CN111391305B - Preparation method of polymer-based 3D printing electromagnetic shielding product - Google Patents
Preparation method of polymer-based 3D printing electromagnetic shielding product Download PDFInfo
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- 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
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- C08K3/041—Carbon nanotubes
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- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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Abstract
The invention provides a preparation method of a polymer-based 3D printing electromagnetic shielding product, which comprises the steps of directionally loading carbon fillers for electromagnetic shielding on the surfaces of pure polymer particles, further extruding and preparing filament yarns capable of being printed in a 3D mode under specific extrusion conditions, and then printing through a fusion deposition molding 3D printing technology to obtain the 3D printing electromagnetic shielding product. The polymer-based 3D printed electromagnetic shielding product not only meets the standard of commercial electromagnetic shielding performance, but also has better mechanical performance than corresponding products prepared from the same pure polymer; the preparation method has the characteristics of high electromagnetic shielding performance of the 3D printing material and excellent 3D printing processing performance, and has the advantages of 3D printing, such as a printable complex shape structure, high personalized customization degree and the like.
Description
Technical Field
The invention relates to the technical field of electromagnetic shielding products, relates to a preparation method of a polymer-based 3D printed electromagnetic shielding product, and particularly relates to an electromagnetic shielding ventilation board applied to 3D printing.
Background
In recent years, with the development of electronic technology, the problem of electromagnetic wave pollution is becoming more serious. The electronic equipment not only causes mutual interference among electronic and electrical equipment and influences the normal operation of the equipment, but also causes certain harm to human health. Therefore, attention is paid to the development of materials for blocking and shielding electromagnetic waves, and among them, a commercial electromagnetic shielding ventilation board, which is one of the applications of electromagnetic shielding products, can effectively shield electromagnetic waves, ensure the normal operation of electronic equipment, and simultaneously prevent electromagnetic radiation from harming human health and information leakage.
The general electromagnetic shielding products, especially the ventilation board, are mostly metal-based materials, but the density is large, the mass is heavy, the oxidation and corrosion are easy, and the processing performance is poor. The existing commercial electromagnetic shielding ventilation board with a complex porous structure usually consumes a large amount of resources from design to preparation. No matter the mold is designed or the metal material is molded, the process is long in period, high in energy consumption, high in manufacturing cost and simple in product structure, and personalized requirements of different electronic equipment are difficult to meet. This has greatly limited the application and development of metal-based electromagnetic shielding ventilation boards.
The polymer-based material can effectively make up the defects of the metal-based material, and has the advantages of light weight, low price, corrosion resistance, good weather resistance and the like compared with the metal-based material, so that the application of the polymer-based material in the field of electromagnetic shielding is expected to realize the replacement of the existing metal-based material. The 3D printing is based on a digital model, and a non-traditional advanced manufacturing technology for manufacturing products by utilizing bondable materials such as metal or plastic powder in a layer-by-layer stacking accumulation mode is utilized, so that one-step molding from materials to products can be realized, and the products with complex, fine and personalized structures which cannot be manufactured by the traditional processing method are manufactured. Therefore, the polymer-based material with the electromagnetic shielding function is combined with the personalized customized extrusion type 3D printing technology, so that the preparation of the polymer-based electromagnetic shielding ventilating plate which is light in weight, low in cost, capable of being produced continuously and meeting personalized requirements is hopeful to be realized, and the restriction of the existing processing technology and conditions is broken through. However, there is only a few literature reports to prepare the polymer-based electromagnetic shielding ventilation board by using a 3D printing technology, so as to realize the application of the polymer-based electromagnetic shielding ventilation board in the field of electromagnetic shielding.
At present, most of the commercialized materials suitable for extrusion type 3D printing are pure polymers, such as polylactic acid, polyamide, polyvinyl alcohol, thermoplastic polyurethane elastomer, ABS resin, polyethylene, polypropylene, etc., which have good processing flowability, however, such pure polymers generally have no functionality and no electromagnetic shielding property. Therefore, it is desirable to incorporate light weight, multifunctional carbon-based functional fillers (e.g., graphene, carbon nanotubes, fullerenes, carbon black, graphite, carbon fibers, etc.) to impart specific functionalities to the polymer. Generally, commercial electromagnetic shielding materials usually need to reach 20dB of standard electromagnetic shielding performance, i.e. 99% of the blocking rate of electromagnetic waves. In order to achieve this standard, according to the traditional conductive percolation threshold theory, a high content of functional filler is introduced to construct a strong filler network structure. However, when the polymer-based material meets the commercial electromagnetic shielding performance standard, the processing flowability of the polymer-based material is seriously deteriorated due to the excessively high content of the filler, a nozzle is blocked in the printing process, or the polymer-based material does not have the printability at all; and if the 3D printing fluidity needs to be coordinated, the electromagnetic shielding performance of the finally printed electromagnetic shielding product cannot meet the requirements of the existing commercial electromagnetic shielding performance standard. Therefore, the polymer-based electromagnetic shielding material meeting the commercial standard in the prior art is still limited to use of a compression molding process, and the processed product has a simple structure, is not continuously produced, has a long production period, cannot meet the personalized customized structure of the product, and cannot endow the product with a complex porous structure to meet the ventilation of the electromagnetic shielding plate; meanwhile, the mould pressing process is restricted by the technology, and defects are easily generated in the product, so that the performance of the product is affected. Compared with the preparation process (mold design-casting molding-fine processing) of the metal-based electromagnetic shielding ventilating plate, the method has no remarkable technical progress.
Therefore, the method solves the defects of the prior art or the materials, breaks through the leap of the polymer-based electromagnetic shielding product prepared by 3D printing, particularly the electromagnetic shielding ventilation board with a complex structure, and still faces great challenges. How to optimize the printability and the performance of the material and fundamentally solve the contradiction between high shielding performance and low printing performance of the material, thereby realizing the personalized customization of the preparation of 3D printing polymer-based electromagnetic shielding products, particularly ventilation boards, meeting the commercial electromagnetic shielding requirements, and being the difficult point and the key point which need to be broken through urgently in the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of a polymer-based 3D printing electromagnetic shielding product aiming at the defects of the prior art, and the polymer-based 3D printing electromagnetic shielding product has better mechanical properties than a product prepared from the same kind of pure polymer on the basis of meeting the commercial electromagnetic shielding performance standard. The 3D printing material prepared by the method has the characteristics of high shielding performance and good printing processability, and has the existing advantages of 3D printing, such as continuous automatic processing, short production period, multi-scale products, complex shape and structure, high personalized customization degree and the like.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a polymer-based 3D printing electromagnetic shielding product comprises the following steps in parts by weight:
(1) adding 100 parts of pure polymer particles and 2-10 parts of carbon-based filler for electromagnetic shielding into water or an organic solvent, standing after uniform dispersion to enable the carbon-based filler for electromagnetic shielding to be loaded on the surfaces of the pure polymer particles, filtering and drying to obtain polymer particles with the surfaces coated with the carbon-based filler;
(2) and (2) extruding and processing the polymer particles coated with the carbon-based filler on the surface obtained in the step (1) to obtain filament yarns capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 2-15 ℃ higher than the melting temperature of the pure polymer particles, and the extrusion speed is 2-15 r/min;
(3) and (3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology according to the three-dimensional digital model of the target electromagnetic shielding product to obtain the 3D printed electromagnetic shielding product.
It is worth to say that the invention solves the contradiction between high shielding performance and low printing performance of the material in the prior art, and obtains the 3D printing filament with the filler non-uniformly distributed in the polymer matrix by directionally loading the carbon-based filler for electromagnetic shielding on the surface of pure polymer particles and strictly controlling the extrusion processing conditions.
Compared with the 3D printing filament with the filler in non-uniform distribution prepared by loading the carbon-based filler on the surface of pure polymer particles and then extruding, the 3D printing filament with the filler in uniform distribution prepared by the traditional simple direct melt blending method is prepared. In comparison, the former filler has high concentration in local area in the matrix, so that a filler network is easier to construct. Therefore, the 3D printing filament with the non-uniformly distributed filler can obtain more excellent electromagnetic shielding performance under the condition of relatively less carbon-based filler content for electromagnetic shielding, and has mechanical properties and processing flowability similar to those of a low-filler-content system prepared by a traditional melt blending method, and excellent FDM 3D printing processability.
Preferably, the pure polymer particles are pure polymer particles which can be used as raw materials of fused deposition modeling 3D printing thread; further preferably, any one of polylactic acid, polyamide 11, polyamide 12, polyvinyl alcohol, thermoplastic polyurethane elastomer, ABS resin, polyethylene and polypropylene is included; still more preferably polyamide 11, polylactic acid, polyethylene or polyvinyl alcohol.
Preferably, the carbon-based filler for electromagnetic shielding comprises any one or more of graphene, carbon nanotubes, carbon black, graphite, football and carbon fibers; further preferably, the material is any one or combination of more of graphene, carbon nanotubes, carbon black and graphite.
In order to facilitate the directional loading of the carbon-based filler for electromagnetic shielding on the surface of the pure polymer particles in step (1) and not to affect the printing performance of the filament formed by extrusion processing, the particle size of the pure polymer particles is preferably 50 μm to 300 μm, and the carbon-based filler for electromagnetic shielding is commercially available standard, such as carbon nanotubes with an average diameter of 9.5nm and an average length of 11.5 μm, and graphene with an average particle size of 8 μm.
It is worth to be noted that, the extrusion processing parameters in the step (2) are as follows: the extrusion temperature is 2-15 ℃ higher than the melting temperature of the pure polymer particles, and the extrusion speed is 2-15 r/min. Wherein, the extrusion temperature is strictly lower than the temperature adopted by the common polymer melt blending, and the extrusion processing temperature is usually 20 ℃ to 40 ℃ higher than the polymer melting temperature in the traditional melt blending technology. If the melt blending extrusion processing temperature in the traditional technology is adopted, the carbon-based filler coated on the surface of the pure polymer particles is easily and homogeneously dispersed in the polymer, the non-uniform dispersion effect of the carbon-based filler in the polymer matrix cannot be realized, and further the high electromagnetic shielding performance cannot be realized; below the extrusion temperature defined in the present invention, the pure polymer particles cannot be extruded normally; meanwhile, the extrusion speed is also strictly limited and needs to be greatly lower than the extrusion speed (50 r/min-150 r/min) adopted by the melt blending extrusion processing of the polymer in the traditional technology. If the extrusion speed in the conventional technology is adopted, the carbon-based filler coated on the surface of the pure polymer particles is also easily and homogeneously dispersed in the polymer, so that the non-uniform dispersion effect of the carbon-based filler in the polymer matrix cannot be realized, and further the high electromagnetic shielding performance cannot be realized; below the extrusion rate defined in the present invention, the polymer particles are not easily extruded continuously.
Furthermore, the inventor researches in the implementation process to find that the electromagnetic shielding performance of the 3D-printable filament prepared in step (2) is mainly limited by the selection and loading of the carbon-based filler for electromagnetic shielding on the premise that the electromagnetic shielding performance of the 3D-printable product meets the commercial electromagnetic shielding performance standard of 20dB, and a stricter extrusion processing condition is matched, so that the construction of a filler network structure can be realized in a polymer matrix under the condition of low filler addition.
Therefore, in order to better explain the present invention and provide a preferred technical solution, on the premise of satisfying the electromagnetic shielding performance up to 20dB, the mechanical performance of the final 3D printed product is improved as much as possible:
the carbon-based filler for electromagnetic shielding in the step (1) is preferably 2-4 parts, and the carbon-based filler for electromagnetic shielding is any one or combination of graphene and carbon nano tubes; more preferably, the carbon-based filler for electromagnetic shielding is graphene and carbon nanotubes, and the mass ratio of the graphene to the carbon nanotubes is 1 (1-2); the extrusion processing parameters in the step (2) are as follows: the extrusion temperature is 2-6 ℃ higher than the melting temperature of the pure polymer particles, and the extrusion speed is 2-7 r/min.
The carbon-based filler for electromagnetic shielding is characterized in that when the carbon-based filler is limited to graphene or/and carbon nano tubes, the adaptive addition amount is 2-4 parts, the shielding performance of the electromagnetic shielding product printed by 3D printing filament lines prepared by extrusion is higher than the standard of commercial electromagnetic shielding performance, the carbon-based filler plays an effective reinforcing role, and the mechanical properties including tensile strength and Young modulus are similar to or slightly better than those of the product prepared by the same pure polymer; compared with the electromagnetic shielding product prepared by the traditional melt blending method and printed by the 3D printing thread line with uniformly distributed filler, the electromagnetic shielding product prepared by the traditional melt blending method can not meet the commercial electromagnetic shielding performance standard.
Further, the inventor researches in the implementation process to find that the 3D printable filament prepared in step (2) has an electromagnetic shielding performance of 40dB by properly increasing the content of the carbon-based filler for electromagnetic shielding on the premise of satisfying fused deposition modeling 3D printing, but the high electromagnetic shielding performance of the filament also needs to satisfy more strict extrusion processing conditions, so that the filament has a printable performance.
Therefore, in order to better explain the present invention and provide a preferred technical solution, on the premise of satisfying 3D printing, the electromagnetic shielding performance of the final 3D printed product is improved as much as possible:
the carbon-based filler for electromagnetic shielding in the step (1) is preferably 8-10 parts, and the carbon-based filler for electromagnetic shielding is any one or combination of graphene and carbon nano tubes; further preferably, in order to obtain higher shielding performance, the carbon-based filler for electromagnetic shielding is a carbon nanotube. The extrusion processing parameters in the step (2) are as follows: the extrusion temperature is 10-15 ℃ higher than the melting temperature of the pure polymer particles, and the extrusion speed is 8-15 r/min.
Under the strictly controlled extrusion processing conditions, the electromagnetic shielding performance of the corresponding 3D printed product can reach 40dB, and compared with the product which has the same filler content and is prepared by traditional melt blending and printed by silk strips, the electromagnetic shielding performance of the product is improved by 40-300%.
It should be noted that, referring to the technical solutions provided by the present invention, those skilled in the art can select more suitable or lower cost carbon-based fillers for electromagnetic shielding according to actual needs to meet the industrial needs, and in order to better illustrate the present invention, the following combination solutions are provided for reference:
firstly, when the carbon series filler for electromagnetic shielding in the step (1) is carbon nano tubes and the pure polymer particles are polylactic acid particles, the weight part of the carbon nano tubes is 5-8 parts; the extrusion processing parameters in the step (2) are as follows: the extrusion temperature is 5-8 ℃ higher than the melting temperature of the pure polymer particles, and the extrusion speed is 4-8 r/min. The obtained printed electromagnetic shielding product has high electromagnetic shielding performance and high printing performance.
The finally obtained printed electromagnetic shielding product has high electromagnetic shielding performance and high printing performance, and the electromagnetic shielding performance of the printed electromagnetic shielding product reaches 37 dB.
Secondly, when the carbon-based filler for electromagnetic shielding in the step (1) is graphene and the pure polymer particles are polyamide 11 particles, the graphene accounts for 5-8 parts by weight; the extrusion processing parameters in the step (2) are as follows: the extrusion temperature is 6-10 ℃ higher than the melting temperature of the pure polymer particles, and the extrusion speed is 6-10 r/min. The obtained printed electromagnetic shielding product has high electromagnetic shielding performance and high printing performance.
According to the technical scheme, the finally prepared printed electromagnetic shielding product has high electromagnetic shielding performance and high printing performance, and the electromagnetic shielding performance can reach 28 dB.
In general, other processing aids such as antioxidants, stabilizers, plasticizers, etc. known in the art may be added to the present invention in addition to the pure polymer particles and the electromagnetic shielding carbon-based filler. However, it is a prerequisite that these processing aids do not adversely affect the achievement of the objects of the present invention and the achievement of the advantageous effects of the present invention.
After the uniform dispersion in the step (1), standing to enable the carbon-based filler for electromagnetic shielding to be loaded on the surface of the pure polymer particles, generally, uniformly dispersing the carbon-based filler for electromagnetic shielding in a solvent in a stirring manner, and standing for at least 30 min.
It is noted that the strand silk capable of being 3D printed in step (2) of the present invention can be generally applied to fused deposition modeling 3D printing equipment, and the strict control of the fused extrusion processing and molding conditions in the technical solution of the present invention is mainly to ensure that the strand silk capable of being 3D printed prepared according to the present invention can be normally used in commercially available 3D printing equipment without special 3D printing equipment and printing process parameters.
Generally, in order to more effectively exert the electromagnetic shielding performance of the 3D printed electromagnetic shielding product obtained by the printing in the step (3), the thickness of the product is at least 0.5mm, preferably at least 1 mm.
The invention has the following beneficial effects:
1. according to the invention, the carbon-based filler for electromagnetic shielding is directionally loaded on the surface of the pure polymer particles, and then the 3D printing filament is prepared by extrusion processing under specific extrusion conditions, compared with the 3D printing filament with the same filler content prepared by the traditional melt blending method, the electromagnetic shielding performance is improved by 40-300%;
2. according to the invention, the carbon-based filler for electromagnetic shielding is directionally loaded on the surface of the pure polymer particles, and then the 3D printing filament is prepared by extrusion processing under a specific extrusion condition, and the finished piece can reach the commercial electromagnetic shielding performance standard under the condition of lower filler content. The process avoids the problem that the 3D printing strand silk is easy to block a printing nozzle after high-content filler is added, the printable performance of the 3D printing strand silk is deteriorated, the filler content is reduced, the raw material cost is saved, the technical problem of high shielding performance-low printability existing in the preparation of the 3D printing strand silk in the prior art is directly solved, the mechanical performance of a pure polymer is kept to the maximum extent, and even when a small amount of carbon-based filler is added, the mechanical performance including tensile strength and Young modulus are superior to that of the pure polymer;
3. according to the invention, the carbon-based filler for electromagnetic shielding is directionally loaded on the surface of the pure polymer particles, and then the 3D printing filament is extruded and prepared under a specific extrusion condition, so that the realization of high electromagnetic shielding performance of a 3D printing product under the condition of limited filler content is further researched, and stricter extrusion processing and forming process parameters are defined, so that the printing performance is still realized under the condition of high filler content, and a foundation is laid for further improving the electromagnetic shielding performance of the 3D printing product in the future;
4. based on the 3D printing strand silk, the invention can print products with complex structures, such as personalized and customized multi-scale electromagnetic shielding ventilating boards with complex shapes according to three-dimensional models, has simple production process, easy operation and strong personalized design, can meet the customization requirements of electronic devices with different sizes and different structures, has wide application and convenient popularization, and directly solves the defects of simple design structure, long period and high cost in the traditional preparation process of the electromagnetic shielding ventilating boards (mold design, casting molding and fine processing).
5. The technology for preparing the electromagnetic shielding product by adopting the 3D printing strand silk can completely realize full-automatic and continuous production on the basis of utilizing the existing commercial 3D printing equipment, and has obvious commercial popularization advantage from personalized modeling to an electromagnetic shielding ventilating plate with a complex structure by one-step molding without improving a printer or adding additional equipment.
Drawings
Fig. 1 is a transmission electron microscope (left image) of a 3D printed polylactic acid/graphene strand prepared by loading graphene with a content of 3% on the surface of polylactic acid particles in example 1 and then extruding under specific extrusion conditions, and a transmission electron microscope (right image) of a 3D printed polylactic acid/graphene strand prepared by conventional melt blending in comparative example 1 with a graphene content of 3%. The left graph result shows that the graphene is non-uniformly distributed in the polylactic acid matrix, the graphene and the graphene are effectively lapped, and a graphene network structure is successfully constructed; the result of the right graph shows that the graphene is uniformly distributed in the polylactic acid matrix, no lap joint exists between the graphene and the graphene, the graphene is distributed in a sea-island structure, and a network structure is not constructed.
Fig. 2 is a 3D printed polylactic acid/graphene strand prepared in example 1 by loading 3% content of graphene on the surface of polylactic acid particles, further extruding under a specific extrusion condition, and then performing 3D printing of a 3 mm-thick electromagnetic shielding ventilation board object photograph with a complex structure by melt deposition molding.
Fig. 3 is an electron microscope image of a 3D printed polylactic acid/graphene/carbon nanotube strand prepared by loading 2% of graphene and 4% of carbon nanotubes on the surface of polylactic acid particles prepared in example 2, extruding under a specific extrusion condition, and then performing 3D printing of a multi-size and multi-structure electromagnetic shielding ventilation board object photo with a thickness of 2.5mm by melt deposition molding and a microstructure thereof.
Fig. 4 is a comparison graph of the electromagnetic shielding performance (upper line) of the electromagnetic shielding ventilation board prepared in example 2, which is prepared by loading 2% of graphene and 4% of carbon nanotubes on the surface of polylactic acid particles, extruding the obtained 3D printed polylactic acid/graphene/carbon nanotube lines under a specific extrusion condition, and preparing the electromagnetic shielding ventilation board with the thickness of 2.5mm by melt deposition molding, and the electromagnetic shielding performance (lower line) of the electromagnetic shielding ventilation board prepared in comparative example 2, which is prepared by preparing 2% of graphene and 4% of carbon nanotubes by conventional melt blending, and preparing the electromagnetic shielding ventilation board with the thickness of 4mm by melt deposition molding. The result shows that the electromagnetic shielding performance of the electromagnetic shielding ventilating board prepared by the method is 35dB, the blocking rate of electromagnetic waves is 99.97 percent, and the electromagnetic shielding performance is completely higher than the commercial electromagnetic shielding performance standard (the electromagnetic shielding performance is 20dB, and the blocking rate of the electromagnetic waves is 99 percent), and the commercial requirement of the electromagnetic shielding ventilating board can be met; the electromagnetic shielding performance of the electromagnetic shielding ventilating board prepared by the traditional method is 14dB, the blocking rate of electromagnetic waves is 96.0 percent, and the commercial standard of electromagnetic shielding is not met. Compared with the electromagnetic shielding ventilating board prepared by the traditional method, the electromagnetic shielding performance of the electromagnetic shielding ventilating board prepared by the invention is improved by 150%.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
It should be noted that Agilent N5230A vector network analyzer is adopted for testing electromagnetic shielding performance in the examples and comparative examples, and the test wave band is 8.2-12.4 GHz.
Example 1
In this embodiment, the pure polymer particles are polylactic acid particles, and the carbon-based filler for electromagnetic shielding is graphene.
(1) Adding 100 parts of polylactic acid particles and 3 parts of graphene into deionized water, mechanically stirring for uniform dispersion, standing for 30min to enable the graphene filler to be loaded on the surfaces of pure polymer particles, performing suction filtration, and performing vacuum drying to obtain polymer particles with surfaces coated with the graphene filler;
(2) and (2) extruding the polymer particles coated with the graphene filler on the surface and obtained in the step (1) to obtain a strand silk capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 175 ℃, and the extrusion speed is 5 r/min;
(3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode into the 3D printing electromagnetic shielding ventilating board with the thickness of 3mm according to the three-dimensional digital model of the electromagnetic shielding ventilating board required by the step by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology; the 3D printing process parameters are as follows: 175 ℃ printing temperature, 400mm/min printing speed.
Through detection, the electromagnetic shielding performance of the prepared 3D printing electromagnetic shielding ventilating plate is 21dB, the tensile strength is improved by 18% compared with that of a polymer product, and the Young modulus is improved by 30%.
Comparative example 1
The comparative example was identical to example 1 except that the conventional melt blending method was used to disperse the filler uniformly and the conventional extrusion molding process was used.
(1) Adding 100 parts of polylactic acid particles and 3 parts of graphene into a double-screw extruder by adopting a traditional melt blending method, and performing melt blending extrusion at the extrusion temperature of 200 ℃ to obtain polylactic acid/graphene master batch with uniformly dispersed graphene;
(2) extruding the polylactic acid/graphene master batch obtained in the step (1) to prepare a strand silk capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 200 ℃, and the extrusion speed is 100 r/min;
(3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode into the 3D printing electromagnetic shielding ventilating board with the thickness of 3mm according to the three-dimensional digital model of the electromagnetic shielding ventilating board required by the step by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology; the 3D printing process parameters are as follows: 175 ℃ printing temperature, 400mm/min printing speed.
Through detection, the electromagnetic shielding performance of the manufactured 3D printing electromagnetic shielding ventilating board is 6dB, and the commercial electromagnetic shielding performance standard is not met.
Example 2
In this embodiment, the pure polymer particles are polylactic acid particles, and the carbon-based filler for electromagnetic shielding is graphene and carbon nanotubes.
(1) Adding 100 parts of polylactic acid particles, 2 parts of graphene and 4 parts of carbon nano tubes into deionized water, mechanically stirring for uniform dispersion, standing for 30min to enable the carbon-based filler for electromagnetic shielding to be loaded on the surfaces of pure polymer particles, performing suction filtration, and performing vacuum drying to obtain polymer particles coated with the carbon-based filler on the surfaces;
(2) and (2) extruding and processing the polymer particles coated with the carbon-based filler on the surface obtained in the step (1) to obtain filament yarns capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 178 ℃, and the extrusion speed is 8 r/min;
(3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode into the 3D printing electromagnetic shielding ventilating plate with the thickness of 2.5mm by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology according to a three-dimensional digital model of the electromagnetic shielding ventilating plate; the 3D printing process parameters are as follows: 178 ℃ printing temperature, 400mm/min printing speed.
Through detection, the electromagnetic shielding performance of the prepared 3D printing electromagnetic shielding ventilating board is 35 dB.
Comparative example 2
The comparative example was identical to example 2 except that the filler was uniformly dispersed by conventional melt blending.
(1) Adding 100 parts of polylactic acid particles, 2 parts of graphene and 4 parts of carbon nano tubes into a double-screw extruder by adopting a traditional melt blending method, and performing melt blending extrusion at the extrusion temperature of 205 ℃ to obtain polylactic acid/graphene/carbon nano tube master batches with uniformly dispersed graphene;
(2) extruding the polylactic acid/graphene/carbon nanotube master batch obtained in the step (1) to prepare a strand silk capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 205 ℃, and the extrusion speed is 150 r/min;
(3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode into the 3D printing electromagnetic shielding ventilating plate with the thickness of 2.5mm by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology according to a three-dimensional digital model of the electromagnetic shielding ventilating plate; the 3D printing process parameters are as follows: 178 ℃ printing temperature, 600mm/min printing speed.
Through detection, the electromagnetic shielding performance of the manufactured 3D printing electromagnetic shielding ventilating board is 14dB, and the commercial electromagnetic shielding performance standard is not met.
Example 3
In this example, the pure polymer particles are polyamide 11 particles, and the carbon-based filler for electromagnetic shielding is carbon nanotubes.
(1) Adding 100 parts of polyamide 11 particles and 2 parts of carbon nano tubes into deionized water, mechanically stirring for uniform dispersion, standing for 30min to enable the carbon-based filler for electromagnetic shielding to be loaded on the surfaces of pure polymer particles, performing suction filtration, and performing vacuum drying to obtain polymer particles coated with the carbon-based filler on the surfaces;
(2) and (2) extruding and processing the polymer particles coated with the carbon-based filler on the surface obtained in the step (1) to obtain filament yarns capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 185 ℃, and the extrusion speed is 8 r/min;
(3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode into a 3D printing electromagnetic shielding product with the thickness of 2mm by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology according to a three-dimensional digital model of the required electromagnetic shielding product; the 3D printing process parameters are as follows: 185 ℃ printing temperature and 500mm/min printing speed.
Through detection, the electromagnetic shielding performance of the prepared 3D printing electromagnetic shielding product is 26 dB.
Example 4
In this example, the pure polymer particles are polyamide 12 particles, and the carbon-based filler for electromagnetic shielding is carbon nanotubes.
(1) Adding 100 parts of polyamide 12 particles and 10 parts of carbon nano tubes into deionized water, mechanically stirring for uniform dispersion, standing for 30min to enable the carbon-based filler for electromagnetic shielding to be loaded on the surfaces of pure polymer particles, performing suction filtration, and performing vacuum drying to obtain polymer particles coated with the carbon-based filler on the surfaces;
(2) and (2) extruding and processing the polymer particles coated with the carbon-based filler on the surface obtained in the step (1) to obtain filament yarns capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 188 ℃, and the extrusion speed is 15 r/min;
(3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode into the 3D printing electromagnetic shielding ventilating plate with the thickness of 1.5mm according to the three-dimensional digital model of the electromagnetic shielding ventilating plate required by the step by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology; the 3D printing process parameters are as follows: 188 ℃ printing temperature and 200mm/min printing speed.
Through detection, the electromagnetic shielding performance of the manufactured 3D printing electromagnetic shielding ventilating board is 40 dB.
Example 5
In this embodiment, the pure polymer particles are polyvinyl alcohol particles, and the carbon-based filler for electromagnetic shielding is graphene.
(1) Adding 100 parts of polyvinyl alcohol particles and 8 parts of graphene into deionized water, mechanically stirring for uniform dispersion, standing for 30min to enable the carbon-based filler for electromagnetic shielding to be loaded on the surfaces of pure polymer particles, performing suction filtration, and performing vacuum drying to obtain polymer particles with the surfaces coated with the carbon-based filler;
(2) and (2) extruding the polymer particles coated with the carbon fillers obtained in the step (1) to prepare a strand silk capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 150 ℃, and the extrusion speed is 12 r/min;
(3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode into a 3D printing electromagnetic shielding ventilation board with the thickness of 2mm according to a three-dimensional digital model of the electromagnetic shielding ventilation board required by the step by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology; the 3D printing process parameters are as follows: printing temperature of 150 ℃ and printing speed of 300 mm/min.
Through detection, the electromagnetic shielding performance of the prepared 3D printing electromagnetic shielding ventilating board is 27 dB.
Example 6
In this embodiment, the pure polymer particles are polyethylene particles, and the carbon-based filler for electromagnetic shielding is graphite.
(1) Adding 100 parts of polyethylene particles and 9 parts of graphite into deionized water, mechanically stirring for uniform dispersion, standing for 30min to load the carbon-based filler for electromagnetic shielding on the surfaces of pure polymer particles, performing suction filtration, and performing vacuum drying to obtain polymer particles coated with the carbon-based filler on the surfaces;
(2) and (2) extruding the polymer particles coated with the carbon fillers obtained in the step (1) to prepare a strand silk capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 140 ℃, and the extrusion speed is 6 r/min;
(3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode into a 3D printing electromagnetic shielding ventilation board with the thickness of 4mm according to a three-dimensional digital model of the electromagnetic shielding ventilation board required by the step by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology; the 3D printing process parameters are as follows: printing temperature of 140 ℃ and printing speed of 500 mm/min.
Through detection, the electromagnetic shielding performance of the manufactured 3D printing electromagnetic shielding ventilating board is 24 dB.
Example 7
In this example, pure polymer particles are used as ABS resin particles, and carbon-based filler for electromagnetic shielding is carbon black.
(1) Adding 100 parts of ABS resin particles and 10 parts of carbon black into deionized water, mechanically stirring for uniform dispersion, standing for 30min to load carbon fillers for electromagnetic shielding on the surfaces of pure polymer particles, performing suction filtration, and performing vacuum drying to obtain polymer particles coated with the carbon fillers on the surfaces;
(2) and (2) extruding the polymer particles coated with the carbon fillers obtained in the step (1) to prepare a strand silk capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 183 ℃, and the extrusion speed is 15 r/min;
(3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode into a 3D printing electromagnetic shielding ventilation board with the thickness of 5mm according to a three-dimensional digital model of the electromagnetic shielding ventilation board required by the step by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology; the 3D printing process parameters are as follows: 183 ℃ printing temperature, 500mm/min printing speed.
Through detection, the electromagnetic shielding performance of the manufactured 3D printing electromagnetic shielding ventilating board is 26 dB.
Example 8
In this embodiment, the pure polymer particles are thermoplastic polyurethane elastomer particles, and the carbon-based filler for electromagnetic shielding is carbon nanotubes.
(1) Adding 100 parts of thermoplastic polyurethane elastomer particles and 10 parts of carbon nano tubes into deionized water, mechanically stirring for uniform dispersion, standing for 30min to enable the carbon-based filler for electromagnetic shielding to be loaded on the surfaces of pure polymer particles, performing suction filtration, and performing vacuum drying to obtain polymer particles coated with the carbon-based filler on the surfaces;
(2) and (2) extruding the polymer particles coated with the carbon fillers obtained in the step (1) to prepare a strand silk capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 85 ℃, and the extrusion speed is 14 r/min;
(3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode into a 3D printing electromagnetic shielding ventilation board with the thickness of 2mm according to a three-dimensional digital model of the electromagnetic shielding ventilation board required by the step by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology; the 3D printing process parameters are 85 ℃ printing temperature and 100mm/min printing speed.
Through detection, the electromagnetic shielding performance of the manufactured 3D printing electromagnetic shielding ventilating board is 38 dB.
Example 9
In this embodiment, pure polymer particles are used as ABS particles, and the carbon-based filler for electromagnetic shielding is graphene.
(1) Adding 100 parts of ABS particles and 5 parts of graphene into deionized water, mechanically stirring for uniform dispersion, standing for 30min to load carbon fillers for electromagnetic shielding on the surfaces of pure polymer particles, performing suction filtration, and performing vacuum drying to obtain polymer particles coated with the carbon fillers on the surfaces;
(2) and (2) extruding the polymer particles coated with the carbon fillers obtained in the step (1) to prepare a strand silk capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 175 ℃, and the extrusion speed is 5 r/min;
(3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode into the 3D printing electromagnetic shielding ventilating plate with the thickness of 2.8mm by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology according to a three-dimensional digital model of the electromagnetic shielding ventilating plate; the 3D printing process parameters are 175 ℃ printing temperature and 500mm/min printing speed.
Through detection, the electromagnetic shielding performance of the manufactured 3D printing electromagnetic shielding ventilating board is 25 dB.
Example 10
In this embodiment, the pure polymer particles are polypropylene particles, and the carbon-based filler for electromagnetic shielding is carbon nanotubes.
(1) Adding 100 parts of polypropylene particles and 2 parts of carbon nano tubes into deionized water, mechanically stirring for uniform dispersion, standing for 30min to enable the carbon-based filler for electromagnetic shielding to be loaded on the surfaces of pure polymer particles, performing suction filtration, and performing vacuum drying to obtain polymer particles coated with the carbon-based filler on the surfaces;
(2) and (2) extruding the polymer particles coated with the carbon fillers obtained in the step (1) to prepare a strand silk capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 166 ℃, and the extrusion speed is 2 r/min;
(3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode into the 3D printing electromagnetic shielding ventilating board with the thickness of 3mm according to the three-dimensional digital model of the electromagnetic shielding ventilating board required by the step by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology; the 3D printing process parameters are 166 ℃ printing temperature and 150mm/min printing speed.
Through detection, the electromagnetic shielding performance of the manufactured 3D printing electromagnetic shielding ventilating board is 22 dB.
Example 11
In this embodiment, the pure polymer particles are polyethylene particles, and the carbon-based filler for electromagnetic shielding is graphene and carbon nanotubes.
(1) Adding 100 parts of polyethylene particles, 2 parts of graphene and 6 parts of carbon nano tubes into deionized water, mechanically stirring for uniform dispersion, standing for 30min to enable the carbon-based filler for electromagnetic shielding to be loaded on the surface of the pure polymer particles, performing suction filtration, and performing vacuum drying to obtain polymer particles coated with the carbon-based filler on the surface;
(2) and (2) extruding the polymer particles coated with the carbon fillers obtained in the step (1) to prepare a strand silk capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 155 ℃, and the extrusion speed is 10 r/min;
(3) printing the filament strips which are prepared in the step (2) and can be printed in a 3D mode into a 3D printing electromagnetic shielding ventilation board with the thickness of 2mm according to a three-dimensional digital model of the electromagnetic shielding ventilation board required by the step by fused deposition modeling (abbreviated as FDM or FFF)3D printing technology; the 3D printing process parameters are as follows: 155 ℃ printing temperature and 400mm/min printing speed.
Through detection, the electromagnetic shielding performance of the manufactured 3D printing electromagnetic shielding ventilating board is 38 dB.
Claims (10)
1. A preparation method of a polymer-based 3D printing electromagnetic shielding product is characterized by comprising the following steps in parts by weight:
(1) adding 100 parts of pure polymer particles and 2-10 parts of carbon-based filler for electromagnetic shielding into water, standing after uniform dispersion to enable the carbon-based filler for electromagnetic shielding to be loaded on the surfaces of the pure polymer particles, filtering and drying to obtain polymer particles with the surfaces coated with the carbon-based filler;
(2) and (2) extruding and processing the polymer particles coated with the carbon-based filler on the surface obtained in the step (1) to obtain filament yarns capable of being printed in a 3D mode, wherein the extrusion processing technological parameters are as follows: the extrusion temperature is 2-15 ℃ higher than the melting temperature of the pure polymer particles, and the extrusion speed is 2-15 r/min;
(3) and (3) printing the filament which is prepared in the step (2) and can be printed in a 3D mode to obtain the 3D printed electromagnetic shielding product through a fused deposition modeling 3D printing technology according to the three-dimensional digital model of the target electromagnetic shielding product.
2. The method of claim 1, wherein: the pure polymer particles in the step (1) comprise any one of polylactic acid, polyamide 11, polyamide 12, polyvinyl alcohol, thermoplastic polyurethane elastomer, ABS resin, polyethylene and polypropylene.
3. The method of claim 1, wherein: the carbon-based filler for electromagnetic shielding in the step (1) comprises any one or combination of a plurality of graphene, carbon nano tubes, carbon black, graphite, football alkene and carbon fibers.
4. The method of claim 2, wherein: the particle size of the pure polymer particles is 50-300 mu m.
5. The method of claim 1, wherein: 2-4 parts of carbon-based filler for electromagnetic shielding, wherein the carbon-based filler for electromagnetic shielding is any one or combination of graphene and carbon nano tubes; the extrusion processing parameters in the step (2) are as follows: the extrusion temperature is 2-6 ℃ higher than the melting temperature of the pure polymer particles, and the extrusion speed is 2-7 r/min.
6. The method according to claim 5, wherein: the carbon-based filler for electromagnetic shielding is graphene and carbon nano tubes, and the mass ratio of the graphene to the carbon nano tubes is 1 (1-2).
7. The method of claim 1, wherein: 8-10 parts of carbon-based filler for electromagnetic shielding, wherein the carbon-based filler for electromagnetic shielding is any one or combination of graphene and carbon nano tubes; the extrusion processing parameters in the step (2) are as follows: the extrusion temperature is 10-15 ℃ higher than the melting temperature of the pure polymer particles, and the extrusion speed is 8-15 r/min.
8. The method according to claim 7, wherein: the carbon series filler for electromagnetic shielding is a carbon nano tube.
9. The method of claim 1, wherein: selecting carbon nano tubes as the carbon series filler for electromagnetic shielding in the step (1), selecting polylactic acid particles as polymer particles, and setting the weight parts of the carbon nano tubes to be 5-8 parts; the extrusion processing parameters in the step (2) are as follows: the extrusion temperature is 5-8 ℃ higher than the melting temperature of the pure polymer particles, and the extrusion speed is 4-8 r/min.
10. The method of claim 1, wherein: the carbon-based filler for electromagnetic shielding in the step (1) is graphene, the polymer particles are polyamide 11 particles, and the weight part of the graphene is 5-8 parts; the extrusion processing parameters in the step (2) are as follows: the extrusion temperature is 6-10 ℃ higher than the melting temperature of the pure polymer particles, and the extrusion speed is 6-10 r/min.
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| CN112373014B (en) * | 2020-10-09 | 2022-07-22 | 青岛大学 | Method for preparing magnetoelectric composite material based on magnetic field assisted 3D printing technology |
| CN112573922A (en) * | 2020-11-25 | 2021-03-30 | 中国科学院上海硅酸盐研究所 | Graphene/carbon nanotube hybrid network reinforced silicon carbide-based composite material and preparation method thereof |
| CN113561473B (en) * | 2021-07-13 | 2022-07-29 | 奇绩(苏州)精密科技有限公司 | Low-reflection high-absorption porous electromagnetic shielding device and preparation method thereof |
| CN113478810B (en) * | 2021-07-26 | 2022-05-03 | 四川大学 | Preparation method of polyvinylidene fluoride-based 3D printed piezoelectric part with porous structure |
| CN114790587B (en) * | 2022-05-16 | 2023-12-15 | 东部湾(扬州)生物新材料有限公司 | Wire material of 3D printing polylactic acid/conductive filler electromagnetic shielding composite material, preparation method and application |
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| US9992917B2 (en) * | 2014-03-10 | 2018-06-05 | Vulcan GMS | 3-D printing method for producing tungsten-based shielding parts |
| KR101712506B1 (en) * | 2014-11-27 | 2017-03-07 | 재단법인 한국탄소융합기술원 | Manufacturing Method of Filament for 3D Print and Filament |
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