CN114669746A - Preparation method of porous metal microspheres for 3D printing - Google Patents

Preparation method of porous metal microspheres for 3D printing Download PDF

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CN114669746A
CN114669746A CN202210217089.1A CN202210217089A CN114669746A CN 114669746 A CN114669746 A CN 114669746A CN 202210217089 A CN202210217089 A CN 202210217089A CN 114669746 A CN114669746 A CN 114669746A
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preparation
metal
microspheres
printing
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CN114669746B (en
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程继贵
方青青
陈鹏起
台运霄
杨建�
许荡
魏邦争
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Hefei University of Technology
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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
    • 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

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 a stable nano metal suspension after ultrasonic dispersion. The preparation method comprises the steps of taking a nano metal suspension as a dispersion phase and silicone oil as a continuous phase, preparing precursor microspheres by using a microfluidic technology, and washing, drying, degreasing and the like to obtain the porous metal microspheres meeting the 3D printing requirements. The preparation method has the beneficial effects that the porous metal microspheres prepared by the method have the advantages of high sphericity, uniform size, high purity, good monodispersity and the like, and can be used for 3D printing technology. The whole preparation process is simple and easy to operate, the raw materials are simple, the flow is short, the cost is low, and the prospect is widened for the combination of the microfluidic technology and the powder metallurgy technology.

Description

Preparation method of porous metal microspheres for 3D printing
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 are difficult to manufacture and manufacture metal parts meeting the requirements. But can now be manufactured by 3D printing techniques. Therefore, the performance requirements to be met by 3D printing metal powder are also becoming important points of attention. The 3D printing metal powder has to meet the requirements of high powder sphericity, good fluidity, fine particle size and the like. The existing methods for preparing 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 particle size control; the particle size difference is obvious, and is as small as tens of microns and as large as hundreds of microns. The preparation of spherical powder has high cost and low efficiency. It is difficult to mass produce multi-grade powder. Today, many people have recognized that the problem of preparing spherical metal powder has become one of the bottlenecks that restrict 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. Microfluidics is a technology that can precisely control microscale fluids, and the prepared microspheres are uniform in size and good in monodispersity. The existing method for preparing the metal microspheres for 3D printing by utilizing the microfluidic technology can tightly link the 3D printing technology with 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 hotspot.
The Chinese invention patent CN 110282642A discloses a method for preparing alumina microspheres by utilizing a microfluidic technology. The method comprises the steps of peptizing a hydrolysate of aluminum sec-butoxide into aluminum sol, adding methylcellulose and hexamethylenetetramine into the aluminum sol as a gel initiator, adding a triblock copolymer to prepare a dispersed phase, introducing a continuous phase into a coaxial circular tube type microchannel for continuous flow by utilizing a microchannel technology, introducing the dispersed phase into an internal channel coaxially embedded into a main channel in the same direction, and forming dispersed phase droplets under the shearing action of the continuous phase. In the solidification process of the dispersed phase liquid drop, under the composite action of temperature initiation and pH initiation, the dispersed phase liquid drop is promoted to rapidly and preliminarily gelatinize in the micro-channel; and further completely solidifying through a coagulating bath, and then drying and calcining to obtain the alumina microspheres. The alumina microspheres prepared by the method have the advantages of high sphericity, uniform size, smooth surface and controllable internal pore structure. At present, in the field of ceramics, the microfluidic technology has already been developed to a certain extent. However, the application of the microfluidic technology in the preparation of metal powder in the field of powder metallurgy is very rare, and especially, the application in 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: a preparation method of porous metal microspheres for 3D printing comprises the steps of preparing a 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 microspheres after a series of treatments after separation.
Further, the preparation method specifically comprises the following steps:
s1) preparing a stable nano fluid suspension by using nano metal powder as a raw material;
s2) dispersing the nano fluid suspension obtained in S1) by adopting a micro-fluidic technology to obtain micro-spherical liquid drops;
s3) processing the microspherical 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 the metal microsphere blank to obtain the porous metal microsphere.
Furthermore, the particle size deviation of the porous metal microspheres is below 5%, the fluidity is 10-30s/50g, the purity is more than 99.9%, and the porosity of pores in the powder is 10-30%.
Further, the specific steps of S1) are:
s1.1) weighing nano metal powder with a certain mass, adding the nano metal powder into absolute ethyl alcohol to prepare a suspension, wherein the mass of the nano metal powder is 5-15 wt% of the absolute ethyl alcohol, and carrying out ultrasonic treatment for 0.8-1.2h by using an ultrasonic cleaner;
s1.2) weighing 10-30wt.% of dispersing agent and 2-5wt.% of light curing agent based on the total mass of the suspension, adding the dispersing agent and the light curing agent into the suspension, adjusting the pH value of the solution to 9-13 until the organic additive is completely dissolved, and performing ultrasonic dispersion and uniform stirring to obtain the nanofluid suspension.
Further, the nano metal powder is aluminum, magnesium, titanium, copper and nickel and an alloy of aluminum, magnesium, titanium, copper and nickel, wherein the content of corresponding elements in the alloy of aluminum, magnesium, titanium, copper and nickel is more than 80%, and the average particle size of the nano metal powder is 10 nm-10 μm.
Further, the dispersant 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,
the pH adjusting solution is NaOH.
Further, the specific steps of S2) are:
s2.1) taking the stable nano fluid suspension as a disperse phase in the micro-fluidic device, taking silicone oil as a continuous phase,
S2.2) shearing the nano fluid suspension into micro spherical droplets under the conditions that the flow rate of the dispersed phase is 0.5-9 mL/min and the flow rate of the continuous phase is 10-230 mu L/min.
Further, the specific step of S3) is to put the obtained microspherical liquid drop into silicone oil, irradiate the microspherical liquid drop in the silicone oil with ultraviolet rays, and excite the photocuring agent in the microspherical liquid drop to cure for 1 to 3 hours to form a metal microsphere blank.
Further, the specific steps of S4) are: s4.1) washing the solidified microspheres for multiple times by using trichloroethylene with the molar concentration of 0.08mol/L, and then using NH3·H2Washing with O to remove impurities, drying at 80-120 ℃ for 2-4 h,
s4.2) degreasing at the temperature of 200-400 ℃ for 2-6 h. The obtained powder has purity of more than 99.9%, particle diameter of 40-120 μm, and particle diameter deviation of below 5%. After high-temperature treatment, organic matters among the microspheres consisting of a plurality of powder particles are removed, so that the inner holes of the microsphere powder 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 microspheres, the printing mode of the 3D printing method is selective laser sintering, selective laser melting, near-net laser or selective electron beam melting technology, and the density of a printed finished product is more than 97%.
Compared with the prior art, the invention has the beneficial effects that:
1. in the invention, the nano fluid suspension is prepared to be used as a dispersed phase in the microfluidic technology, the mass fraction of the dispersing agent in the suspension is changed, the pH value of the suspension is adjusted, and the continuous phase is used for shearing microspheres with different sizes. The invention breaks through the situation that most of the traditional micro-fluidic technologies are used for preparing ceramic and polymer microspheres, develops a method for preparing metal microspheres by directly using the micro-fluidic technology and successfully combines the micro-fluidic technology with the powder metallurgy field.
2. Different from the traditional microfluidic technology that metal nitrate is used as a raw material, the metal powder is used for preparing the suspension, the self-curing effect cannot be obtained through a gel method in the preparation process, and the fusion difficulty exists after liquid drops are contacted, so that an additional light curing agent is required to be added for realizing the curing of the microspheres, the effects of quick curing and particle dispersion can be realized, and the preparation of the microspheres with the metal powder as the raw material is realized innovatively.
3. Compared with the metal microspheres prepared by the traditional method, the metal microspheres prepared by the micro-fluidic 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 required raw material metal powder. The metal microsphere particles prepared by the method disclosed by the invention are good in fluidity, so that the powder feeding and powder laying are more uniform, and the density of a 3D printed part is favorably improved.
4. The metal microspheres prepared by the method have uniform size and good monodispersity, and the deviation of the particle size 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 can be realized.
Drawings
Fig. 1 is a flow chart of a preparation method of porous metal microspheres for 3D printing according to the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, 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 of the present invention includes preparing a stable nano metal fluid suspension at room temperature, dispersing the precursor solution into droplets by using a microfluidic technology, forming a metal microsphere blank after treatment, and obtaining the porous metal microsphere after a series of treatments after separation.
The preparation method specifically comprises the following steps:
s1) preparing a stable nano fluid suspension by using nano metal powder as a raw material;
S2) dispersing the nano fluid suspension obtained in the S1) by adopting a micro-fluidic technology to obtain micro-spherical liquid drops;
s3) processing the microspherical liquid drops obtained in the S2) to form metal microspherical blanks;
s4) separating the metal microsphere blank obtained in the step S3), and then washing, drying and degreasing the metal microsphere blank to obtain the porous metal microsphere.
The particle size deviation of the porous metal microspheres is below 5%, the fluidity is 10-30s/50g, the purity is more than 99.9%, the particle size is 40-120 mu m, and the porosity of inner pores of the porous metal microspheres is 10-30%.
The S1) comprises the following specific steps:
s1.1) weighing nano metal powder with a certain mass, adding the nano metal powder into absolute ethyl alcohol to prepare a suspension, wherein the mass of the metal powder is 5-15 wt% of the 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 light curing agent in the total mass of the suspension, adding the dispersing agent and the light curing agent into the suspension, adjusting the pH value of the solution to 9-13 until the organic additive is completely dissolved, and performing ultrasonic dispersion and uniform stirring to obtain the nanofluid suspension.
The nano metal powder is aluminum, magnesium, titanium, copper, nickel and an alloy of the aluminum, the magnesium, the titanium, the copper and the nickel, wherein the content of corresponding elements in the alloy of the aluminum, the magnesium, the titanium, the copper and the nickel is more than 80%, and the average particle size range of the nano metal powder is 10 nm-10 mu m.
The dispersant 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,
the pH adjusting solution is NaOH.
The S2) comprises the following specific steps:
s2.1) taking the stable nano fluid suspension as a disperse phase in the micro-fluidic device, taking silicone oil as a continuous phase,
s2.2) shearing the nano fluid suspension into micro spherical droplets under the conditions that the flow rate of the dispersed phase is 0.5-9 mL/min and the flow rate of the continuous phase is 10-230 mu L/min.
And S3) specifically, placing the obtained microsphere liquid drop into silicone oil, irradiating the microsphere liquid drop in the silicone oil with ultraviolet rays for 1-3h, and exciting a light curing agent in the microsphere liquid drop to cure to form a metal microsphere blank.
The S4) comprises the following specific steps: s4.1) washing the solidified microspheres for multiple times by using trichloroethylene with the molar concentration of 0.08mol/L, and then using NH3·H2Washing with O to remove impurities, drying at 80-120 ℃ for 2-4 h,
s4.2) degreasing 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 microspheres as raw materials, the printing mode of the 3D printing method is selective laser sintering, selective laser melting, near-net laser or selective electron beam melting technology, and the density of a printed finished product is more than 97%.
Example 1
S1.1) weighing 10g of nano-copper powder by using an electronic balance, dispersing the nano-copper powder into 100mL of absolute ethyl alcohol by using an ultrasonic cleaner, and preparing a nano suspension.
S1.2) adding 15wt.% of sodium dodecyl sulfate, 3wt.% of photosensitive resin and photoinitiator (1: 1) to the solution in S1.1), and adjusting the pH of the solution to 11 with NaOH. Ultrasonic dispersion and magnetic stirring are carried out for 1.5 h.
S2) taking the copper nano-fluid suspension prepared in S1.2) as a dispersion phase in a microfluidic device, taking silicone oil as a continuous phase, and shearing the dispersion 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 dispersion phase droplets.
S3) placing the microsphere liquid drops obtained in the step S2) into silicone oil, irradiating the microsphere liquid drops in the silicone oil for 30min by ultraviolet rays, and exciting a light curing agent in the microsphere liquid drops to cure to form a metal copper microsphere blank body with the particle size of 65 mu m.
S4) separating the metal microsphere blank from the silicone oil, washing the gel microspheres for 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. Drying the metal microsphere blank at 100 ℃ for 3h, wherein the degreasing temperature is 400 ℃. The duration was 3h to remove organics. The particle size of the obtained copper powder microspheres is 60 micrometers, the impurity content is less than 0.1wt.%, and the porosity of inner pores of the microsphere powder is 23%.
And (3) introducing model information of a metal casting to be prepared into a computer of printing equipment, placing 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 be 900 ℃, and finally obtaining a 3D printing sample meeting the requirement.
Example 2
S1.1) weighing 13g of nano nickel powder by using an electronic balance, dispersing the nano nickel powder into 100mL of absolute ethyl alcohol by using an ultrasonic cleaner, and preparing a nano suspension.
S1.2) adding 20wt.% of sodium dodecyl benzene sulfonate, 3wt.% of photosensitive resin and photoinitiator (1: 1) into the solution in S1.1), and adjusting the pH of the solution to 10 by using NaOH. Ultrasonic dispersion and magnetic stirring are carried out for 2 hours.
S2) taking the nickel nano-fluid suspension prepared in S.1.2) as a dispersed phase in a micro-fluidic device, taking silicone oil as a continuous phase, and shearing the dispersed phase with the flow rate of 3.5mL/min into dispersed phase droplets by the continuous phase with the flow rate of 180 muL/min in a micro-channel of the micro-fluidic device.
S3) placing the microsphere liquid drops obtained in the step S2) into silicone oil, irradiating the microsphere liquid drops in the silicone oil for 30min by ultraviolet rays, and exciting a light 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 with 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 at 120 ℃ for 1.5 h. 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 0.1 wt%, and the porosity of an inner hole of the microsphere powder is 25%.
Introducing model information of a metal casting to be prepared into a computer of printing equipment, placing 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, and adopting a laser selective sintering metal 3D printing technology, wherein the printing temperature is set to 1200 ℃. And finally obtaining the 3D printing sample meeting the requirement.
Example 3
S1.1) weighing 15g of nano-aluminum powder by using an electronic balance, dispersing the nano-aluminum powder into 100mL of deionized water by using an ultrasonic cleaner, and preparing a nano suspension.
S1.2) adding 15wt.% of sodium dodecyl sulfate, 3wt.% of photosensitive resin and photoinitiator (1: 1) to the solution in S1.1), and adjusting the pH of the solution to 12 with NaOH. Ultrasonic dispersion and magnetic stirring are carried out for 2 hours.
S2) taking the aluminum nanofluid suspension prepared in 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 droplets by using 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 drop obtained in the S2) into silicon oil, irradiating the microsphere liquid drop in the silicon oil for 30min by ultraviolet rays, and exciting a light curing agent in the microsphere liquid drop 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 with trichloroethylene with the molar concentration of 0.8mol/L, wherein the washing time is 30min each time, and better removing the silicone oil. And drying the metal microsphere blank at 90 ℃ for 2 h. The degreasing temperature was 300 ℃. The duration was 3h to remove organics. The obtained aluminum powder microspheres have the particle size of 75 microns, the impurity content of less than 0.1wt.%, and the porosity of inner pores of the microsphere powder is 28%.
And (3) introducing model information of the metal casting to be prepared into a computer of printing equipment, placing 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 be 600 ℃, and finally obtaining a 3D printing sample meeting the requirement.
The preparation method of the porous metal microsphere for 3D printing provided in the embodiments of the present application is described in detail above. The above description of the embodiments is only for the purpose of helping to understand the method of the present application and its core idea; meanwhile, for a person skilled in the art, according to the idea of the present application, the specific implementation manner and the application scope may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present application.
As some terms are used throughout the description and claims to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of 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 good 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 good or system. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of additional like elements in the article of commerce or system in which the element is comprised.
It should be understood that the term "and/or" as used herein is merely a relationship that describes an associated object, meaning that three relationships may exist, e.g., a and/or B, may represent: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter associated objects are in an "or" relationship.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, and is not to be construed as excluding other embodiments, but rather is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.

Claims (10)

1. A preparation method of porous metal microspheres for 3D printing is characterized in that stable nano metal fluid suspension is prepared at room temperature, a precursor solution is dispersed into liquid drops by utilizing a microfluidic technology, a metal microsphere blank is formed after treatment, and porous metal microspheres are obtained after a series of treatments after separation.
2. The preparation method according to claim 1, characterized in that it comprises in particular the steps of:
s1) preparing a stable nano fluid suspension by using nano metal powder as a raw material;
s2) dispersing the nano fluid suspension obtained in S1) by adopting a micro-fluidic technology to obtain micro-spherical liquid drops;
s3) processing the microspherical liquid drops obtained in the S2) to form metal microspherical blanks;
s4) separating the metal microsphere blank obtained in the step S3), and then washing, drying and degreasing the metal microsphere blank to obtain the porous metal microsphere.
3. The method according to claim 2, wherein the porous metal microspheres have a particle size deviation of 5% or less, a flowability of 10-30s/50g, a purity of more than 99.9%, a particle size of 40-120 μm, and an inner pore porosity of 10-30%.
4. The preparation method according to claim 2, wherein 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, and carrying out ultrasonic treatment for 0.8-1.2h by using an ultrasonic cleaner to obtain a stable suspension;
s1.2) weighing 10-30wt.% of dispersing agent and 2-5wt.% of light curing agent in the total mass of the suspension obtained in the step S1.1), adding the dispersing agent and the light curing agent into the suspension, adding the pH adjusting solution to adjust the pH to 9-13, and performing ultrasonic dispersion and uniform stirring to obtain the nanofluid suspension.
5. The preparation method according to claim 4, characterized in that the nano metal powder in S1.1) is added in an amount of 5-15wt.% based on the mass of the absolute ethyl alcohol;
the nano metal powder is aluminum, magnesium, titanium, copper, nickel and an alloy of aluminum, magnesium, titanium, copper and nickel, wherein the content of corresponding elements in the alloy of aluminum, magnesium, titanium, copper and nickel is more than 80%, and the average particle size of the nano metal powder is 10 nm-10 mu m.
6. The preparation method according to claim 4, wherein the dispersant in S1.2) 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,
the pH adjusting solution is NaOH.
7. The preparation method according to claim 2, wherein the specific steps of S3) are as follows: and (4) 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 for 1-3h, and exciting a light curing agent in the microspherical liquid drops to cure to form a metal microsphere blank.
8. The preparation method according to claim 2, wherein the specific steps of S4) are as follows: s4.1) washing the solidified microspheres for multiple times by using trichloroethylene with the molar concentration of 0.08mol/L, and then using NH3·H2Washing with O to remove impurities, drying at 80-120 ℃ for 2-4 h,
s4.2) degreasing at the temperature of 200-400 ℃ for 2-6 h.
9. A porous metal microsphere, wherein the metal microsphere is prepared by the preparation method of any one of claims 1 to 8.
10. A3D printing method, the porous metal microspheres of claim 9 are used as printing raw materials in the 3D printing method, the printing mode of the 3D printing method is selective laser sintering, selective laser melting, near-net laser or selective electron beam melting, and the density of a printed finished product is more than 97%.
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