CN114559049A - Batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive - Google Patents
Batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive Download PDFInfo
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- CN114559049A CN114559049A CN202210319222.4A CN202210319222A CN114559049A CN 114559049 A CN114559049 A CN 114559049A CN 202210319222 A CN202210319222 A CN 202210319222A CN 114559049 A CN114559049 A CN 114559049A
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/10—Formation of a green body
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/38—Process control to achieve specific product aspects, e.g. surface smoothness, density, porosity or hollow structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/60—Treatment of workpieces or articles after build-up
- B22F10/62—Treatment of workpieces or articles after build-up by chemical means
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/60—Treatment of workpieces or articles after build-up
- B22F10/64—Treatment of workpieces or articles after build-up by thermal means
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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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
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- 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
- B33Y80/00—Products made by additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/04—Tubes; Rings; Hollow bodies
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/241—Chemical after-treatment on the surface
- B22F2003/242—Coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention provides a batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive materials, which comprises the steps of preprocessing a printed base material, and efficiently printing a metal mesh grid structure on the preprocessed base material by adopting a single-flat-plate electrode electric field driving multi-nozzle jet deposition micro-nano 3D printing method; sintering the printed metal mesh at high temperature or low temperature; cleaning the sintered sample piece, removing dirt attached to the base material and the surfaces of the grids generated in the sintering process, and air-drying to remove redundant water; placing the air-dried metal mesh grid into an electroforming pool, electroforming by using a micro-electroforming power supply, and depositing a layer of magnetic material on the surface of the conductive mesh grid structure and wrapping the magnetic material to form a conductive/magnetic composite material; taking the electroformed structure out of the electroforming tank, ultrasonically shaking and washing the electroformed structure by deionized water, removing residual materials on a plated part, and drying the electroformed structure by nitrogen; the invention realizes the large-scale manufacture of the oversized broadband high-performance transparent electromagnetic shielding glass by the additive manufacturing technology.
Description
Technical Field
The invention relates to the technical field of transparent electromagnetic shielding glass processing, in particular to a batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive materials.
Background
The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.
The electromagnetic shielding glass is a light-transmitting observation window device with the function of attenuating the radiation power of electromagnetic waves, can effectively prevent harmful electromagnetic energy from being transmitted from one side of the window to the other side, and also has higher visible light (infrared light and the like) transmittance so as to ensure that the transmission of optical signals is not influenced. Its main functions include: electromagnetic radiation interference is effectively shielded, and normal work of instrument equipment is guaranteed; electromagnetic wave signals passing through the window are effectively reduced, information leakage is prevented, and the safety of confidential information is guaranteed; the electromagnetic radiation pollution is effectively reduced, and the radiation damage to the human body is reduced; the electromagnetic stealth of an aircraft and the like is realized. At present, the electromagnetic shielding glass is widely applied to various electromagnetic compatibility occasions, including civil fields such as cabinets, cases, power systems, thermotechnical instruments, precision laboratories, medical instruments, electronic communications, government offices, banks and financial security institutions, and national defense military safety fields such as cabin transparent pieces of fifth generation fighters, cruise missile optical windows, spacecraft optical windows, shelter communication vehicles, missiles and radar covers, military flat panel displays, military reinforcement computers, aircraft windows and instruments, and especially along with the wide application of 5G communications, the electromagnetic shielding glass is more and more widely applied to the fields such as information communications, autopilot and modern electromagnetic warfare, and the performance requirements of the electromagnetic shielding glass are higher and higher.
At present, the most common electromagnetic shielding glass is mesh grid type or film coating type electromagnetic shielding glass. The film-coated electromagnetic shielding glass is usually formed by depositing a layer of transparent conductive film on the surface of various transparent base materials by adopting the processes of magnetron sputtering and the like; most of the materials used for the electromagnetic shielding glass are Indium Tin Oxide (ITO), metal alloys and other oxides, the materials are scarce and expensive, and only can effectively transmit visible light, so that the shielding efficiency is low. Because the reflection loss of the electromagnetic wave in the medium and high frequency band (more than 100kHz) is related to the conductivity of the electromagnetic shielding material, stronger electromagnetic reflection can be obtained only by lower surface resistance, but the improvement of the surface resistance requires the improvement of the thickness of a coating film, so that the light transmittance of the electromagnetic shielding material is greatly reduced, and the electromagnetic shielding performance and the light transmittance have a mutual restriction relationship, so that the high-performance requirement is difficult to meet. The grid type electromagnetic shielding glass is formed by combining a metal grid with electromagnetic shielding effect and glass, and simultaneously realizes the functions of electromagnetic protection and light transmission. The implementation modes of the electromagnetic shielding glass mainly include two types, namely interlayer metal wire mesh electromagnetic shielding glass and etching mesh grid electromagnetic shielding glass. The mesh area of the electromagnetic shielding glass without patterns is a transparent substrate, light can normally penetrate through the mesh area, and the mesh area is made of high-conductivity metal materials such as silver, copper, nickel, stainless steel and the like, and simultaneously meets the light transmission and electromagnetic shielding performances. The electromagnetic shielding glass with sandwiched metal wire net is made of transparent material such as organic or inorganic glass and film and metal wire net through high-temp. and high-pressure sandwich process. The electromagnetic shielding glass has the performances of noise reduction, explosion prevention, weather resistance, corrosion resistance, high stability and the like. The etching of the mesh electromagnetic shielding glass is to etch a mesh groove on the surface of organic or inorganic glass coated with photoresist by utilizing processes such as laser, plasma etching and the like, then plate a high-conductivity metal film on the surface, finally wash away the photoresist and the metal film on the surface of the photoresist, retain the metal in the groove in a glass substrate to obtain a metal mesh, and effectively improve the conductivity while ensuring high light transmittance by increasing the depth-to-width ratio of the mesh structure. The grid type electromagnetic shielding glass has variable structural parameters, can be flexibly designed according to the use environment, and simultaneously realizes the broadband high light transmittance from near infrared to visible light. The metal mesh gradually becomes one of the most potential and effective techniques in the optical window electromagnetic shielding technology by virtue of the diversity of the structural parameters and materials, and the excellent light transmission and electromagnetic shielding properties.
The inventor finds that the existing metal mesh electromagnetic shielding glass manufacturing technology such as an interlayer process, a photoetching process, a nano-imprinting process, a laser process, an etching process and the like has complex production process, high equipment cost and low efficiency, especially the existing technology can not realize the high-efficiency low-cost manufacturing of the large-size metal mesh, and particularly the manufacturing of the metal mesh with the super-large size of more than 18 inches seriously restricts the wide industrial application of the product. In addition, most of the existing products are made of single high-conductivity materials, and although the products have excellent high-frequency electromagnetic shielding performance, the products have poor shielding effect on low-frequency electromagnetic waves. With the development and utilization of electromagnetic wave bands becoming wider and wider, the electromagnetic shielding material should be developed in the directions of wide band and high shielding effect, and the shielding material with single function cannot meet the requirement of full-band strong electromagnetic shielding performance.
Disclosure of Invention
In order to solve the defects of the prior art, the invention adopts a micro-nano 3D printing technology of single-flat-plate electrode electric field driving multi-nozzle jet deposition, and the multi-nozzle parallel printing is integrally formed, so that a large-area metal mesh grid structure can be printed on a printing substrate at high precision, high light transmittance can be ensured, and batch manufacturing can be realized; the invention adopts a precise micro-electroforming technology to deposit a metal layer with high magnetic conductivity on the surface of a metal grid with high electric conductivity so as to form an electric conduction/magnetic conduction composite material structure; on one hand, the invention solves the problem that a single shielding material cannot simultaneously meet the electromagnetic shielding of low frequency and high frequency bands, can realize full-frequency (wide-band) strong electromagnetic shielding, on the other hand, particularly, the production efficiency is greatly improved (the electroforming time of large-size electromagnetic shielding glass is reduced to 5 minutes) by a single-step through body forming precise micro electroforming technology, and the invention also has good weather resistance and corrosion resistance and can be used in harsh natural environment; the novel composite micro-nano additive manufacturing process provided by the invention realizes the manufacturing of the ultra-large-size high-performance metal mesh transparent electromagnetic shielding glass completely through the additive manufacturing technology, solves the problem that the manufacturing of the ultra-large-size high-performance metal mesh cannot be realized in the prior art, and has the outstanding advantages of high efficiency, low cost, high material utilization rate, no pollution, green manufacturing and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a large-size electromagnetic shielding glass batch production method based on composite micro-nano additive manufacturing is characterized in that an electromagnetic shielding material of the large-size electromagnetic shielding glass is a conductive/magnetic conductive composite material structure formed by wrapping at least one layer of magnetic conductive material with high magnetic conductivity on the surface of a high-conductive metal grid;
the batch production method comprises the following processes:
pre-treating a print substrate, the pre-treating comprising: cleaning, drying and dewatering;
a conductive metal mesh grid structure is efficiently printed on a pretreated base material by adopting a single-plate electrode electric field driven multi-nozzle jet deposition micro-nano 3D printing method, the material of the conductive metal mesh grid structure comprises but is not limited to conductive silver paste and conductive copper paste, the type of the metal mesh grid comprises but is not limited to square, diamond, triangle and hexagon, the line width of the metal mesh grid structure is 0.5-50 mu m, the period is 20-500 mu m, and the height is 2-20 mu m; the number of the multiple nozzles is not less than 5, and the nozzle spacing is determined according to the period of printing the metal mesh grid;
sintering the printed metal mesh grid at high temperature or low temperature in a vacuum environment or under the protection of inert gas;
cleaning the sintered sample piece, removing dirt attached to the base material and the surface of the grid in the sintering process, and air-drying to remove redundant moisture;
placing the air-dried metal mesh grid into an electroforming pool, electroforming by using a micro electroforming power supply, depositing a layer of magnetic material on the surface of the conductive mesh grid structure and wrapping the magnetic material to form a conductive/magnetic composite material, wherein the magnetic material comprises but is not limited to nickel and iron-nickel alloy, and the thickness of the magnetic material is 3-20 micrometers;
taking the electroformed structure out of the electroforming tank, ultrasonically shaking and washing the electroformed structure by using deionized water, removing residual materials on a plated part, and drying the electroformed structure by using nitrogen;
wherein, the electroforming process comprises the following steps:
attaching a conductive copper adhesive tape to one side of the conductive metal mesh grid subjected to air drying treatment, connecting the conductive copper adhesive tape to a cathode of micro-electroforming equipment, connecting an electroforming deposition metal with an anode, placing the electroforming deposition metal in electroforming liquid, adding an anode activator into the electroforming liquid to improve the solubility of the anode, adding a buffer to slow down the increase of the pH value of the solution in an anode area, and adding a pinhole-preventing agent to reduce the surface tension of the solution;
starting the micro electroforming equipment, controlling the temperature and the PH value of the electroforming solution within a preset range through a constant temperature system and a PH value monitoring system, wherein the current density is smaller than a preset value; flushing by using a circulating pump, and stirring the plating solution; the ultrasonic generator is used for discharging bubbles attached to the surface of the electrode in the processing process, and simultaneously, concentration polarization is reduced and the flow field characteristic is improved.
As an alternative implementation, the pretreatment of the printing substrate includes:
cleaning, namely cleaning the printing substrate by using deionized water to completely remove dirt and dust on the surface;
drying, then drying by using nitrogen or drying in a heating box, removing residual deionized water on the surface and ensuring the cleanness of the surface of the base material;
and (3) performing hydrophobic treatment, and finally coating a layer of ultrathin coating on the printing substrate by adopting a precise coating mode such as spin coating or slit coating and the like and curing, so that the printing quality is improved conveniently.
As an alternative implementation, the substrate material includes, but is not limited to, glass, sapphire, polyimide, PMMA, and the like.
As an alternative implementation, the drying manner includes, but is not limited to, oven drying and inert gas drying.
Coatings are applied to a print substrate for the purpose of improving print quality, and as an alternative implementation, the coatings include, but are not limited to, nanocoating liquids and resins.
As an alternative realization, the coating thickness is 3 μm to 10 μm.
Alternatively, coating means include, but are not limited to, spin coating, knife coating, and slot coating.
As an alternative implementation, the coating curing means includes, but is not limited to, heat curing, uv curing, and infrared curing.
Further, a metal mesh structure is efficiently printed on the pretreated base material by adopting a single-plate electrode electric field driving multi-nozzle jet deposition micro-nano 3D printing method, which comprises the following steps:
designing the size and the period of a required grid according to requirements, generating a corresponding processing code by using data processing software, and inputting the processing code into a single-flat-plate electrode electric field driven multi-nozzle jet deposition micro-nano 3D printing device;
placing a printing material into a cartridge of a printing device; connecting a nitrogen cylinder to the charging barrel through a pneumatic valve; connecting a direct current power supply to a flat electrode of the printing device through a lead;
the coated printing substrate is placed on a printing platform of a printing apparatus. And starting the 3D printing device, and finishing the printing of the whole metal grid by combining the optimized 3D printing process parameters according to the designed and optimized parameters of the grid type (square, diamond, triangle, hexagon and the like), the size (line width, period and the like), the geometric arrangement and the like.
As an optional implementation mode, a needle head with the inner diameter of 1-100 microns is selected as the used printing spray head, the distance between the printing spray head and the printing substrate is 20-200 microns, the air pressure of the printing device is 50-200 kpa, the power supply voltage of the printing device is 100-1500V, and the printing speed of the printing device is 5-50 mm/s.
As an optional implementation manner, the high-temperature or low-temperature sintering of the printed metal grid in a vacuum environment or under the protection of inert gas includes:
placing the printed metal mesh grid in a sintering furnace for sintering, wherein the sintering process is carried out in a vacuum environment or under the protection of inert gas; the coated coating is removed under the action of high temperature, so that the metal mesh grid and the substrate are fully combined, and the bonding strength between the metal mesh grid and the substrate is improved; and the high-temperature sintering can also remove the polymer auxiliary agent contained in the printed metal slurry, so that the metal mesh grid has better conductivity and the electromagnetic shielding performance of the metal mesh grid in a high-frequency band is improved.
As an optional implementation manner, cleaning the sintered sample, removing the contaminants attached to the substrate and the surface of the mesh during the sintering process, and air-drying to remove excess water includes:
cleaning, cleaning the sintered sample piece with deionized water to remove dirt attached to the substrate and the surface of the grid in the sintering process;
air-dry, then blow the deionized water on the sample surface with nitrogen.
As an alternative implementation, the sintering method includes, but is not limited to, vacuum sintering, atmosphere protection sintering, photonic sintering, and the like.
As an optional implementation mode, the sintering temperature is 100-700 ℃, and the sintering time is 3-30 min.
As an alternative implementation, the electroforming process, more specifically, includes:
pre-treating, adhering conductive copper adhesive tape on one side of the conductive metal grid, connecting to the cathode of the precise micro-electroforming equipment, connecting the metal plate to the anode, and placing in electroforming solution; an anode activator is added into the electroforming solution to improve the solubility of the anode, improve the conductivity and improve the dispersion capacity of the solution; the buffer is added to slow down the increase of the pH value of the solution in the anode area, so that higher anode current density can be used without precipitating hydroxide on the anode, and the effects of improving cathode polarization and improving cast layer properties are achieved; the anti-pinhole agent is added to reduce the surface tension of the solution, so that hydrogen bubbles are not easy to stay on the surface of the cathode, and the formation of pinholes is prevented;
electroforming, turning on a micro electroforming device, and adopting a smaller current density in order to reduce the surface roughness. Controlling the temperature and the pH value of the electroforming solution within a certain range through a constant temperature system and a pH value monitoring system; the circulating pump is used for flushing the plating solution, so that the plating solution is stirred; and the ultrasonic generator is used to quickly discharge bubbles attached to the surface of the electrode in the processing process and play a role in reducing concentration polarization and improving the flow field characteristics.
As an optional implementation mode, the temperature of the electroforming solution is 45-55 ℃, the pH value is 3-4.5, and the current density is 0.5A/m in the electroforming process2～3A/m2In the electroforming process, a circulating pump is used for sucking electroforming liquid out, filtering and discharging the electroforming liquid into an electroforming pool for flushing, wherein the flushing speed is 1-2 m/s.
Alternatively, the electroforming solution may be stirred by a method including, but not limited to, mechanical stirring, magnetic stirring, ultrasonic stirring, and the like.
As an optional implementation manner, taking the electroformed structure out of the electroforming tank, ultrasonically shaking and washing the electroformed structure with deionized water, removing residual materials on a plated part, and drying the electroformed structure with nitrogen, the method comprises the following steps:
and taking the electroformed structure down from the cathode, removing the copper adhesive tape on one side, ultrasonically shaking and washing the electroformed structure by using deionized water to completely remove residual materials (electroforming solution, impurities and the like) on the plated part, and drying redundant water by using nitrogen.
As an optional implementation mode, the ultrasonic vibration washing time is 3-5 min.
Compared with the prior art, the invention has the beneficial effects that:
1. the manufacturing method has the advantages that the manufacturing method is large in size, the existing manufacturing technology of the metal mesh electromagnetic shielding glass, such as an interlayer process, a photoetching process, a nanoimprint process, a laser process, a plasma etching process and the like, the production process is complex, the requirement on equipment is high, especially the existing technology cannot realize simple manufacturing of large-size metal meshes, and especially the manufacturing of the metal meshes with the size larger than 18 inches is realized; the micro-nano 3D printing technology adopting the single-flat-plate electrode electric field to drive the multiple spray heads to spray and deposit is simple in process, and can be used for directly printing an oversized metal grid structure, and meanwhile, the single-step efficient body forming is realized by combining and adopting precise micro-electroforming nickel (nickel-iron alloy and the like), so that the production efficiency is greatly improved.
2. The printing method has high performance, on one hand, the micro-nano 3D printing technology of multi-nozzle jet deposition driven by a single-plate electrode electric field can simply print the line width of 0.2-100 mu m, and the light transmittance is more than 90% by controlling the grid period; on the other hand, the electromagnetic shielding material also has excellent full-band electromagnetic shielding performance; the metal mesh grid printed by the printing technology has very low resistance (square resistance) and more mesh number after high-temperature sintering, so that the metal mesh grid has excellent shielding performance in medium-high frequency magnetic fields (more than 100 kHz); meanwhile, the surface layer of the electroformed composite metal grid structure is made of metal materials with high magnetic permeability, such as nickel, iron-nickel alloy and the like, and the shielding material has excellent shielding performance in a low-frequency magnetic field less than 100 kHz; therefore, the transparent electromagnetic shielding device prepared by the method has the outstanding advantages of excellent performance (low sheet resistance, high light transmittance, wide frequency band and strong electromagnetic shielding effectiveness).
3. The metal grid prepared by the invention has a composite structure, and the inner layer is made of high-conductivity materials such as metal silver and the like; the outer layer is made of magnetic conductive material such as metallic nickel, and the conductive/magnetic conductive composite structure has very low resistance and magnetic resistance, and can particularly realize full-spectrum electromagnetic shielding (low frequency, medium-high frequency, near infrared, far infrared and millimeter wave).
4. High efficiency, and the traditional single-nozzle printing time is too long to meet the requirements of actual production. The invention adopts the array type nozzles, and multiple nozzles are printed in parallel and integrally formed, thereby greatly reducing the preparation period; and, through electroforming (single step body shaping), can prepare the electric conduction/magnetic conduction structure simply and high-efficiently, suitable for the large-scale production in batches.
5. The micro-nano 3D printing technology is manufactured in batch, the single flat plate electrode electric field used by the invention drives multiple spray heads to spray and deposit, the printing efficiency is high by using the multiple spray heads to print in parallel, and the electroforming technology is also an efficient additive manufacturing technology and can form a single step (greatly improving the production efficiency); therefore, the method can realize the batch manufacturing of the oversized high-performance metal mesh transparent electromagnetic shielding glass and meet the industrial production requirements.
6. The defect self-repairing capacity, high stability and consistency are realized; the defects of breakage, unevenness and the like exist in the directly printed conductive grid, so that the conductivity and the stability and consistency of the product are seriously influenced; according to the invention, through a precise micro-electroforming technology, the surface fracture and defect of the printing grid can be repaired, a continuous and compact conductive network is formed, and the stability and consistency of the product performance can be ensured by controlling electroplating parameters; the problem of the biggest super large-size electromagnetic shielding glass is solved.
7. The composite structure metal grid has the advantages of good weather resistance, corrosion resistance and high stability, has good bonding property with a glass substrate, has good service life, has excellent weather resistance and corrosion resistance, and can be used in harsh natural environment.
8. The invention provides a novel composite micro-nano additive manufacturing process, which is low in cost and flexible in manufacturing, and realizes the manufacturing of the ultra-large-size high-performance metal mesh transparent electromagnetic shielding glass completely by an additive manufacturing technology; the additive manufacturing technology has the remarkable advantages of metal saving, strong adaptability and customization; the ordered grid structure with various shapes (squares, diamonds and the like), periods and line widths can be flexibly printed according to the requirement with high precision, and various application requirements are met.
9. The invention combines the single-plate electrode electric field driving multi-nozzle jet deposition micro-nano 3D printing and precise micro-electroforming technology, realizes the high-efficiency low-cost batch manufacturing method of the oversized high-performance metal mesh grid transparent electromagnetic shielding glass, and provides a subversive technical solution for the large-scale production of the oversized high-performance metal mesh grid transparent electromagnetic shielding glass.
Advantages of additional aspects of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a schematic view of a transparent electromagnetic shielding glass with a double-layer metal grid according to an embodiment of the present invention.
FIG. 2 is a flow chart of a manufacturing process according to an embodiment of the present invention.
Fig. 3 is a schematic diagram of micro-nano 3D printing of single-plate electrode electric field driven multi-nozzle jet deposition.
Fig. 4 is a schematic view of a micro electroforming process according to an embodiment of the present invention.
Wherein, 1-glass; 2-nickel; 3-silver; 4-a high voltage power supply; 5-a printing module; 6-printing nozzle; 7-a feeding module; 8-a glass substrate; 9-copper plate electrodes; 10-back pressure; 11-a magnetically permeable layer; 12-highly conductive material.
Detailed Description
The invention is further described with reference to the following figures and examples.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
Example 1:
fig. 1 is a schematic view of an Ag/Ni composite double-layer metal grid transparent electromagnetic shielding glass to be manufactured by the present invention, which includes: glass 1, nickel 2 and silver 3, parameters of the Ag/Ni composite transparent electromagnetic shielding glass to be manufactured by the embodiment: the line width was 7 μm and the period was 200. mu.m.
Taking the Ag/Ni composite transparent electromagnetic shielding glass of this embodiment as an example, a specific process for manufacturing the Ag/Ni composite transparent electrical shielding glass based on the method and apparatus proposed in this embodiment will be specifically described with reference to fig. 1, fig. 2, fig. 3, and fig. 4.
S1: and (4) pretreating the glass substrate.
(1) And (4) cleaning, namely repeatedly cleaning the printing substrate by using deionized water to thoroughly remove dirt, dust and the like on the surface.
(2) And (4) drying, and then drying in a heating box at 70 ℃ for 30min to remove residual deionized water on the surface and ensure the cleanness of the surface.
(3) Performing surface hydrophobic treatment, namely selecting float glass with the thickness of 2mm and the size of 400mm multiplied by 400mm as a printing substrate, ultrasonically cleaning the printing substrate by deionized water for 10min, and then drying the printing substrate by nitrogen to ensure the cleanness of the surface. The glass substrate was coated with a 6 μm thick nanocoating solution using a slot coating process. And finally, placing the float glass substrate coated with the nano coating in a vacuum drying oven, heating and curing for 1h at 70 ℃, and taking out for later use after the coating is completely cured, wherein the thickness of the prepared coating is about 5 mu m.
S2: and printing a nano Ag metal mesh grid.
The method comprises the following steps of adopting a single-plate electrode electric field to drive a multi-nozzle jet deposition micro-nano 3D printing device to print a silver mesh grid on a high-light-transmission glass substrate coated with a nano coating, wherein the overall size of the mesh grid in the embodiment is 400 x 400mm, and the high light transmission rate can be realized by controlling the line width and the period of the printed silver mesh grid, wherein the line width is controlled to be 7 microns, and the period is 200 microns; the printing material is selected from conductive silver paste, and the working principle of the printing device is shown in fig. 3.
A single-plate electrode electric field driven multi-nozzle jet deposition micro-nano 3D printing device comprises a high-voltage power supply 4, a printing module 5, a printing nozzle 6, a feeding module 7, a glass substrate 8, a copper plate electrode 9 and backpressure 10.
The specific process comprises the following steps:
(1) preprocessing, namely designing the size and line period of a required grid according to requirements, generating corresponding processing codes by using data processing software, and inputting the processing codes into a single-flat-plate electrode electric field driven multi-nozzle jet deposition micro-nano 3D printing device; placing printing material conductive silver paste into a charging barrel of a printing device; connecting a nitrogen cylinder to the upper part of the charging barrel through a conduit; and connecting the direct-current high-voltage power supply to a printing nozzle of the printing device through a lead.
(2) Printing a metal mesh grid, and placing the glass printing substrate coated with the nano coating on a printing platform of a printing device; the method comprises the following steps of starting a single-flat-plate electrode electric field to drive a multi-nozzle jet deposition micro-nano 3D printing device, starting a direct-current power supply, and having the following main process parameters: voltage 1000V, air pressure 100kPa, printing speed 50mm/s, height between the nozzle and the hard printing substrate 100 μm. And according to the designed and optimized parameters such as the type and the geometric arrangement of the grid, the printing of the whole silver grid is completed by combining the optimized 3D printing process parameters.
S3: and (6) conducting treatment.
In the embodiment, the silver mesh grid printed in the step 2 is placed in a sintering furnace for sintering, and the sintering temperature is 600 ℃. Sintering for 5min, rapidly taking out and cooling to room temperature; the coated coating is removed under the action of high temperature, so that the printed mesh grid and the glass substrate are fully combined, and the bonding strength between the printed mesh grid and the glass substrate is improved; and the high-temperature sintering can also remove the polymer auxiliary agent contained in the printed conductive silver paste, so that the silver grid has better conductivity, and the electromagnetic shielding performance of the silver grid in a high-frequency band is improved.
S4: cleaning and air-drying.
(1) And (3) cleaning, namely repeatedly cleaning the sintered sample piece by using deionized water to remove dirt and the like attached to the base material and the surface of the grid in the sintering process.
(2) Air-dry, then blow the deionized water on the sample surface with nitrogen.
S5: and micro-electroforming a Ni magnetic conduction layer.
In this embodiment, a layer of Ni metal layer with high magnetic conductivity is deposited on the surface of the Ag mesh with high electrical conductivity by using a precision micro electroforming technique to form a conductive/magnetic conductive composite structure, so as to shield the full-band electromagnetic wave, as shown in fig. 4, and finally, a conductive/magnetic conductive composite structure formed by the high electrical conductive material 12 and the magnetic conductive layer 11 is formed.
The specific process comprises the following steps:
(1) and (4) preprocessing.
And (3) attaching a conductive copper adhesive tape to one side of the conductive silver grid subjected to high-temperature sintering and cleaning in the steps, connecting the conductive silver grid to a cathode of precise micro-electroforming equipment, connecting a pure Ni plate to an anode, and placing the pure Ni plate in 500g/L nickel sulfamate electroforming solution. Adding 15g/L nickel chloride as an anode activator into the electroforming solution, so that the solubility of an anode is improved, the conductivity is improved, and the dispersion capacity of the solution is improved; adding 30g/L boric acid as buffering agent to slow down the increase of the pH value of the solution in the anode area, so that higher anode current density can be used without separating hydroxide on the anode, and the effects of improving cathode polarization and casting layer properties are achieved; 0.15g/L sodium dodecyl sulfate is added as a pinhole preventing agent to reduce the surface tension of the solution, so that the generated hydrogen bubbles are not easy to stay on the surface of the cathode, thereby preventing the formation of pinholes.
(2) And (4) electroforming.
Starting a precise micro-electroforming device, and selecting a lower current density to reduce the surface roughness, wherein the current density is 0.6A/dm2The electroforming time is 3 min. The temperature of the electroforming solution is controlled at 50 ℃ through a constant temperature system, the pH value is controlled at 4 through a pH value monitoring system, the solution is flushed through a circulating pump at the flushing speed of 1.5m/s, the plating solution is stirred, and the concentration polarization is reduced; and an ultrasonic generator (with the power of 500W) is used for rapidly discharging bubbles attached to the surface of the electrode in the processing process and simultaneously playing the roles of reducing concentration polarization and improving the flow field characteristics.
S6: and (5) post-treatment.
And taking the electroformed structure down from the cathode, removing the copper adhesive tape on one side, ultrasonically shaking and washing for 5min by using deionized water, completely removing residual materials (electroforming solution, impurities and the like) on the plated part, and drying by using nitrogen.
The equipment used in this embodiment mainly includes: the single-plate electrode electric field drives a multi-nozzle jet deposition micro-nano 3D printing device; precision fine electroforming equipment; a spin coater; sintering furnace; a vacuum drying oven; ultrasonic cleaning machines, and the like.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Example 2:
the parameters of the copper/iron-nickel alloy composite transparent electromagnetic shielding glass to be manufactured by the embodiment are as follows: the line width is 10 μm, the period is 150 μm, and the specific process for manufacturing the copper/iron-nickel alloy composite transparent electric shielding glass based on the method and the device is as follows:
s1: and (4) pretreating the glass substrate.
(1) And (4) cleaning, namely repeatedly cleaning the printing substrate by using deionized water to thoroughly remove impurities such as dust on the surface.
(2) And (4) drying, and then drying in a heating box at 70 ℃ for 30min to remove residual deionized water on the surface and ensure the cleanness of the surface.
(3) And (3) performing hydrophobic treatment, namely selecting float glass with the thickness of 2mm and the size of 400mm multiplied by 400mm as a printing substrate, ultrasonically cleaning the printing substrate by deionized water for 10min, and blow-drying the printing substrate by nitrogen to ensure the cleanness of the surface. Then about 5g of the liquid nano-coating is dropped on the float glass with a hard substrate and is spin-coated on a spin coater at the rotating speed of 2000r/min for 60 s. And finally, placing the float glass substrate spin-coated with the nano coating in a vacuum drying oven, heating and curing for 1h at 70 ℃, taking out for later use after the coating is completely cured, wherein the thickness of the prepared coating is about 5 mu m.
S2: and printing a nano Cu metal mesh grid.
The method comprises the following steps of adopting a self-developed single-plate electrode electric field to drive a multi-nozzle jet deposition micro-nano 3D printing device to print a copper grid on a high-light-transmission glass substrate coated with a nano coating, wherein the overall size of the grid is 400 x 400mm, and the high light transmission rate can be realized by controlling the line width and the period of the printed copper grid, wherein the line width is controlled to be 0 mu m, and the period is selected to be 150 mu m; the printing material is selected from conductive copper paste.
The specific process comprises the following steps:
(1) and (4) pretreatment.
Designing the size and line period of a required mesh grid according to requirements, generating a corresponding processing code by using data processing software, and inputting the corresponding processing code into a single-flat-plate electrode electric field driving multi-nozzle jet deposition micro-nano 3D printing device; placing printing material conductive copper paste into a charging barrel of a printing device; connecting a nitrogen cylinder to the upper part of the charging barrel through a conduit; and connecting the direct-current high-voltage power supply to a printing nozzle of the printing device through a lead.
(2) Printing a copper grid.
And (3) placing the glass printing substrate coated with the nano coating on a printing platform of a printing device. The method comprises the following steps of starting a single-flat-plate electrode electric field to drive a multi-nozzle jet deposition micro-nano 3D printing device, starting a direct-current power supply, and having the following main process parameters: the voltage is 1200V, the air pressure is 150kPa, the printing speed is 60mm/s, and the height between the spray head and the hard printing substrate is 100 mu m; and according to the design and the optimized parameters such as the type and the geometric arrangement of the mesh grid, the printing of the whole copper mesh grid is completed by combining the optimized 3D printing process parameters.
S3: and (6) conducting treatment.
In the embodiment, the copper grid printed in the step 2 is placed in a sintering furnace for sintering, and N is introduced into the furnace before sintering2As a protective gas, the copper mesh gate oxidation is prevented from influencing the conductivity, and the sintering temperature is 600 ℃. Sintering for 5min, quickly taking out and cooling to room temperature; the coated coating is removed under the action of high temperature, so that the printed mesh grid and the glass substrate are fully combined, and the bonding strength between the printed mesh grid and the glass substrate is improved; and the high-temperature sintering can also remove the polymer auxiliary agent contained in the printed conductive copper paste, so that the copper grid has better conductive performance, and the electromagnetic shielding performance of the copper grid in a high-frequency band is improved.
And 4, step 4: cleaning and air drying.
(1) And (3) cleaning, namely repeatedly cleaning the sintered sample piece by using deionized water to remove dirt and the like attached to the base material and the surface of the grid in the sintering process.
(2) Air-dry, then blow the deionized water on the sample surface with nitrogen.
S5: electroforming the iron-nickel alloy magnetic conduction layer.
In the embodiment, a layer of iron-nickel alloy with high magnetic conductivity is deposited on the surface of a Cu grid with high electric conductivity by using a precise micro electroforming technology to form a conductive/magnetic conductive composite structure so as to realize shielding of full-band electromagnetic waves.
The specific process comprises the following steps:
(1) and (4) preprocessing.
And (4) attaching a conductive copper adhesive tape to one side of the conductive copper grid cleaned and air-dried in the step (4), connecting the conductive copper adhesive tape to a cathode of precise micro-electroforming equipment, connecting a pure Ni plate to an anode, and placing the pure Ni plate in electroforming liquid with 180g/L nickel sulfate and 60g/L ferrous sulfate as main salts. Adding 15g/L sodium chloride into the electroforming solution to provide Cl & lt- & gt for the solution, improve the solubility of an anode, improve the conductivity and improve the dispersion capacity of the solution; adding 30g/L boric acid as buffer to slow down the increase of pH value of the solution in the anode region, so that the use of the solution can be realizedThe higher anode current density does not cause hydroxide precipitation on the anode, and simultaneously has the effects of improving cathode polarization and improving cast layer properties; 2g/L saccharin is added, so that the brightness of the electrodeposited layer is improved, the electrodeposited layer has compressive stress, the brittleness of the electrodeposited layer is reduced, and the ductility of the electrodeposited layer is increased; adding 1g/L antioxidant to prevent Fe2+Oxidation of (2); 0.15g/L sodium dodecyl sulfate is added as a pinhole preventing agent to reduce the surface tension of the solution, so that the generated hydrogen bubbles are not easy to stay on the surface of the cathode, thereby preventing the formation of pinholes.
(2) And (4) electroforming.
Starting a precise micro-electroforming device, and selecting a lower current density to reduce the surface roughness, wherein the current density is 1A/dm2The electroforming time is 2 min. The temperature of the electroforming solution is controlled at 55 ℃ through a constant temperature system, the pH value is controlled at 3 through a pH value monitoring system, the solution is flushed through a circulating pump at the flushing speed of 1.5m/s, the plating solution is stirred, and the concentration polarization is reduced; and an ultrasonic generator (with the power of 500W) is used for rapidly discharging bubbles attached to the surface of the electrode in the processing process and simultaneously playing the roles of reducing concentration polarization and improving the flow field characteristics.
S6: and (5) post-treatment.
And taking the electroformed structure down from the cathode, removing the copper adhesive tape on one side, ultrasonically shaking and washing for 5min by using deionized water, completely removing residual materials on the plated part, and drying by using nitrogen.
The equipment used in this embodiment mainly includes: the single-plate electrode electric field drives a multi-nozzle jet deposition micro-nano 3D printing device; precision fine electroforming equipment; a slit coater; a spin coater; sintering furnace; a vacuum drying oven; ultrasonic cleaning machines, and the like.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive materials is characterized by comprising the following steps of:
the electromagnetic shielding material of the large-size electromagnetic shielding glass is a conductive/magnetic conductive composite material structure formed by wrapping at least one layer of magnetic conductive material with high magnetic conductivity on the surface of a high-conductive metal mesh grid;
the batch production method comprises the following processes:
pre-treating a print substrate, the pre-treating comprising: cleaning, drying and dewatering;
a conductive metal mesh grid structure is efficiently printed on a pretreated base material by adopting a single-plate electrode electric field driven multi-nozzle jet deposition micro-nano 3D printing method, the material of the conductive metal mesh grid structure comprises but is not limited to conductive silver paste and conductive copper paste, the type of the metal mesh grid comprises but is not limited to square, diamond, triangle and hexagon, the line width of the metal mesh grid structure is 0.5-50 mu m, the period is 20-500 mu m, and the height is 2-20 mu m; the number of the multiple nozzles is not less than 5, and the nozzle spacing is determined according to the period of printing the metal mesh grid;
sintering the printed metal mesh grid at high temperature or low temperature in a vacuum environment or under the protection of inert gas;
cleaning the sintered sample piece, removing dirt attached to the base material and the surfaces of the grids generated in the sintering process, and air-drying to remove redundant water;
placing the air-dried metal mesh grid into an electroforming pool, electroforming by using a micro electroforming power supply, depositing a layer of magnetic material on the surface of the conductive mesh grid structure and wrapping the magnetic material to form a conductive/magnetic composite material, wherein the magnetic material comprises but is not limited to nickel and iron-nickel alloy, and the thickness of the magnetic material is 3-20 micrometers;
taking the electroformed structure out of the electroforming tank, ultrasonically shaking and washing the electroformed structure by using deionized water, removing residual materials on a plated part, and drying the electroformed structure by using nitrogen;
wherein, the electroforming process comprises the following steps:
attaching a conductive copper adhesive tape to one side of the conductive metal mesh grid subjected to air drying treatment, connecting the conductive copper adhesive tape to a cathode of micro-electroforming equipment, connecting an electroforming deposition metal with an anode, placing the electroforming deposition metal in electroforming liquid, adding an anode activator into the electroforming liquid to improve the solubility of the anode, adding a buffer to slow down the increase of the pH value of the solution in an anode area, and adding a pinhole-preventing agent to reduce the surface tension of the solution;
starting the micro electroforming equipment, controlling the temperature and the PH value of the electroforming solution within a preset range through a constant temperature system and a PH value monitoring system, wherein the current density is smaller than a preset value; flushing liquid by using a circulating pump, and stirring the plating solution; the ultrasonic generator is used for discharging bubbles attached to the surface of the electrode in the processing process, and simultaneously, concentration polarization is reduced and the flow field characteristic is improved.
2. The batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive materials according to claim 1, characterized by comprising the following steps:
pre-treating a print substrate comprising:
cleaning, namely cleaning the printing substrate by using deionized water to remove dirt and dust on the surface;
drying, namely drying by using nitrogen or drying in a heating box to remove residual deionized water on the surface;
and (3) performing hydrophobic treatment, coating an ultrathin coating on the printing substrate and curing.
3. The batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive materials according to claim 2, characterized by comprising the following steps:
substrate materials include, but are not limited to, glass, sapphire, PMMA, and polyimide;
alternatively, the first and second electrodes may be,
drying modes include, but are not limited to, heating box drying and inert gas drying;
alternatively, the first and second electrodes may be,
coatings include, but are not limited to, nanocoating liquids and resins;
alternatively, the first and second electrodes may be,
the thickness of the coating is 3-10 μm;
alternatively, the first and second electrodes may be,
coating means include, but are not limited to, spin coating, blade coating, and slot coating;
alternatively, the first and second electrodes may be,
coating curing means include, but are not limited to, heat curing, ultraviolet curing, and infrared curing.
4. The batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive materials according to claim 1, characterized by comprising the following steps:
a method for printing a metal mesh grid structure on a pretreated high-light-transmittance base material by adopting a single-flat-plate electrode electric field driving multi-nozzle jet deposition micro-nano 3D printing method comprises the following steps:
designing the type, size and geometric arrangement parameters of the required grid according to preset requirements;
placing a printing material into a charging barrel of a single-flat-plate electrode electric field driven multi-nozzle jet deposition micro-nano 3D printing device;
connecting a nitrogen cylinder to the charging barrel through a pneumatic valve;
connecting a direct current power supply to a flat electrode of the printing device through a lead;
and placing the printing substrate coated with the coating on a printing platform of a printing device, starting the 3D printing device, and finishing the printing of the whole metal grid by combining optimized 3D printing process parameters according to the designed grid type, size and geometric arrangement parameters.
5. The batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive materials according to claim 4, characterized by comprising the following steps:
printing materials include, but are not limited to, conductive silver paste and conductive copper paste;
alternatively, the first and second electrodes may be,
a printing nozzle of the printing device selects a needle head with the inner diameter of 1-100 mu m;
alternatively, the first and second electrodes may be,
the distance between the printing nozzle and the printing substrate is 20-200 μm, the air pressure of the printing device is 50-200 kpa, the power voltage of the printing device is 100-1500V, and the printing speed of the printing device is 5-50 mm/s.
6. The batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive materials according to claim 1, characterized by comprising the following steps:
sintering the printed metal mesh grid at high temperature or low temperature in a vacuum environment or under the protection of inert gas, wherein the sintering process comprises the following steps:
and (3) placing the printed metal mesh grid into a sintering furnace for sintering, wherein the sintering process is carried out in a vacuum environment or under the protection of inert gas, the coated coating is removed under the action of high temperature, and the polymer additive contained in the printed metal slurry is removed.
7. The batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive materials according to claim 1, characterized by comprising the following steps:
the sample after will sintering is washd, gets rid of the filth that produces in sintering process attached to on the substrate and the net surface, and the air-dry is got rid of unnecessary moisture, includes:
and cleaning the sintered sample piece with deionized water to remove dirt attached to the substrate and the surface of the grid in the sintering process, and blowing the deionized water on the surface of the sample piece with nitrogen.
8. The batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive materials according to claim 7, characterized by comprising the following steps:
sintering methods include, but are not limited to, vacuum sintering, atmosphere protection sintering, and photonic sintering;
alternatively, the first and second electrodes may be,
the sintering temperature is 100-700 ℃, and the sintering time is 3-30 min.
9. The batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive materials according to claim 1, characterized by comprising the following steps:
the temperature of the electroforming solution is 45-55 ℃, the pH value is 3-4.5, and the current density is 0.5A/m in the electroforming process2～3A/m2In the electroforming process, the electroforming solution is sucked out by a circulating pump, filtered and discharged into an electroforming pool for electroformingFlushing, wherein the flushing speed is 1-2 m/s;
alternatively, the first and second electrodes may be,
the manner of stirring the electroforming solution includes, but is not limited to, mechanical stirring, magnetic stirring, and ultrasonic stirring.
10. The batch production method for manufacturing large-size electromagnetic shielding glass based on composite micro-nano additive materials according to claim 1, characterized by comprising the following steps:
taking out the electroformed structure from the electroforming tank, ultrasonically shaking and washing the electroformed structure by deionized water, removing residual materials on a plated part, and drying the electroformed structure by nitrogen, wherein the method comprises the following steps:
taking the electroformed structure off the cathode, removing the copper adhesive tape on one side, ultrasonically shaking and washing the electroformed structure by using deionized water to completely remove residual materials on the plated part, and drying redundant moisture by using nitrogen;
alternatively, the first and second electrodes may be,
the ultrasonic vibration washing time is 3 min-5 min.
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