CN113507829B - Electromagnetic shielding silicone rubber grid liquid metal composite material structure and manufacturing method - Google Patents

Electromagnetic shielding silicone rubber grid liquid metal composite material structure and manufacturing method Download PDF

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CN113507829B
CN113507829B CN202110912495.5A CN202110912495A CN113507829B CN 113507829 B CN113507829 B CN 113507829B CN 202110912495 A CN202110912495 A CN 202110912495A CN 113507829 B CN113507829 B CN 113507829B
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liquid metal
composite material
silicon rubber
extrusion mechanism
silicone rubber
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CN113507829A (en
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王震宇
夏栩婷
朱萌
张行乐
刘禹
姜晶
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Jiangnan University
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Jiangnan University
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/171—Processes of additive manufacturing specially adapted for manufacturing multiple 3D objects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/205—Means for applying layers
    • B29C64/209—Heads; Nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/364—Conditioning of environment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/386—Data acquisition or data processing for additive manufacturing
    • B29C64/393—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y50/00—Data acquisition or data processing for additive manufacturing
    • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • 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
    • 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
    • H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2028/00—Nets or the like
    • 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
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention relates to an electromagnetic shielding silicon rubber grid liquid metal composite material structure and a manufacturing method thereof. By using the hyperelastic silicon rubber grid as a supporting structure and adopting the liquid metal to establish the three-dimensionally communicated liquid conductive path in the silicon rubber grid, higher electromagnetic shielding efficiency can be still ensured under the deformation conditions of static large-strain stretching and cyclic stretching, the defects of unstable electromagnetic shielding performance under external deformation, reduced flexibility after the conductive filler is added and complex manufacturing process in the prior art are overcome, and the advantages of simple manufacturing process and greatly improved performance reliability are achieved.

Description

Electromagnetic shielding silicon rubber grid liquid metal composite material structure and manufacturing method thereof
Technical Field
The invention relates to the technical field of flexible composite material 3D printing, in particular to an electromagnetic shielding silicone rubber grid liquid metal composite material structure and a manufacturing method thereof.
Background
With the continuous progress of science and technology, the problems of electromagnetic pollution and electromagnetic interference caused by electronic and electrical equipment become more serious day by day, so that the research and development of electromagnetic shielding materials have important values in both civil and military fields. However, as electronic devices are developed to be flexible and portable, the conventional rigid electromagnetic shielding material cannot meet the use requirements, so that the electromagnetic shielding material of the new generation is required to have the advantages of flexibility, light weight, easy processing and the like while having excellent electromagnetic shielding performance. In the case of flexible electronic devices, the flexible electronic devices are often subjected to large external loads and complex deformation during use, which often causes unpredictable damage to the materials and thus leads to a reduction in the electromagnetic shielding effectiveness.
At present, the electromagnetic shielding composite material mainly has the following limitations:
(1) the conductive filler of the composite material is usually a metal or carbon filler and the like, and although the conductive and electromagnetic shielding properties of the composite material can be effectively improved by the fillers, the flexibility and stretchability of the composite material are sharply reduced along with the increase of the content of the fillers;
(2) the existing preparation method of the electromagnetic shielding composite material usually needs a complex dispersion process, has a long preparation period and is difficult to meet the increasing personalized customization requirements of users;
(3) under the condition of large external deformation, the traditional rigid conductive filler is difficult to cooperatively deform with the elastic matrix, and slippage is generated inside the material, so that the conductive network structure is changed, the electromagnetic shielding effectiveness is reduced/unstable, and the normal functional requirements cannot be met.
Disclosure of Invention
The applicant provides an electromagnetic shielding silicone rubber grid liquid metal composite material structure and a manufacturing method aiming at the defects in the prior art, so that the performance of the composite material can be ensured, the use requirement can be met, and the processing is simple and convenient.
The technical scheme adopted by the invention is as follows:
the utility model provides an electromagnetic shield's silicon rubber net liquid metal composite structure, includes the bottom plate, the upper surface of bottom plate is provided with main grid structure, infiltration has liquid metal in main grid structure's the space, main grid structure's periphery is provided with the net leg, main grid structure's top surface is provided with roof, main grid structure.
As a further improvement of the technical scheme:
the top plate and the bottom plate are made of silicon rubber.
A manufacturing method of an electromagnetic shielding silicon rubber grid liquid metal composite material structure comprises the following steps:
the first step is as follows: preparing a silicon wafer;
the second step is that: immersing a silicon wafer in a fluorinated silane solution, standing for one day, taking out the silicon wafer, and airing the residual solution at a ventilated position to be used as a printing substrate;
the third step: preparing a first extrusion mechanism and a second extrusion mechanism which are arranged side by side, wherein a first spray nozzle is arranged at the output port of the first extrusion mechanism, a second spray nozzle is arranged at the output port of the second extrusion mechanism, a first connecting pipe is arranged at the inlet of the first extrusion mechanism, and a second connecting pipe is arranged at the inlet of the second extrusion mechanism;
the fourth step: silicon rubber is loaded into a first extrusion mechanism, and gallium indium tin alloy is loaded into a second extrusion mechanism;
the fifth step: respectively connecting the first connecting pipe and the second connecting pipe with an external air source;
and a sixth step: establishing a model for the main grid structure by using three-dimensional modeling software and importing slicing software,
the seventh step: setting the air pressure of a first extrusion mechanism to be 22psi, printing a bottom plate on a substrate by a spray head at the speed of 7mm/s, and then sequentially printing a main grid structure and grid surrounding walls on the bottom plate;
eighth step: setting the air pressure of the second extrusion mechanism to be 20psi, and printing liquid metal accounting for 5-50 wt% of the composite material on the main grid structure by a spray head at the speed of 1 mm/s;
the ninth step: placing the structure prepared in the eighth step in a vacuum oven, and vacuumizing for 30 minutes;
the tenth step: setting the air pressure of the first extrusion mechanism to be 22psi, and printing the top layer silicon rubber above the main grid structure by the nozzle at the speed of 7mm/s to form a top plate;
the eleventh step: prefabricating a composite material;
the eleventh step: curing the prepared composite material in an oven at 150 ℃ for 30 minutes;
the twelfth step: taking out the composite material, and separating the silicon wafer;
the thirteenth step: obtaining a final product;
a fourteenth step of: and (4) finishing.
As a further improvement of the above technical solution:
in the second step, the fluorinated silane solution is a 1% volume fraction ethanol solution.
The silicone rubber is Dow Corning SE1700 silica gel, Dow Corning SE1700 curing agent and tributynediol according to the ratio of 100: 10: 1, and uniformly mixing the mixture.
In the third step, the inner diameters of the first spray head and the second spray head are both 250 μm.
In the sixth step, the following settings are made in the slicing software: the thickness of each layer of the bottom plate, the outer wall of the grid and the top plate is 0.25mm, the center distance of the lines is 0.25mm, the thickness of each layer of the main grid structure is 0.25mm, and the center distance of the lines is 0.5 mm.
The invention has the following beneficial effects:
the invention has compact and reasonable structure and convenient operation, can still ensure higher electromagnetic shielding efficiency under the deformation conditions of static large-strain stretching and cyclic stretching by taking the hyperelastic silicon rubber grid as a supporting structure and adopting the liquid metal to establish the three-dimensionally communicated liquid conductive path in the silicon rubber grid, solves the defects of unstable electromagnetic shielding performance under external deformation, reduced flexibility after the conductive filler is added and complex manufacturing process in the prior art, and has the advantages of simple manufacturing process and greatly improved performance reliability.
The invention adopts the silicon rubber grid with superelasticity and regular internal pore structure as a matrix, and constructs a three-dimensional communicated and liquid gallium indium tin alloy conductive path in the silicon rubber grid, thereby not only greatly improving the flexibility of the material, but also ensuring the stability of the conductive and electromagnetic shielding performances of the material under external deformation such as stretching, bending, torsion and the like
According to the invention, through a bi-material 3D printing process, firstly, a silicon rubber grid (comprising bottom silicon rubber, a main grid structure, a grid outer wall and top silicon rubber) is printed, secondly, liquid metal droplets are printed inside the silicon rubber grid, and liquid metal is completely filled inside each grid by using a vacuum pumping method, so that the manufacturing of the whole composite material structure is completed.
Drawings
FIG. 1 is a schematic structural view of the composite material of the present invention.
Fig. 2 is an exploded view of a composite material of the present invention.
FIG. 3 is a schematic structural diagram of a process step of the present invention.
FIG. 4 is a schematic structural diagram of the process step of the present invention (II).
FIG. 5 is a schematic diagram of the structure in the process step (III) of the present invention.
FIG. 6 is a schematic diagram (IV) of the structure in the process step of the present invention.
Fig. 7 is a graph showing the electromagnetic shielding effectiveness of the present invention under different degrees of tensile deformation.
Wherein: 1. a top plate; 2. the outer wall of the grid; 3. a base plate; 4. a main body lattice structure; 5. a liquid metal; 6. a first extruder; 7. a second extruder;
601. a first connecting pipe; 602. a first nozzle;
701. a second connecting pipe; 702. and a second spray head.
Detailed Description
The following describes embodiments of the present invention with reference to the drawings.
As shown in fig. 1 to 7, the electromagnetic shielding silicone rubber grid liquid metal composite structure of the present embodiment includes a bottom plate 3, a main grid structure 4 is disposed on an upper surface of the bottom plate 3, a liquid metal 5 permeates into a gap of the main grid structure 4, a grid surrounding wall 2 is disposed on a periphery of the main grid structure 4, a top plate 1 is disposed on a top surface of the main grid structure 4, and the main grid structure 4 is disposed on the top surface of the main grid structure 4.
The top plate 1 and the bottom plate 3 are made of silicon rubber.
The method for manufacturing the electromagnetic shielding silicon rubber grid liquid metal composite material structure comprises the following steps:
the first step is as follows: preparing a silicon wafer;
the second step is that: immersing a silicon wafer in a fluorinated silane solution, standing for one day, taking out the silicon wafer, and airing the residual solution at a ventilated position to be used as a printing substrate;
the third step: preparing a first extruding mechanism 6 and a second extruding mechanism 7 which are arranged side by side, wherein a first spray nozzle 601 is arranged at the output port of the first extruding mechanism 6, a second spray nozzle 602 is arranged at the output port of the second extruding mechanism 7, a first connecting pipe 601 is arranged at the inlet of the first extruding mechanism 6, and a second connecting pipe 701 is arranged at the inlet of the second extruding mechanism 7;
the fourth step: silicon rubber is loaded into a first extrusion mechanism 6, and gallium indium tin alloy is loaded into a second extrusion mechanism 7;
the fifth step: connecting the first connecting pipe 601 and the second connecting pipe 701 with an external air source respectively;
and a sixth step: the subject mesh structure 4 is modeled with three-dimensional modeling software and sliced with the software,
the seventh step: setting the air pressure of a first extrusion mechanism 6 to be 22psi, printing a bottom plate 3 on a substrate at the speed of 7mm/s by a spray head, and then sequentially printing a main grid structure 4 and a grid surrounding wall 2 on the bottom plate 3;
eighth step: setting the air pressure of the second extrusion mechanism 7 to be 20psi, and printing liquid metal accounting for 5wt% -50wt% of the composite material on the main grid structure 4 at the speed of 1mm/s by a spray head;
the ninth step: placing the structure prepared in the eighth step in a vacuum oven, and vacuumizing for 30 minutes;
the tenth step: setting the air pressure of the first extrusion mechanism 6 to be 22psi, and printing the top layer silicon rubber on the main grid structure 4 by a nozzle at the speed of 7mm/s to form a top plate 1;
the eleventh step: prefabricating a composite material;
the eleventh step: curing the prepared composite material in an oven at 150 ℃ for 30 minutes;
the twelfth step: taking out the composite material, and separating the silicon wafer;
the thirteenth step: obtaining a final product;
the fourteenth step is that: and (4) finishing.
In the second step, the fluorinated silane solution is a 1% volume fraction ethanol solution.
The silicone rubber is Dow Corning SE1700 silica gel, Dow Corning SE1700 curing agent and tributyne-ol according to the ratio of 100: 10: 1, and uniformly mixing the mixture.
In the third step, the inner diameters of the first and second showerheads 602 and 702 are both 250 μm.
In the sixth step, the following settings are made in the slicing software: the thickness of each layer of the bottom plate 3, the grid outer wall 2 and the top plate 1 is 0.25mm, the line center distance is 0.25mm, the thickness of each layer of the main grid structure 4 is 0.25mm, and the line center distance is 0.5 mm.
The diameter of the silicon rubber grid line is 100-600 mu m
The printing material is one or more of thermosetting or thermoplastic silicone rubber.
The filling material is one or more of liquid metals.
The bottom layer silicon rubber, the outer wall of the grid and the top layer silicon rubber are solids with the line spacing of 0, the main body of the grid is a fiber array structure with four layers or more than four layers, the fiber array structures of adjacent layers are mutually crossed, the included angle is alpha, and alpha is more than 0 degree and less than or equal to 90 degrees.
The first embodiment is as follows:
the method for manufacturing the electromagnetic shielding silicon rubber grid liquid metal composite material structure comprises the following steps:
immersing a silicon wafer into an ethanol solution of fluorinated silane with the integral percentage of 1%, standing for one day, taking out the silicon wafer, and airing the residual solution at a ventilation position to serve as a printing substrate of the embodiment;
(II) mixing Dow Corning SE1700 silica gel, Dow Corning SE1700 curing agent and tributyne-ol according to the ratio of 100: 10: 1 and loading into a first extrusion mechanism 6;
thirdly, the gallium indium tin alloy is filled into the second extruding mechanism 7;
fourthly, the first extrusion mechanism 6 and the second extrusion mechanism 7 are respectively connected with respective spray heads, and the inner diameters of the spray heads are 250 mu m;
connecting the first extruding mechanism 6 and the second extruding mechanism 7 with an external air source;
and (VI) establishing a model for the silicon rubber grid structure by using three-dimensional modeling software, importing slicing software, and setting the following settings in the slicing software: the thickness of each layer of the bottom layer silicon rubber, the outer wall of the grid and the top layer silicon rubber is 0.25mm, the line center distance is 0.25mm, the thickness of each layer of the main grid structure is 0.25mm, and the line center distance is 0.5 mm;
setting the air pressure of a silicon rubber extrusion mechanism to be 22psi, and printing the bottom layer silicon rubber, the grid main body structure and the outer wall of the grid on the substrate at the speed of 7mm/s by a spray head;
(eighth) setting the air pressure of a liquid metal extrusion mechanism to be 20psi, and printing liquid metal accounting for 10 wt% of the composite material on the silicon rubber grid by a spray head at the speed of 1 mm/s;
putting the prepared structure in a vacuum oven, and vacuumizing for 30 minutes;
setting the air pressure of a silicon rubber extrusion mechanism to be 22psi, and printing the top layer silicon rubber on the silicon rubber grid by a spray head at the speed of 7 mm/s;
(eleventh) curing the prepared silicone rubber grid/liquid metal composite material in an oven at 150 ℃ for 30 minutes;
(twelfth) in this example, the electrical conductivity of the silicone rubber mesh/liquid metal composite is 7.5 × 10 "3S/m, the electromagnetic shielding effectiveness in the X band is 20dB, and the rate of change of the electromagnetic shielding effectiveness in the 100% stretch is 15%;
example two:
the method for manufacturing the electromagnetic shielding silicon rubber grid liquid metal composite material structure comprises the following steps:
immersing a silicon wafer into an ethanol solution of fluorinated silane with the integral percentage of 1%, standing for one day, taking out the silicon wafer, and airing the residual solution at a ventilation position to serve as a printing substrate of the embodiment;
(II) mixing Dow Corning SE1700 silica gel, Dow Corning SE1700 curing agent and tributyne-ol according to the ratio of 100: 10: 1 and loading the mixture into a first extruding mechanism 6;
thirdly, the gallium indium tin alloy is filled into the second extruding mechanism 7;
fourthly, the first extruding mechanism 6 and the second extruding mechanism 7 are connected with a spray head, and the inner diameter of the spray head is 250 mu m;
connecting the first extruding mechanism 6 and the second extruding mechanism 7 with an external air source;
and (VI) establishing a model for the silicon rubber grid structure by using three-dimensional modeling software, importing slicing software, and setting the following settings in the slicing software: the thickness of each layer of the bottom layer silicon rubber, the outer wall of the grid and the top layer silicon rubber is 0.25mm, the line center distance is 0.25mm, the thickness of each layer of the main grid structure is 0.25mm, and the line center distance is 0.5 mm;
setting the air pressure of a silicon rubber extrusion mechanism to be 22psi, and printing the bottom layer silicon rubber, the grid main body structure and the outer wall of the grid on the substrate at the speed of 7mm/s by a spray head;
setting the air pressure of a liquid metal extrusion mechanism to be 20psi, and printing liquid metal accounting for 15wt% of the composite material on the silicon rubber grid by a spray head at the speed of 1 mm/s;
putting the prepared structure in a vacuum oven, and vacuumizing for 30 minutes;
(ten) setting the air pressure of a silicon rubber extrusion mechanism to be 22psi, and printing the top layer silicon rubber on the silicon rubber grid by a spray head at the speed of 7 mm/s;
(eleventh) curing the prepared product in an oven at 150 ℃ for 30 minutes;
(twelfth) in this embodiment, the electrical conductivity of the silicone rubber mesh/liquid metal composite is 7 × 103S/m, the electromagnetic shielding effectiveness in the X band is 37dB, and the rate of change of the electromagnetic shielding effectiveness in the 100% stretch is within 2%.
Example three:
the method for manufacturing the electromagnetic shielding silicon rubber grid liquid metal composite material structure comprises the following steps:
immersing a silicon wafer into an ethanol solution of fluorinated silane with the integral percentage of 1%, standing for one day, taking out the silicon wafer, and airing the residual solution at a ventilation position to serve as a printing substrate of the embodiment;
(II) mixing Dow Corning SE1700 silica gel, Dow Corning SE1700 curing agent and tributyne-ol according to the ratio of 100: 10: 1 and loading the mixture into a first extruding mechanism 6;
thirdly, the gallium indium tin alloy is filled into the second extruding mechanism 7;
fourthly, the first extruding mechanism 6 and the second extruding mechanism 7 are connected with a spray head, and the inner diameter of the spray head is 250 mu m;
connecting the first extruding mechanism 6 and the second extruding mechanism 7 with an external air source;
and (VI) establishing a model for the silicon rubber grid structure by using three-dimensional modeling software, importing slicing software, and setting the following settings in the slicing software: the thickness of each layer of the bottom layer silicon rubber, the outer wall of the grid and the top layer silicon rubber is 0.25mm, the line center distance is 0.25mm, the thickness of each layer of the main grid structure is 0.25mm, and the line center distance is 0.5 mm;
setting the air pressure of a silicon rubber extrusion mechanism to be 22psi, and printing the bottom layer silicon rubber, the grid main body structure and the outer wall of the grid on the substrate at the speed of 7mm/s by a spray head;
(eighth) setting the air pressure of the liquid metal extrusion mechanism to be 20psi, and printing the liquid metal accounting for 5wt% of the composite material on the silicon rubber grid by a spray head at the speed of 1 mm/s;
putting the prepared structure in a vacuum oven, and vacuumizing for 30 minutes;
(ten) setting the air pressure of a silicon rubber extrusion mechanism to be 22psi, and printing the top layer silicon rubber on the silicon rubber grid by a spray head at the speed of 7 mm/s;
(eleventh) curing the prepared product in an oven at 150 ℃ for 30 minutes;
(twelfth) in this example, the electrical conductivity of the silicone rubber mesh/liquid metal composite was 6 x 10-4S/m, the electromagnetic shielding effectiveness at the X wave band is 15dB, and the electromagnetic shielding effectiveness change rate under the 100% stretching condition is 30%.
Example four:
the method for manufacturing the electromagnetic shielding silicon rubber grid liquid metal composite material structure comprises the following steps:
immersing a silicon wafer into an ethanol solution of fluorinated silane with the integral percentage of 1%, standing for one day, taking out the silicon wafer, and airing the residual solution at a ventilation position to serve as a printing substrate of the embodiment;
(II) mixing Dow Corning SE1700 silica gel, Dow Corning SE1700 curing agent and tributyne-ol according to the ratio of 100: 10: 1 and loading the mixture into a first extruding mechanism 6;
thirdly, the gallium indium tin alloy is filled into the second extruding mechanism 7;
fourthly, the first extruding mechanism 6 and the second extruding mechanism 7 are connected with a spray head, and the inner diameter of the spray head is 250 mu m;
connecting the first extruding mechanism 6 and the second extruding mechanism 7 with an external air source;
and (VI) establishing a model for the silicon rubber grid structure by using three-dimensional modeling software, importing slicing software, and setting the following settings in the slicing software: the thickness of each layer of the bottom layer silicon rubber, the outer wall of the grid and the top layer silicon rubber is 0.25mm, the line center distance is 0.25mm, the thickness of each layer of the main grid structure is 0.25mm, and the line center distance is 0.5 mm;
setting the air pressure of a silicon rubber extrusion mechanism to be 22psi, and printing the bottom layer silicon rubber, the grid main body structure and the outer wall of the grid on the substrate at the speed of 7mm/s by a spray head;
(eighth) setting the air pressure of a liquid metal extrusion mechanism to be 20psi, and printing liquid metal accounting for 50wt% of the composite material on the silicon rubber grid by a spray head at the speed of 1 mm/s;
putting the prepared structure in a vacuum oven, and vacuumizing for 30 minutes;
(ten) setting the air pressure of a silicon rubber extrusion mechanism to be 22psi, and printing the top layer silicon rubber on the silicon rubber grid by a spray head at the speed of 7 mm/s;
(eleventh) curing the prepared product in an oven at 150 ℃ for 30 minutes;
(twelfth) in this example, the electrical conductivity of the silicone rubber mesh/liquid metal composite was 6 x 104S/m, the electromagnetic shielding effectiveness at the X wave band is 65dB, and the electromagnetic shielding effectiveness change rate under the 100% stretching condition is within 2%.
The invention relates to a stretchable electromagnetic shielding silicon rubber grid/liquid metal solid-liquid two-phase composite structure which is integrally formed and manufactured by a double-material printing process, wherein a silicon rubber grid (comprising bottom silicon rubber, a main grid structure, a grid outer wall and top silicon rubber) is printed by a silicon rubber material, and the liquid metal filling inside is printed by gallium indium tin alloy. The bottom silicon rubber, the outer wall of the grid and the top silicon rubber are entities with the line spacing of 0, the grid main body is a fiber array structure with four layers or more than four layers, the fiber array structures of adjacent layers are mutually crossed, and the internal liquid metal is uniformly filled into the silicon rubber grid structure through a 3D printing process. The composite structure has the excellent stretchability of the silicon rubber grid and the electrical conductivity of liquid metal, and can ensure higher electrical conductivity and electromagnetic shielding performance under the condition of external complex and large deformation. Different from the traditional electromagnetic shielding material manufacturing process, the invention avoids the complex and fussy mixing and dispersing process in the prior art and solves the problems that the mechanical property of the existing electromagnetic shielding composite material is reduced after the conductive filler is added and the conductivity and the electromagnetic shielding effectiveness are unstable under the external complex and large deformation condition. Meanwhile, the silicon rubber grid/liquid metal composite material for stretchable electromagnetic shielding provided by the invention explains a brand-new composite material system, and has the advantages of high forming precision, customizable structure and performance, mass production and the like.
The above description is intended to be illustrative and not restrictive, and the scope of the invention is defined by the appended claims, which may be modified in any manner within the scope of the invention.

Claims (8)

1. An electromagnetic shielding silicon rubber grid liquid metal composite structure is characterized in that: the metal-clad plate comprises a bottom plate (3), wherein a main grid structure (4) is arranged on the upper surface of the bottom plate (3), liquid metal (5) permeates into gaps of the main grid structure (4), a grid surrounding wall (2) is arranged on the periphery of the main grid structure (4), a top plate (1) is arranged on the top surface of the main grid structure (4), and the main grid structure (4) is arranged on the top surface of the main grid structure (4); the top plate (1) and the bottom plate (3) are both made of silicon rubber; the manufacturing method comprises the following steps:
the first step is as follows: preparing a silicon wafer;
the second step is that: immersing a silicon wafer in a fluorinated silane solution, standing for one day, taking out the silicon wafer, and airing the residual solution at a ventilated position to be used as a printing substrate;
the third step: preparing a first extrusion mechanism (6) and a second extrusion mechanism (7) which are arranged side by side, wherein a first spray head (601) is arranged at an output port of the first extrusion mechanism (6), a second spray head (602) is arranged at an output port of the second extrusion mechanism (7), a first connecting pipe (601) is arranged at an inlet of the first extrusion mechanism (6), and a second connecting pipe (701) is arranged at an inlet of the second extrusion mechanism (7);
the fourth step: silicon rubber is loaded into a first extrusion mechanism (6), and gallium indium tin alloy is loaded into a second extrusion mechanism (7);
the fifth step: respectively connecting the first connecting pipe (601) and the second connecting pipe (701) with an external air source;
and a sixth step: a three-dimensional modeling software is used for establishing a model for the main body grid structure (4) and importing slicing software,
the seventh step: setting the air pressure of a first extrusion mechanism (6) to be 22psi, printing a base plate (3) on a substrate by a spray head at the speed of 7mm/s, and then sequentially printing a main grid structure (4) and a grid surrounding wall (2) on the base plate (3);
eighth step: setting the air pressure of the second extrusion mechanism (7) to be 20psi, and printing liquid metal accounting for 5wt% -50wt% of the composite material on the main grid structure (4) by a spray head at the speed of 1 mm/s;
the ninth step: placing the structure prepared in the eighth step in a vacuum oven, and vacuumizing for 30 minutes;
the tenth step: setting the air pressure of a first extrusion mechanism (6) to be 22psi, and printing top layer silicon rubber above the main grid structure (4) by a spray head at the speed of 7mm/s to form a top plate (1);
the eleventh step: prefabricating a composite material;
the eleventh step: putting the prepared composite material into an oven at 150 ℃ for curing for 30 minutes;
the twelfth step: taking out the composite material, and separating the silicon wafer;
the thirteenth step: obtaining a final product;
the fourteenth step is that: and (4) finishing.
2. The electromagnetically shielded silicone rubber mesh liquid metal composite structure of claim 1, wherein: in the second step, the fluorinated silane solution is a 1% volume fraction ethanol solution.
3. The electromagnetically shielded silicone rubber mesh liquid metal composite structure of claim 1, wherein: the silicone rubber is Dow Corning SE1700 silica gel, Dow Corning SE1700 curing agent and tributynediol according to the ratio of 100: 10: 1, and uniformly mixing the mixture.
4. The electromagnetically shielded silicone rubber mesh liquid metal composite structure of claim 1, wherein: in the third step, the inner diameters of the first spray head (602) and the second spray head (702) are both 250 μm.
5. The electromagnetically shielded silicone rubber mesh liquid metal composite structure of claim 1, wherein: in the sixth step, the following settings are made in the slicing software: the thickness of each layer of the bottom plate (3), the outer wall (2) of the grid and the top plate (1) is 0.25mm, and the center distance of the lines is 0.25 mm; the thickness of each layer of the main grid structure (4) is 0.25mm, and the center distance of the lines is 0.5 mm.
6. The electromagnetically shielded silicone rubber mesh liquid metal composite structure of claim 1, wherein: in the eighth step, liquid metal accounting for 15wt% of the composite material is used.
7. The electromagnetically shielded silicone rubber mesh liquid metal composite structure of claim 1, wherein: and eighthly, adopting liquid metal accounting for 5wt% of the composite material.
8. The electromagnetically shielded silicone rubber mesh liquid metal composite structure of claim 1, wherein: and eighthly, adopting liquid metal accounting for 50wt% of the composite material.
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