CN113351827B - Metal-based metamaterial preparation method based on indirect additive manufacturing - Google Patents
Metal-based metamaterial preparation method based on indirect additive manufacturing Download PDFInfo
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- B22C9/043—Removing the consumable pattern
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- 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
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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Abstract
A preparation method of a metal-based metamaterial based on indirect additive manufacturing comprises the following steps: immersing the resin primary mould in a molten secondary mould material, solidifying the secondary mould material, completely coating the resin primary mould, polishing the solidified secondary mould material to completely expose the upper surface of the resin primary mould, removing the exposed resin primary mould through a resin removal primary mould process, and uniformly coating a layer of metal film in an evaporation machine to obtain the secondary mould; pouring the liquid metal-based material into a secondary mould by an electrowetting method and solidifying the liquid metal-based material; removing the metal film coated on any surface of the secondary die to expose the secondary die material coated by the metal film, placing the secondary die material in a secondary die dissolving agent to remove the secondary die, and then placing the secondary die material in a metal film dissolving agent to remove the metal film to obtain the required metal-based metamaterial; the invention can form the metal-based metamaterial with low, medium and high melting points and a complex structure.
Description
Technical Field
The invention is suitable for the technical field of micro-nano manufacturing, in particular to a method for preparing a metal-based metamaterial based on indirect additive manufacturing, and is particularly suitable for a three-dimensional structured forming process of liquid metals with different melting points and metal-based composite materials thereof.
Background
The metamaterial is an artificially manufactured, three-dimensional composite material with a periodic structure, and the basic structural unit of the metamaterial is an artificial structure and has extraordinary physical properties different from natural materials. The metamaterial has supernormal physical properties widely relating to the fields of sound, light, heat, force, electromagnetism and the like, and has very wide application prospects in the fields of industry, military and the like. In recent years, the metamaterial taking the liquid metal matrix composite material as the physical carrier is widely applied to strategic leading-edge technical fields of aerospace invisible cloak, novel passive electronic devices, multi-frequency shockproof mechanisms and the like due to the excellent electromagnetic property of the metamaterial, and has the advantages of capability of absorbing electromagnetic waves, excellent mechanical property, controllable property of functional materials and the like.
From the perspective of comprehensive regulation of mechanical properties, functional properties and the like of liquid metal matrix composite materials, the composite materials are usually made of gallium (Ga), indium (In), tin (Sn) and liquid metal alloys thereof with relatively low melting points, and the gallium (Ga), indium (In), tin (Sn) and liquid metal alloys thereof are mixed In a soft polymer structure to realize a remarkable toughening effect, and liquid metal reinforced toughened polymers represented by the gallium indium (In) and the indium (In) are designed to have excellent designable characteristics In a design mode similar to natural materials. For example, Kazem et al prepared a new composite material (EGaIn) with micron-sized liquid metal metamaterials embedded in a soft elastomer by mechanical mixing, which had higher toughness due to the highly deformable liquid metal dissipating the stress generated in the crack tips after the composite material was damaged; cooper et al have toughened soft styrene-ethylene-butylene-styrene hollow elastomer fibers with high stiffness solid Ga cores, the toughness resulting from repeated fracture of the higher modulus Ga cores, preventing catastrophic fracture of the composite core, and enhancing the stiffness of the metamaterial. In addition, due to the low melting point characteristic of the liquid metal matrix composite material in the preparation process, the metal matrix composite metamaterial also shows the comprehensive capability of thermal restoration and shape memory.
Although liquid metal matrix composites have excellent mechanical properties, these biologically inspired liquid metal-polymer composite structures are still limited to films or fibers, the structural design and spatial orientation are still limited by the manufacturing process and the functional properties of the composite materials, and the formation of the corresponding three-dimensional liquid metal matrix composite material still has certain challenges and few reports. With the rapid development of 3D printing technology, the three-dimensional liquid metal matrix composite material is an effective strategy for manufacturing the three-dimensional liquid metal matrix composite material. On one hand, in terms of a direct printing process, the difficulty of printing and forming is increased by the characteristics of high surface energy, low melting point, poor extrusion thinning capability, no photosensitive cross-linking forming and the like of liquid metal, so that the liquid metal cannot be suitable for a typical 3D printing process method; on the other hand, in the indirect forming process, the polymer mold and the liquid metal have poor interface compatibility, low filling rate of heterogeneous interfaces and poor fluidity of the composite material, so that the indirect printing and forming of the liquid metal matrix composite material are difficult, and the manufacturing efficiency is low.
Zhang et al propose vacuum filling to fill hollow lattice scaffolds for 3D printing, which is efficient and has few defects compared to traditional syringe injection. Due to the adjustable characteristics of mechanical property and functional property of gallium (Ga) in a relatively low temperature range, Lu and the like prepare the novel liquid metal filled polymer micro-lattice metamaterial by projection micro-stereolithography 3D printing and vacuum filling of gallium, and the metamaterial has the thickness of 0.8MJ/m 3 While it exhibits a shape memory effect and can even substantially recover its original shape upon severe fracture. It has been demonstrated that liquid metal matrix composites can fill polymer channels when the applied pressure exceeds the critical pressure, but the critical pressure is inversely related to the channel size, and in current research methods, the resulting meta-material after indirect forming is not a pure metal matrix composite due to the metal matrix compositeThe functional characteristics of the material are limited by the limitations of the melting point, the forming precision, the forming range, the mechanical design target and the material curing property.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing a metal-based metamaterial based on indirect additive manufacturing, which realizes indirect printing and forming of the metal-based metamaterial with adjustable and controllable forming temperature from three aspects of surface energy regulation, heterogeneous interface filling, demolding forming and the like.
In order to achieve the purpose, the invention provides a specific technical scheme as follows:
a preparation method of a metal-based metamaterial based on indirect additive manufacturing comprises the following steps:
(1) preparing an alkali soluble resin primary mould with a required three-dimensional structure by using a 3D printing technology;
(2) immersing an alkali-soluble resin primary mould in a molten secondary mould material, solidifying the secondary mould material, completely coating the resin primary mould, polishing the solidified secondary mould material to completely expose the upper surface of the resin primary mould, removing the exposed resin primary mould through a resin primary mould removing process, and then uniformly coating a layer of metal film in an evaporation machine to obtain a secondary mould;
(3) preparing a required liquid metal-based material, and pouring the liquid metal-based material into a secondary mould by an electrowetting method and solidifying the liquid metal-based material;
(4) and removing the metal film coated on any surface of the secondary die to expose the secondary die material coated by the metal film, placing the secondary die material in a secondary die dissolving agent to remove the secondary die, and then placing the secondary die material in a metal film dissolving agent to remove the metal film to obtain the required metal-based metamaterial.
The preparation method of the alkali-soluble resin comprises the following steps: according to parts by weight: selecting 40-60 parts of comonomer N, N-dimethylacrylamide, 40-60 parts of methyl methacrylate and 40-50 parts of crosslinking cracking agent methacrylic anhydride, mixing under the heating of an oil bath at 40-60 ℃, then respectively adding 10-20 parts of filler polyvinylpyrrolidone and 10-20 parts of photoinitiator aroylphosphine oxide or bis-benzoylphenylphosphine oxide, and uniformly dispersing.
The coated metal film adopts copper or nickel, and the coated metal film has the function of preventing the formed metal-based metamaterial from being dissolved due to direct contact with a secondary mold dissolving agent.
The liquid metal-based material includes, but is not limited to, one of the following: gallium, indium, tin, bismuth tin silver alloy, metal matrix composite; the metal matrix composite material comprises a composite material of metal electronic ink and carbon fiber powder.
The secondary mold material includes but is not limited to one of the following: paraffin wax, or molten paraffin wax and S i O 2 The mixed solution of the nano particles, molten paraffin accounts for 25-50% of the total mass.
The resin removing primary die process comprises the following steps: when the secondary mould material is paraffin, placing the secondary mould material in aqueous solution of sodium hydroxide or other alkaline solution to remove the resin primary mould; when the secondary mold material is a mixed solution of molten paraffin and SiO2, the mixture is placed into a box-type heating furnace and is burnt at a high temperature of 300-350 ℃ for 1-1.5 hours to remove the primary resin mold.
The electrowetting process comprises the following steps: adding electrode plates on the upper surface and the lower surface of a mould to be poured, contacting the upper electrode plate with a metal-based material, and applying a voltage of 150-200V, so that the wettability of liquid drops on the surface of the mould is changed, and the pouring effect is improved.
The solidification process comprises the following steps: the resulting mold/metal material composite is left standing in an environment at a temperature lower than the melting point of the metal to be solidified.
The secondary mold dissolving agent is prepared by fully dissolving a secondary mold material and not reacting with a metal film, and when the secondary mold material is paraffin, the secondary mold dissolving agent comprises but is not limited to toluene, xylene and CCl 4 (ii) a When the secondary mold material is molten paraffin and S i O 2 The secondary mold dissolving agent is 30-50 wt% hydrofluoric acid liquid.
The metal film dissolving agent is used for fully dissolving the plated metal film and does not react with the metal-based metamaterial, and comprises but not limited to 10-20 wt% ferric trichloride solution or 25-28 wt% concentrated ammonia water with oxygen.
The invention has the beneficial effects that:
(1) the forming effect is good. The indirect additive manufacturing process provided by the invention can overcome the defects of high surface energy, no photosensitive cross-linking forming, high curing difficulty and the like of the original direct 3D printing, and realizes the forming of a microstructure with higher precision.
(2) The application range is wide. The rollover process can meet the molding requirements of various metalloids and composite materials thereof to a certain extent. The material composition of the die in the secondary die turnover process is dynamically adjusted, so that the limitation of different melting points of different metal materials is solved, and the metal-based metamaterial within a wide melting point range is formed.
(3) Simple process and high preparation efficiency. Compared with the traditional forming process of the metal-based metamaterial, the process for preparing the mold through 3D printing and mold overturning and liquid metal pouring and forming greatly simplifies the preparation process. Simple and convenient working procedure and high preparation efficiency, and is suitable for the requirement of industrial production.
Drawings
Fig. 1 is a technical route diagram of a metal-based metamaterial preparation method based on indirect additive manufacturing provided by the invention.
Fig. 2 is a schematic view of the preparation of a secondary mold according to the present invention, including an alkali-soluble resin primary mold 1 and a liquid secondary mold material 2.
FIG. 3 is a schematic diagram showing the dissolution of the alkali-soluble resin mold according to the present invention, which comprises a paraffin resin complex 3 and an aqueous sodium hydroxide solution 4.
Fig. 4 is a schematic diagram of a secondary mold according to the present invention, which includes a front cross-sectional structure 5 and a three-dimensional wire-frame structure 6.
Fig. 5 is a schematic illustration of an electrowetting process according to the present invention comprising a liquid metal material 7.
FIG. 6 is a schematic diagram of the demolding of the metal-based metamaterial provided by the present invention, including a secondary mold dissolver 8.
Fig. 7 is a real object diagram of the metal-based metamaterial provided by the invention, which is as follows from left to right: fig. 7(a) shows a gallium metamaterial, fig. 7(b) shows a gallium and carbon fiber composite metamaterial, and fig. 7(c) shows a tin and ceramic composite metamaterial.
Detailed Description
The present invention will be described in further detail with reference to preferred examples thereof.
It should be added that the specific examples described herein are only for explaining the preparation method according to the present invention, and are not intended to limit the present invention and the embodiments thereof.
Example 1
The embodiment aims to realize three-dimensional structural molding of the metal-based metamaterial gallium, and the specific preparation process is as shown in figure 1, and comprises the following steps:
(1) preparing an alkali soluble resin primary mould with a required three-dimensional structure by using a 3D printing technology;
the method specifically comprises the following steps: 40g of comonomer N, N-dimethylacrylamide and 60g of comonomer methyl methacrylate were weighed using an electronic balance and both were poured into a beaker and mixed well. Subsequently, 40g of the crosslinking cleavage agent methacrylic anhydride was weighed out and poured into a beaker to mix well. The mixed solution is put into a magnetic stirring water bath kettle and stirred for 40 minutes in a 50 ℃ oil bath, and then 10g of bulking agent polyvinylpyrrolidone and 20g of photosensitizer aroylphosphine oxide are sequentially added. The temperature is kept and stirring is continued for 3 hours, and the alkali-soluble photosensitive resin can be obtained. And printing the resin mold by using a 3D printer. And washing the uncured photosensitive resin on the surface of the photosensitive resin mold by using alcohol, and performing post-curing treatment for 15min in a UV curing box to improve the crosslinking degree of the photosensitive resin.
(2) Immersing the resin primary mould in a molten secondary mould material, solidifying the secondary mould material, completely coating the resin primary mould, polishing the solidified secondary mould material to completely expose the upper surface of the resin primary mould, removing the exposed resin primary mould through a resin removal primary mould process, and uniformly coating a layer of metal film in an evaporation machine to obtain the secondary mould;
the method specifically comprises the following steps: 50g of paraffin is put into a beaker and placed in a water bath heating pot at the temperature of 60 ℃, and the mixture is stirred until the paraffin is completely melted. Referring to fig. 2, the alkali-soluble resin primary mold 1 is completely immersed in the secondary mold material 2, paraffin, for 1 hour and then taken out, and the temperature is reduced to solidify the paraffin. And (5) polishing the paraffin on the surface of the mould to completely expose the upper surface of the primary resin mould. Referring to fig. 3, placing the resin-paraffin complex 3 in a sodium hydroxide solution 4 with the mass fraction of 5% for standing for 2 hours until the alkali-soluble resin is completely dissolved, taking out, washing with deionized water, drying, referring to fig. 4, and obtaining the required paraffin secondary mold, wherein the paraffin secondary mold comprises a front-view section structure 5 and a three-dimensional wire-frame diagram structure 6, and placing the paraffin secondary mold in a copper film evaporator for 1 minute to obtain the copper/paraffin composite material with the surface coated with a layer of copper film.
(3) Preparing a required liquid metal-based material, and pouring the liquid metal-based material into a secondary mould by an electrowetting method and solidifying the liquid metal-based material;
the method specifically comprises the following steps: 50g of 99% pure gallium were preheated to 40 ℃ in a beaker to melt it well. Referring to fig. 5, electrode plates were added to the upper and lower surfaces of a paraffin mold by an electrowetting method, a liquid metal material 7, liquid metal gallium, was poured into the mold at a voltage of 150V to fill the cavity of the mold, and then it was placed in an environment at 0 ℃ for 1 hour to completely solidify the liquid metal.
(4) Removing the metal film coated on any surface of the secondary die to expose the secondary die material coated by the metal film, placing the secondary die material in a secondary die dissolving agent to remove the secondary die, and then placing the secondary die material in a metal film dissolving agent to remove the metal film to obtain the required metal-based metamaterial:
the method specifically comprises the following steps: this step will be carried out while maintaining an environment of 20 ℃. And (3) grinding the metal film on the outer surface of one side of the paraffin mould by using sand paper to expose the paraffin in the paraffin mould. Referring to fig. 6, the mold was completely immersed in the secondary mold solvent 8-toluene liquid, left to stand until the paraffin was completely dissolved, and taken out. After being washed and dried by absolute ethyl alcohol and deionized water in sequence, the copper film is placed in 100ml of ferric trichloride solution with the mass fraction of 20% to completely dissolve the copper film, and ice blocks are added during the process to keep the temperature of the solution below 20 ℃. And taking out the gallium with the copper film removed, washing with deionized water, drying, and referring to fig. 7, thus obtaining the structured metal-based metamaterial gallium.
Example 2
The embodiment aims to realize three-dimensional structural molding of the medium and high melting point alloy metal-based metamaterial bismuth tin silver alloy, and the specific preparation process comprises the following steps:
(1) preparing an alkali soluble resin primary mould with a required three-dimensional structure by using a 3D printing technology;
the method specifically comprises the following steps: 60g of comonomer N, N-dimethylacrylamide and 40g of comonomer methyl methacrylate were weighed using an electronic balance and both were poured into a beaker and mixed well. Subsequently 50g of the crosslinking cleavage agent methacrylic anhydride was weighed out and poured into a beaker to mix well. The mixed solution is put into a magnetic stirring water bath kettle and stirred for 40 minutes in a 50 ℃ oil bath, and then 20g of bulking agent polyvinylpyrrolidone and 10g of photosensitizer aroylphosphine oxide are sequentially added. The temperature is kept and stirring is continued for 3 hours, and the alkali-soluble photosensitive resin can be obtained. And printing the resin mold by using a 3D printer. And washing the uncured photosensitive resin on the surface of the photosensitive resin mold by using alcohol, and performing post-curing treatment for 15min in a UV curing box to improve the crosslinking degree of the photosensitive resin.
(2) Immersing the resin primary mould in a molten secondary mould material, solidifying the secondary mould material, completely coating the resin primary mould, polishing the solidified secondary mould material to completely expose the upper surface of the resin primary mould, removing the exposed resin primary mould through a resin removal primary mould process, and uniformly coating a layer of metal film in an evaporation machine to obtain the secondary mould;
the method specifically comprises the following steps: 50g of paraffin wax is placed in a beaker and put into an oven, the temperature is set to be 60 ℃, the paraffin wax is heated for 1 hour to be completely melted, and then 100g of SiO is weighed 2 And adding the nano particles into the melted paraffin, putting the glass container into an oven, uniformly mixing to obtain SiO 2/paraffin mixed slurry, and taking out. Completely immersing the photosensitive resin mould printed in the first step in a SiO 2/paraffin wax mixed system, standing for 1h, taking out the photosensitive resin mould infused with SiO 2/paraffin wax by using a scalpel after the SiO 2/paraffin wax mixed slurry is completely solidified, putting the mould into a box-type heating furnace, and arranging additivesThe hot temperature is 300 ℃, and after 1h, the resin and the paraffin are completely removed, thus obtaining the SiO2 die. Placing the mixture in a copper film evaporator for 1 minute to obtain copper/SiO with a copper film coated on the surface 2 A composite material.
(3) Preparing a required liquid metal-based material, and pouring the liquid metal-based material into a secondary mould by an electrowetting method and solidifying the liquid metal-based material;
the method specifically comprises the following steps: 100g of bismuth-tin-silver alloy is taken and preheated to 150 ℃ in a beaker to be fully melted. By electrowetting on SiO 2 Adding electrode plates on the upper surface and the lower surface of the die, pouring the liquid bismuth-tin-silver alloy into the die under the voltage of 150V to fill the cavity of the die, and then placing the die in an environment at 0 ℃ for 1 hour to completely solidify the liquid alloy.
(4) Removing the metal film coated on any surface of the secondary die to expose the secondary die material coated by the metal film, placing the secondary die material in a secondary die dissolving agent to remove the secondary die, and then placing the secondary die material in a metal film dissolving agent to remove the metal film to obtain the required metal-based metamaterial;
the method specifically comprises the following steps: grinding SiO with abrasive paper 2 A metal film on the outer surface of one side of the mold to form SiO in the mold 2 And (4) exposing. Completely immersing the substrate in 40 wt% hydrofluoric acid liquid and standing until SiO is obtained 2 Completely dissolving and taking out. And (3) sequentially washing and drying the alloy by using absolute ethyl alcohol and deionized water, putting the alloy into 25-28 wt% of concentrated ammonia water with oxygen introduced to completely dissolve the copper film, washing the copper film by using the deionized water, and drying the copper film to obtain the required structured alloy metal-based metamaterial, namely bismuth tin silver.
Example 3
The embodiment aims to realize three-dimensional structural molding of the metal electronic ink composite material, and the specific preparation process comprises the following steps:
(1) preparing an alkali soluble resin primary mould with a required three-dimensional structure by using a 3D printing technology;
the method specifically comprises the following steps: 50g of the comonomer N, N-dimethylacrylamide and 50g of the comonomer methyl methacrylate were weighed using an electronic balance and both were poured into a beaker and mixed well. Subsequently 45g of the crosslinking cleavage agent methacrylic anhydride was weighed out and poured into a beaker to mix well. And placing the mixed solution in a magnetic stirring water bath kettle, carrying out oil bath stirring at 50 ℃ for 40 minutes, and then sequentially adding 15g of filling agent polyvinylpyrrolidone and 15g of photosensitizer aroylphosphine oxide. The temperature is kept and stirring is continued for 3 hours, and the alkali-soluble photosensitive resin can be obtained. And printing the resin mold by using a 3D printer.
(2) Immersing the resin primary mould in a molten secondary mould material, solidifying the secondary mould material, completely coating the resin primary mould, polishing the solidified secondary mould material to completely expose the upper surface of the resin primary mould, removing the exposed resin primary mould through a resin removal primary mould process, and uniformly coating a layer of metal film in an evaporation machine to obtain the secondary mould;
the method specifically comprises the following steps: the resulting alkali-soluble photosensitive resin mold was washed with deionized water and dried. 100g of paraffin is put into a beaker and placed in a water bath heating pot at the temperature of 60 ℃, and the mixture is stirred until the paraffin is completely melted. And (3) completely immersing the resin mould in the paraffin for 1 hour, then taking out the resin mould, and cooling to solidify the paraffin. And polishing the paraffin on the surface of the mould to completely expose the upper surface of the primary resin mould, standing the mould in a sodium hydroxide solution with the mass fraction of 5% for 2 hours until the alkali-soluble resin is completely dissolved, taking out the mould, washing the mould with deionized water, and drying to obtain the required paraffin secondary mould. Placing the composite material in a copper film evaporator for 1 minute to obtain the copper/paraffin composite material with the surface coated with a layer of copper film.
(3) Preparing a required metal electronic ink composite material, and pouring the metal electronic ink composite material into a secondary mould by an electrowetting method and solidifying the metal electronic ink composite material;
the method specifically comprises the following steps: 50ml of liquid metal electronic ink (ZXYT YM-02) is put into a beaker, 5g of chopped carbon fiber powder is added, and the mixture is placed into a magnetic stirrer to be stirred for 2 hours until the carbon fibers are uniformly dispersed in the liquid metal electronic ink. Adding electrode plates on the upper and lower surfaces of a paraffin wax mould by an electrowetting method, pouring the metal electronic ink composite material into the mould under the voltage of 150V to fill the cavity of the mould, and then placing the mould in an environment at 0 ℃ for 1 hour to completely solidify the metal electronic ink composite material.
(4) Removing the metal film coated on any surface of the secondary die to expose the secondary die material coated by the metal film, placing the secondary die material in a secondary die dissolving agent to remove the secondary die, and then placing the secondary die material in a metal film dissolving agent to remove the metal film to obtain the required metal-based metamaterial;
the method specifically comprises the following steps: this step will be carried out while maintaining an environment of 20 ℃. And (3) grinding the metal film on the outer surface of one side of the paraffin mould by using sand paper to expose the paraffin in the paraffin mould. Completely immersing it in carbon tetrachloride CCl 4 Standing in the liquid until the paraffin is completely dissolved, and taking out. After being washed and dried by absolute ethyl alcohol and deionized water in sequence, the copper film is placed in 100ml of ferric trichloride solution with the mass fraction of 20% to completely dissolve the copper film, and ice blocks are added during the process to keep the temperature of the solution below 20 ℃. And taking out the metal electronic ink composite material without the copper film, washing with low-temperature deionized water, and drying to obtain the required structured metal electronic ink composite material.
The present invention includes but is not limited to the embodiments described above, and any equivalent or partial modifications made under the spirit of the present invention are considered to be within the scope of the present invention.
Claims (5)
1. A preparation method of a metal-based metamaterial based on indirect additive manufacturing is characterized by comprising the following steps:
(1) preparing an alkali soluble resin primary mould with a required three-dimensional structure by using a 3D printing technology;
(2) immersing an alkali-soluble resin primary mould in a molten secondary mould material, solidifying the secondary mould material, completely coating the alkali-soluble resin primary mould, polishing the solidified secondary mould material to completely expose the upper surface of the alkali-soluble resin primary mould, removing the exposed alkali-soluble resin primary mould by using a primary mould removing process, and then uniformly coating a layer of metal film in a vapor deposition machine to obtain a secondary mould;
(3) preparing a required liquid metal-based material, and pouring the liquid metal-based material into a secondary mould by an electrowetting method and solidifying the liquid metal-based material;
(4) removing the metal film coated on any surface of the secondary die to expose the secondary die material coated by the metal film, placing the secondary die material in a secondary die dissolving agent to remove the secondary die, and then placing the secondary die material in a metal film dissolving agent to remove the metal film to obtain the required metal-based metamaterial;
the coated metal film adopts copper or nickel, and the coated metal film has the function of preventing the formed metal-based metamaterial from being dissolved due to direct contact with a secondary mold dissolving agent;
the secondary mould material comprises one of the following components: paraffin wax, molten paraffin wax and S i O 2 Mixed solution of nano particles, wherein molten paraffin accounts for 25-50% of the total mass;
the secondary mold dissolving agent is used for fully dissolving a secondary mold material and does not react with the metal film, and when the secondary mold material is paraffin, the secondary mold dissolving agent comprises one of the following components: toluene, xylene, CCl 4 (ii) a When the secondary mold material is molten paraffin and S i O 2 When the liquid is mixed, the secondary mold dissolving agent is hydrofluoric acid liquid with the weight percentage of 30-50 percent;
the metal film dissolving agent is used for fully dissolving the plated metal film and does not react with the metal-based metamaterial, and comprises one of the following conditions: 10-20 wt% ferric trichloride solution, 25-28 wt% strong ammonia water with oxygen.
2. The method for preparing the metal-based metamaterial based on indirect additive manufacturing as claimed in claim 1, wherein the alkali-soluble resin is prepared by: according to parts by weight: selecting 40-60 parts of comonomer N, N-dimethylacrylamide, 40-60 parts of methyl methacrylate and 40-50 parts of crosslinking cracking agent methacrylic anhydride, mixing under oil bath heating at 40-60 ℃, then respectively adding 10-20 parts of filling polyvinylpyrrolidone and 10-20 parts of photoinitiator aroylphosphine oxide or bis-benzoylphenylphosphine oxide, and uniformly dispersing.
3. The method for preparing the metal-based metamaterial based on indirect additive manufacturing as claimed in claim 1, wherein the liquid metal-based material comprises one of: gallium, indium, tin, bismuth tin silver alloy, metal matrix composite.
4. The method for preparing the metal-based metamaterial based on indirect additive manufacturing as claimed in claim 1, wherein the primary mold process for removing the alkali-soluble resin comprises: when the secondary mould material is paraffin, placing the secondary mould material in an aqueous solution of sodium hydroxide or other alkaline solutions to remove the alkali-soluble resin primary mould; when the secondary mold material is molten paraffin and SiO 2 The mixed solution is placed into a box-type heating furnace, and is burned at the high temperature of 300-350 ℃ for 1-1.5 hours to remove the alkali soluble resin primary mould.
5. The method for preparing the metal-based metamaterial based on indirect additive manufacturing as claimed in claim 1, wherein the electrowetting method is: adding electrode plates on the upper surface and the lower surface of a mould to be poured, contacting the upper electrode plate with a metal-based material, and applying a voltage of 150-200V, so that the wettability of liquid drops on the surface of the mould is changed, and the pouring effect is improved.
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