238000000016 photochemical curing Methods 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 238000007639 printing Methods 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000011282 treatment Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 238000001723 curing Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004663 powder metallurgy Methods 0.000 abstract description 6
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000010008 shearing Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005058 metal casting Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000006070 nanosuspension Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
-
- 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
- B22F10/20—Direct sintering or melting
- B22F10/25—Direct deposition of metal particles, e.g. direct metal deposition [DMD] or laser engineered net shaping [LENS]
-
- 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
- B22F10/20—Direct sintering or melting
- B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
-
- 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
- B33Y40/10—Pre-treatment
-
- 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
-
- 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)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to the technical field of powder metallurgy, and particularly relates to a preparation method of porous metal microspheres for 3D printing. The method takes nano metal powder as a raw material, adds the nano metal powder into a mixed solution, and obtains stable nano metal suspension after ultrasonic dispersion. The nano metal suspension is used as a disperse phase, silicone oil is used as a continuous phase, a precursor microsphere is prepared by utilizing a microfluidic technology, and the porous metal microsphere meeting the 3D printing requirement is obtained through the steps of washing, drying, degreasing and the like. The porous metal microsphere prepared by the method has the advantages of high sphericity, uniform size, high purity, good monodispersity and the like, and can be used for a 3D printing technology. The whole preparation process has simple operation, simple raw materials, short flow and low cost, and widens the prospect for combining the two technical fields of micro-fluidic technology and powder metallurgy technology.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy, and particularly relates to a preparation method of porous metal microspheres for 3D printing.
Technical Field
In recent years, metal additive manufacturing techniques have been rapidly developed. Many conventional methods have difficulty in manufacturing metal parts that meet the requirements. But can now be manufactured by 3D printing techniques. Therefore, the performance requirements that 3D printed metal powders need to meet are also becoming an important concern. The 3D printing metal powder must meet the requirements of high sphericity, good fluidity, fine particle size and the like. The current methods for preparing the metal spherical powder mainly comprise an atomization method, a plasma fuse method and a rotating electrode method. However, the microspheres obtained by the methods have uneven particle size distribution and difficult control of the particle size; the particle size difference is obvious, as small as tens of micrometers and as large as hundreds of micrometers. The cost for preparing spherical powder is high and the efficiency is low. It is difficult to mass produce multi-grade powders. Today, many people have recognized that the problem of preparing spherical metal powders has become one of the bottlenecks that limit the development of 3D printing technology. Therefore, the preparation of the high-performance spherical metal raw material powder for 3D printing has important value significance. As a technology capable of precisely controlling micro-scale fluid, the prepared microsphere has uniform size and good monodispersity. The current method for preparing the metal microspheres for 3D printing by using the microfluidic technology will enable the 3D printing technology to be closely related to the field of powder metallurgy. How to prepare metal spherical powder suitable for various 3D printing with low cost and high efficiency becomes a research hot spot.
Chinese patent No. CN 110282642A discloses a method for preparing alumina microsphere by using microfluidic technology. The method comprises the steps of peptizing hydrolysis products of aluminum sec-butoxide into aluminum sol, adding methyl cellulose and hexamethylenetetramine as gel initiators into the aluminum sol, adding triblock copolymers to prepare a disperse phase, introducing the continuous phase into a coaxial annular type micro-channel to continuously flow by utilizing a micro-channel technology, introducing the disperse phase from an inner channel coaxially embedded into a main channel in the same direction, and forming disperse phase liquid drops under the shearing action of the continuous phase. In the solidification process of the dispersed phase liquid drops, under the composite action of temperature initiation and pH initiation, the rapid preliminary gelation of the dispersed phase liquid drops in the micro-channel is promoted; and further completely solidifying by using a coagulating bath, and drying and calcining to obtain the alumina microspheres. The alumina microsphere prepared by the method has high sphericity, uniform size, smooth surface and controllable internal pore structure. At present, in the ceramic field, a microfluidic technology has been developed to some extent. However, the application of the microfluidic technology in the preparation of metal powder in the field of powder metallurgy is very rare, and particularly, the preparation of metal microspheres is rarely studied.
Disclosure of Invention
The invention discloses a preparation method of porous metal microspheres for 3D printing, which aims to solve any one of the above and other potential problems in the prior art.
In order to solve the problems, the technical scheme of the invention is as follows: the preparation method comprises the steps of preparing stable nano metal fluid suspension at room temperature, dispersing precursor solution into liquid drops by utilizing a microfluidic technology, forming a metal microsphere blank after treatment, and obtaining the porous metal microsphere after a series of treatments after separation.
Further, the preparation method specifically comprises the following steps:
s1) preparing stable nanofluid suspension by taking nano metal powder as a raw material;
s2) dispersing the nano fluid suspension obtained in the step S1) by adopting a microfluidic technology to obtain microspherical liquid drops;
s3) treating the microsphere liquid drops obtained in the step S2) to form a metal microsphere blank;
s4) separating the metal microsphere blank obtained in the step S3), and then washing, drying and degreasing to obtain the porous metal microsphere.
Further, the particle size deviation of the porous metal microsphere is below 5%, the fluidity is 10-30s/50g, the purity is more than 99.9%, and the powder inner pore porosity is 10-30%.
Further, the specific steps of S1) are as follows:
s1.1) weighing nano metal powder with a certain mass, adding the nano metal powder into absolute ethyl alcohol to prepare suspension, wherein the mass of the nano metal powder is 5-15wt.% of absolute ethyl alcohol, and performing ultrasonic treatment for 0.8-1.2h by using an ultrasonic cleaner;
s1.2) weighing 10-30wt.% of dispersing agent and 2-5wt.% of photo-curing agent of the total mass of the suspension, adding the dispersing agent and the photo-curing agent into the suspension, adjusting the pH of the solution to 9-13 until the organic additives are completely dissolved, performing ultrasonic dispersion and stirring uniformly to obtain the nano fluid suspension.
Further, the nano metal powder is aluminum, magnesium, titanium, copper, nickel and alloys of aluminum, magnesium, titanium, copper and nickel, wherein the content of corresponding elements in each alloy of aluminum, magnesium, titanium, copper and nickel is more than 80%, and the average grain diameter of the nano metal powder is 10 nm-10 mu m.
Further, the dispersing agent is one or more of polyvinylpyrrolidone, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate,
the light curing agent comprises photosensitive resin and photoinitiator, the mass ratio of the photosensitive resin to the photoinitiator is 1-1.5:1,
the pH adjusting solution is NaOH.
Further, the specific steps of S2) are as follows:
s2.1) taking stable nano fluid suspension as a disperse phase in a microfluidic device, silicone oil as a continuous phase,
s2.2) shearing the nano fluid suspension into microsphere droplets under the conditions that the flow rate of a disperse phase is 0.5-9 mL/min and the flow rate of a continuous phase is 10-230 mu L/min.
And further, the specific step of the S3) is to place the obtained microspherical liquid drops in silicone oil, irradiate the microspherical liquid drops in the silicone oil with ultraviolet rays, and excite a photo-curing agent in the microspherical liquid drops to cure for 1-3 hours to form a metal microsphere blank.
Further, the specific steps of S4) are as follows: s4.1) washing the solidified microspheres with trichloroethylene with the molar concentration of 0.08mol/L for a plurality of times, and then using NH 3 ·H 2 O is washed to remove impurities, the drying time is 2-4 hours at the temperature of 80-120 ℃,
s4.2) degreasing is carried out at the temperature of 200-400 ℃ for 2-6 h. The obtained powder has a purity of more than 99.9%, a particle size of 40-120 μm and a particle size deviation of below 5%. Organic matters among the microspheres consisting of a plurality of powder particles are removed after high-temperature treatment, so that the inner holes of the powder of the microspheres form a certain porosity, and the porous metal microspheres are obtained.
The porous metal microsphere is prepared by the preparation method.
The 3D printing method adopts the porous metal microsphere, and the printing mode of the 3D printing method is laser selective sintering, laser selective melting, laser near-net type or electron beam selective melting technology, and the density of the printed finished product is more than 97%.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the nano fluid suspension is prepared as a disperse phase in a microfluidic technology, the mass fraction of a dispersing agent in the suspension is changed, the pH value of the suspension is regulated, and microspheres with different sizes are sheared by using a continuous phase. The invention breaks through the situation that most of the prior art utilizes the micro-fluidic technology to prepare ceramic and polymer microspheres, and develops a method for directly utilizing the micro-fluidic technology to prepare metal microspheres, thereby successfully combining the micro-fluidic technology with the field of powder metallurgy.
2. Unlike traditional microfluidic technology, which uses metal nitrate as the material, the method of the invention uses metal powder to prepare suspension, which can not obtain self-curing effect by gel method in the preparation process, and has the difficulty of fusion after liquid drops contact, so that additional photo-curing agent is needed to be added to realize curing of microspheres, thereby realizing rapid curing and particle dispersion effect and creatively realizing preparation of microspheres with metal powder as the material.
3. Compared with the metal microspheres prepared by the traditional method, the metal microspheres prepared by the microfluidic technology have the advantages of high sphericity, uniform and controllable size, high purity, good monodispersity and the like, and can more easily meet the requirements of the 3D printing technology on the needed raw material metal powder. The metal microsphere particles prepared by the method have good fluidity, so that the powder feeding and spreading are more uniform, and the density of the 3D printing workpiece is improved.
4. The metal microspheres prepared by the method have uniform size and good monodispersity, and the grain diameter deviation can be stably controlled below 5%; and the reagent consumption is low, the experimental safety coefficient is high, the internal composition content can be controlled, and a more ordered internal structure is realized.
Drawings
FIG. 1 is a flow chart of a method for preparing porous metal microspheres for 3D printing according to the invention.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are given as detailed embodiments and specific operation procedures based on the technical scheme of the present invention, but the scope of the present invention is not limited to the following examples.
As shown in fig. 1, the preparation method of the porous metal microsphere for 3D printing comprises the steps of preparing stable nano metal fluid suspension at room temperature, dispersing precursor solution into liquid drops by using a microfluidic technology, forming a metal microsphere blank after treatment, and obtaining the porous metal microsphere after separation and a series of treatments.
The preparation method specifically comprises the following steps:
s1) preparing stable nanofluid suspension by taking nano metal powder as a raw material;
s2) dispersing the nano fluid suspension obtained in the step S1) by adopting a microfluidic technology to obtain microspherical liquid drops;
s3) treating the microsphere liquid drops obtained in the step S2) to form a metal microsphere blank;
s4) separating the metal microsphere blank obtained in the step S3), and then washing, drying and degreasing to obtain the porous metal microsphere.
The particle size deviation of the porous metal microsphere is below 5%, the fluidity is 10-30s/50g, the purity is greater than 99.9%, the particle size is 40-120 mu m, and the porosity of the inner hole of the porous metal microsphere is 10-30%.
The specific steps of S1) are as follows:
s1.1) weighing nano metal powder with a certain mass, adding the nano metal powder into absolute ethyl alcohol to prepare suspension, wherein the mass of the metal powder is 5-15wt.% of absolute ethyl alcohol, and performing ultrasonic treatment for 0.8-1.2h by using an ultrasonic cleaner;
s1.2) weighing 10-30wt.% of dispersing agent and 2-5wt.% of photo-curing agent of the total mass of the suspension, adding the dispersing agent and the photo-curing agent into the suspension, adjusting the pH of the solution to 9-13 until the organic additives are completely dissolved, performing ultrasonic dispersion and stirring uniformly to obtain the nano fluid suspension.
The nano metal powder is aluminum, magnesium, titanium, copper, nickel and alloys of aluminum, magnesium, titanium, copper and nickel, wherein the content of corresponding elements in each alloy of aluminum, magnesium, titanium, copper and nickel is more than 80%, and the average grain diameter of the nano metal powder is 10 nm-10 mu m.
The dispersing agent is one or more of polyvinylpyrrolidone, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate,
the light curing agent comprises photosensitive resin and photoinitiator, the mass ratio of the photosensitive resin to the photoinitiator is 1-1.5:1,
the pH adjusting solution is NaOH.
The specific steps of S2) are as follows:
s2.1) taking stable nano fluid suspension as a disperse phase in a microfluidic device, silicone oil as a continuous phase,
s2.2) shearing the nano fluid suspension into microsphere droplets under the conditions that the flow rate of a disperse phase is 0.5-9 mL/min and the flow rate of a continuous phase is 10-230 mu L/min.
The specific step of the S3) is that the obtained microsphere liquid drops are placed in silicone oil, ultraviolet rays are used for irradiating the microsphere liquid drops in the silicone oil, the photo-curing time is 1-3h, and the photo-curing agent in the microsphere liquid drops is excited to cure, so that a metal microsphere blank body is formed.
The specific steps of the S4) are as follows: s4.1) washing the solidified microspheres with trichloroethylene with the molar concentration of 0.08mol/L for a plurality of times, and then using NH 3 ·H 2 O is washed to remove impurities, the drying time is 2-4 hours at the temperature of 80-120 ℃,
s4.2) degreasing is carried out at the temperature of 200-400 ℃ for 2-6 h.
The porous metal microsphere is prepared by the preparation method.
The 3D printing method adopts the porous metal microsphere as a raw material, and the printing mode of the 3D printing method is laser selective sintering, laser selective melting, laser near-net type or electron beam selective melting technology, and the density of a printed finished product is more than 97%.
Example 1
S1.1) 10g of nano copper powder was weighed by an electronic balance, and the nano copper powder was dispersed in 100mL of absolute ethanol by an ultrasonic cleaner to prepare a nano suspension.
S1.2) sodium dodecyl sulfate 15wt.%, 3wt.% photosensitive resin and photoinitiator (1:1) were added to the solution in S1.1), and the pH of the solution was adjusted to 11 with NaOH. Ultrasonic dispersion and magnetic stirring are carried out for 1.5 hours.
S2) taking the copper nanofluid suspension prepared in the step S1.2) as a disperse phase in a microfluidic device, taking silicone oil as a continuous phase, and shearing the disperse phase with the flow rate of 3 mu L/min by the continuous phase with the flow rate of 200 mu L/min to form disperse phase liquid drops.
S3) placing the microsphere liquid drops obtained in the S2) into silicone oil, irradiating the microsphere liquid drops in the silicone oil with ultraviolet rays for 30min, and exciting a photo-curing agent in the microsphere liquid drops to cure to form a metal copper microsphere blank body, wherein the granularity is 65 mu m.
S4) separating the metal microsphere blank from the silicone oil, washing the gel microsphere 3 times by using trichloroethylene with the molar concentration of 0.8mol/L, wherein the washing time is 40min each time, and better removing the silicone oil. And drying the metal microsphere blank for 3 hours at the temperature of 100 ℃ and the degreasing temperature is 400 ℃. The duration was 3h to remove organics. The particle size of the obtained copper powder microsphere is 60 mu m, the impurity content is less than 0.1wt.%, and the inner pore porosity of the microsphere powder is 23%.
And (3) importing model information of the metal casting to be prepared into a computer of printing equipment, putting the porous metal copper microspheres prepared in the step (S4) into a powder supply groove in 3D printing equipment, paving the porous metal copper microspheres into a thin layer, adopting a laser selective sintering metal 3D printing technology, setting the printing temperature to 900 ℃, and finally obtaining the 3D printing sample meeting the requirements.
Example 2
S1.1) 13g of nano nickel powder was weighed by an electronic balance, and the nano nickel powder was dispersed in 100mL of absolute ethanol by an ultrasonic cleaner to prepare a nano suspension.
S1.2) sodium dodecylbenzenesulfonate, 3wt.% photosensitive resin and photoinitiator (1:1) were added to the solution in S1.1), and the pH of the solution was adjusted to 10 with NaOH. Dispersing by ultrasonic wave and stirring by magnetic force for 2 hours.
S2) taking the nickel nano fluid suspension prepared in the step S.1.2) as a disperse phase in a microfluidic device, taking silicone oil as a continuous phase, and shearing the disperse phase with the flow rate of 3.5mL/min into disperse phase liquid drops by the continuous phase with the flow rate of 180 mu L/min in a micro-channel of the microfluidic device.
S3) placing the microsphere liquid drops obtained in the S2) into silicone oil, irradiating the microsphere liquid drops in the silicone oil with ultraviolet rays for 30min, and exciting a photo-curing agent in the microsphere liquid drops to cure to form a metal nickel microsphere blank.
S4) separating the metal microsphere blank from the silicone oil, washing the gel microsphere 3 times by using trichloroethylene with the molar concentration of 0.8mol/L, wherein the washing time is 1h each time, and better removing the silicone oil. And drying the metal microsphere blank for 1.5 hours at 120 ℃. The degreasing temperature was 450 ℃. The duration was 3h to remove organics. The particle size of the obtained nickel powder microsphere is 65 mu m, the impurity content is less than 0.1wt.%, and the inner pore porosity of the microsphere powder is 25%.
And (3) importing model information of the metal casting to be prepared into a computer of printing equipment, putting the porous metal nickel microspheres prepared in the step (S4) into a powder supply groove in 3D printing equipment, paving the porous metal nickel microspheres into a thin layer, adopting a laser selective sintering metal 3D printing technology, and setting the printing temperature to be 1200 ℃. And finally obtaining the 3D printing sample meeting the requirement.
Example 3
S1.1) weighing 15g of nano aluminum powder by an electronic balance, dispersing the nano aluminum powder into 100mL of deionized water by an ultrasonic cleaner, and preparing a nano suspension.
S1.2) sodium dodecyl sulfate 15wt.%, 3wt.% photosensitive resin and photoinitiator (1:1) were added to the solution in S1.1), and the pH of the solution was adjusted to 12 with NaOH. Dispersing by ultrasonic wave and stirring by magnetic force for 2 hours.
S2) taking the aluminum nano fluid suspension prepared in the step S1.2) as a disperse phase in a microfluidic device, taking silicone oil as the disperse phase, and shearing the disperse phase with the flow rate of 5mL/min into disperse phase liquid drops by a continuous phase with the flow rate of 210 mu L/min in a micro-channel of the microfluidic device.
S3) placing the microsphere liquid drops obtained in the S2) into silicone oil, irradiating the microsphere liquid drops in the silicone oil with ultraviolet rays for 30min, and exciting a photo-curing agent in the microsphere liquid drops to cure to form a metal aluminum microsphere blank.
S4) separating the metal microsphere blank from the silicone oil, washing the gel microsphere 3 times by using trichloroethylene with the molar concentration of 0.8mol/L, wherein the washing time is 30min each time, and the silicone oil is better removed. And drying the metal microsphere blank for 2 hours at 90 ℃. The degreasing temperature was 300 ℃. The duration was 3h to remove organics. The particle size of the obtained aluminum powder microsphere is 75 mu m, the impurity content is less than 0.1wt.%, and the inner pore porosity of the microsphere powder is 28%.
And (3) importing model information of the metal casting to be prepared into a computer of printing equipment, putting the porous metal aluminum microspheres prepared in the step (S4) into a powder supply groove in 3D printing equipment, paving the porous metal aluminum microspheres into a thin layer, adopting a laser selective sintering metal 3D printing technology, setting the printing temperature to 600 ℃, and finally obtaining the 3D printing sample meeting the requirements.
The preparation method of the porous metal microsphere for 3D printing provided by the embodiment of the application is described in detail. The above description of embodiments is only for aiding in understanding the method of the present application and its core ideas; meanwhile, as those skilled in the art will have modifications in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will appreciate that a hardware manufacturer may refer to the same component by different names. The description and claims do not take the form of an element differentiated by name, but rather by functionality. As referred to throughout the specification and claims, the terms "comprising," including, "and" includes "are intended to be interpreted as" including/comprising, but not limited to. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a certain error range, substantially achieving the technical effect. The description hereinafter sets forth the preferred embodiment for carrying out the present application, but is not intended to limit the scope of the present application in general, for the purpose of illustrating the general principles of the present application. The scope of the present application is defined by the appended claims.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
While the foregoing description illustrates and describes the preferred embodiments of the present application, it is to be understood that this application is not limited to the forms disclosed herein, but is not to be construed as an exclusive use of other embodiments, and is capable of many other combinations, modifications and environments, and adaptations within the scope of the teachings described herein, through the foregoing teachings or through the knowledge or skills of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the present invention are intended to be within the scope of the appended claims.
Claims (4)
1. The preparation method for the porous metal microsphere for 3D printing is characterized by comprising the following steps of preparing stable nano metal fluid suspension at room temperature, dispersing a precursor solution into liquid drops by utilizing a microfluidic technology, forming a metal microsphere blank after treatment, and obtaining the porous metal microsphere after a series of treatments after separation: s1) taking nano metal powder as a raw material to prepare stable nano fluid suspension;
the method comprises the following specific steps: s1.1) weighing nano metal powder with certain mass, adding the nano metal powder into absolute ethyl alcohol, and carrying out ultrasonic treatment for 0.8-1.2h by using an ultrasonic cleaner to obtain stable suspension;
s1.2) weighing 10-30wt.% of dispersing agent and 2-5wt.% of photo-curing agent which are obtained by the step S1.1) and are in total mass of the suspension, adding the dispersing agent and the photo-curing agent into the suspension, adding a pH adjusting solution to adjust the pH to 9-13, performing ultrasonic dispersion and stirring uniformly to obtain a nanofluid suspension;
the nano metal powder is added into the mixture, wherein the mass of the nano metal powder is 5-15 wt% of that of the absolute ethyl alcohol; the nano metal powder is aluminum, magnesium, titanium, copper, nickel and alloys of aluminum, magnesium, titanium, copper and nickel, wherein the content of corresponding elements in each alloy of aluminum, magnesium, titanium, copper and nickel is more than 80 percent, and the average grain diameter of the nano metal powder is 10 nm-10 mu m; the dispersing agent is one or more of polyvinylpyrrolidone, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate, the light curing agent comprises photosensitive resin and a photoinitiator, the mass ratio of the photosensitive resin to the photoinitiator is 1-1.5:1, and the pH adjusting solution is NaOH;
s2) dispersing the nano fluid suspension obtained in the step S1) by adopting a microfluidic technology to obtain microspherical liquid drops;
s3) treating the microsphere liquid drops obtained in the step S2) to form a metal microsphere blank;
the method comprises the following specific steps: placing the microspherical liquid drops obtained in the step S2) into silicone oil, irradiating the microspherical liquid drops in the silicone oil with ultraviolet rays, and exciting a photo-curing agent in the microspherical liquid drops to cure for 1-3 hours to form a metal microspherical blank;
s4) separating the metal microsphere blank obtained in the step S3), and then washing, drying and degreasing to obtain the porous metal microsphere; the particle size deviation of the porous metal microsphere is below 5%, the fluidity is 10-30s/50g, the purity is greater than 99.9%, the particle size is 40-120 mu m, and the porosity of the inner hole of the porous metal microsphere is 10-30%.
2. The preparation method according to claim 1, wherein the specific steps of S4) are: s4.1) washing the solidified microspheres with trichloroethylene with the molar concentration of 0.08mol/L for multiple times, washing with NH 3H 2O to remove impurities, degreasing at the temperature of 80-120 ℃ for 2-4H and at the temperature of 200-400 ℃ for 2-6H by S4.2).
3. A porous metal microsphere, wherein the metal microsphere is prepared by the preparation method of any one of claims 1 or 2.
4. The 3D printing method adopts the porous metal microsphere as the printing raw material according to claim 3, and is characterized in that the printing mode of the 3D printing method is laser selective sintering, laser selective melting, laser near-net type or electron beam selective melting technology, and the density of a finished product after printing is more than 97%.
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