CN112208157B - Carbon foam filled carbon nanotube honeycomb electromagnetic shielding material and preparation method and application thereof - Google Patents

Carbon foam filled carbon nanotube honeycomb electromagnetic shielding material and preparation method and application thereof Download PDF

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CN112208157B
CN112208157B CN201910629221.8A CN201910629221A CN112208157B CN 112208157 B CN112208157 B CN 112208157B CN 201910629221 A CN201910629221 A CN 201910629221A CN 112208157 B CN112208157 B CN 112208157B
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carbon
carbon nanotube
electromagnetic shielding
nano tube
honeycomb
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CN112208157A (en
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胡东梅
张鹏飞
晁卓
巩倩
邸江涛
李清文
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/12—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a layer of regularly- arranged cells, e.g. a honeycomb structure
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/18—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by an internal layer formed of separate pieces of material which are juxtaposed side-by-side
    • B32B3/20—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by an internal layer formed of separate pieces of material which are juxtaposed side-by-side of hollow pieces, e.g. tubes; of pieces with channels or cavities
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/107—Ceramic
    • B32B2264/108—Carbon, e.g. graphite particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/12—Mixture of at least two particles made of different materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/04—Inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/06—Open cell foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/022—Foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/024—Honeycomb
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/026—Porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/028—Hollow fillers; Syntactic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212—Electromagnetic interference shielding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/60—In a particular environment

Abstract

The invention discloses a carbon foam filled carbon nanotube honeycomb electromagnetic shielding material and a preparation method and application thereof. The preparation method of the carbon foam filled carbon nanotube honeycomb electromagnetic shielding material comprises the following steps: connecting a plurality of carbon nanotube films, and shaping by adopting shaping resin to form a carbon nanotube honeycomb core structure; filling a carbon foam material serving as a filling material in the carbon nanotube honeycomb core structure, wherein the carbon foam material has a porous structure consisting of a three-dimensional network space structure; and encapsulating the carbon nano tube composite film serving as the honeycomb plate on the top surface and the bottom surface of the carbon nano tube honeycomb core structure to obtain the carbon foam filled carbon nano tube honeycomb electromagnetic shielding material. According to the invention, the biomass raw material is foamed and carbonized to obtain the carbon foam material as the honeycomb core filling material, and the carbon nanotube film with extremely light weight is used as the honeycomb core and the panel, so that the density of the honeycomb plate is reduced, the material with excellent electromagnetic shielding efficiency is prepared, and the preparation of a novel electromagnetic protection material is realized.

Description

Carbon foam filled carbon nanotube honeycomb electromagnetic shielding material and preparation method and application thereof
Technical Field
The invention relates to a preparation method of an electromagnetic shielding material, in particular to a carbon foam filled carbon nanotube honeycomb electromagnetic shielding material, and a preparation method and application thereof, and belongs to the technical field of composite materials.
Background
To date, researchers in various countries have made intensive researches in the field of electromagnetic shielding, and a large amount of electromagnetic shielding materials are developed and applied to various industries. The demand of electromagnetic shielding materials for military and civil use is becoming more important, and the problems of light weight and cost are more necessary to be considered on the premise of ensuring shielding effectiveness. The conventional electromagnetic shielding material cannot satisfy these new requirements, and therefore, it is of great significance to develop a novel electromagnetic shielding material.
The conventional electromagnetic shielding material mainly uses a metal material or a shielding coating material, which have certain limitations. The prior art mainly has the following defects: 1) The traditional electromagnetic shielding honeycomb plate is made of metal materials such as copper, aluminum, stainless steel and the like, and has heavy mass and high density (CN 205219945U and CN 206475511U), and the coating has the defect of easy falling (CN 108359368A and CN 108034313A); 2) The traditional material adopts a large amount of metal materials, which causes certain harm to the environment; 3) The traditional metal material has high cost.
Nowadays, in order to meet the requirements of aerospace, military and civil fields, researchers shift their attention to the development of efficient and light nano or micro-nano electromagnetic shielding materials.
Disclosure of Invention
The invention mainly aims to provide a carbon foam filled carbon nanotube honeycomb electromagnetic shielding material and a preparation method thereof, so as to overcome the defects in the prior art.
The invention also aims to provide application of the carbon foam filled carbon nanotube honeycomb electromagnetic shielding material.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a carbon foam filled carbon nanotube honeycomb electromagnetic shielding material, which comprises the following steps:
providing a carbon nanotube film;
connecting a plurality of carbon nanotube films, and shaping by adopting shaping resin to form a carbon nanotube honeycomb core structure;
filling a carbon foam material serving as a filling material in the carbon nanotube honeycomb core structure, wherein the carbon foam material has a porous structure consisting of a three-dimensional network space structure; and the number of the first and second groups,
and packaging the carbon nano tube composite film serving as the honeycomb plate on the top surface and the bottom surface of the carbon nano tube honeycomb core structure to obtain the carbon foam filled carbon nano tube honeycomb electromagnetic shielding material.
In some embodiments, the method of making comprises: filling a uniform mixing system containing foaming raw materials, water and a foaming agent into a through hole structure of the carbon nano tube honeycomb core structure, steaming and taking out, and then heating and carbonizing in a protective atmosphere to obtain the carbon nano tube honeycomb core structure filled with carbon foam.
Further, the preparation method specifically comprises the following steps: in protective atmosphere, heating to 120-140 ℃ at the speed of 2-4 ℃/min, preserving heat for 30-40 min, heating to 790-810 ℃ at the speed of 4-6 ℃/min, preserving heat for 100-120 min, and carbonizing.
The embodiment of the invention also provides a carbon foam filled carbon nanotube honeycomb electromagnetic shielding material prepared by the method, which comprises the following steps:
the carbon nanotube honeycomb core structure is characterized in that a carbon foam material is filled in a through hole structure of the carbon nanotube honeycomb core structure, and the carbon foam material has a porous structure consisting of a three-dimensional network space structure; and the number of the first and second groups,
and the carbon nano tube composite films are packaged on the top surface and the bottom surface of the carbon nano tube honeycomb core structure.
The embodiment of the invention also provides application of the carbon foam filled carbon nanotube honeycomb electromagnetic shielding material in preparation of electromagnetic protection materials.
Compared with the prior art, the invention has the beneficial effects that:
1) According to the invention, the biomass raw material is foamed and carbonized to obtain the carbon foam material as the honeycomb core filling material, and the carbon nanotube film with extremely light weight is used as the honeycomb core and the panel, so that the density of the honeycomb panel is fully reduced, the material with excellent electromagnetic shielding efficiency is prepared, various applications can be met, and the preparation of a novel electromagnetic protection material is realized;
2) According to the honeycomb core filling material, biomass raw materials (flour, potato starch and the like) are foamed and carbonized to serve as the honeycomb core filling material, the raw materials are wide in source, widely available renewable resources are fully utilized, the environment is friendly, and the material cost is low; the prepared honeycomb plate fully utilizes the structural porosity and excellent conductivity of the material, so that the honeycomb plate has excellent electromagnetic shielding performance;
3) The carbon nanotube film and the carbon foam material have strong interface bonding capability, and the whole body cannot collapse or separate after carbonization, so that the carbon nanotube film has certain structural stability;
4) The main materials used in the invention are biomass materials, carbon nanotube films, foaming agents and adhesives such as macromolecules, setting resin, yeast and the like, and toxic and harmful products are not used, so that the invention conforms to the concept of green and environmental protection.
5) The electromagnetic shielding material prepared by the invention has simple process and lower cost, can enlarge batch production and realizes commercialization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a flow chart illustrating a process for preparing a carbon foam filled carbon nanotube honeycomb electromagnetic shielding material according to an exemplary embodiment of the present invention.
FIG. 2 is a schematic illustration of the fabrication of a carbon nanotube honeycomb core in an exemplary embodiment of the invention.
Fig. 3 is a schematic structural diagram of a carbon foam filled carbon nanotube honeycomb electromagnetic shielding material according to an exemplary embodiment of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a great deal of practice, wherein biomass raw material foaming carbonized foam is mainly adopted as a honeycomb core filling material, and a carbon nanotube film composite material is adopted as a honeycomb core and a panel, so that a material with excellent electromagnetic shielding efficiency is prepared, and the preparation of a novel electromagnetic protection material is realized. The technical solution, its implementation and principles, etc. will be further explained as follows.
The carbon foam structure has the performance of light weight and low density, and simultaneously has excellent electromagnetic shielding characteristics; the honeycomb structure has the advantages of being not easy to crack and deform, simultaneously having the effects of shock absorption and sound insulation, and further expanding the rich application of the electromagnetic shielding material by adopting the carbon nano tubes with excellent performances such as high conductivity, high modulus, high strength, low density, high temperature resistance and the like as the honeycomb core and panel materials.
Due to the characteristics of porosity and low density of the foam, the carbon foam material with a unique structure can be prepared after high-temperature carbonization treatment, the internal three-dimensional network space structure of the carbon foam material enables the carbon foam material to have better electric conductivity, and meanwhile, the porous structure enables electromagnetic waves to be reflected and dissipated in pores for many times, so that more excellent electromagnetic shielding efficiency is shown. The light weight and excellent conductivity of the carbon nanotube film determine the excellent electromagnetic shielding effectiveness of the carbon nanotube film as a material of the honeycomb core and the panel.
One aspect of the embodiments of the present invention provides a method for preparing a carbon foam filled carbon nanotube honeycomb electromagnetic shielding material, comprising:
providing a carbon nanotube film;
connecting a plurality of carbon nano tube films, and shaping by adopting shaping resin to form a carbon nano tube honeycomb core structure;
filling a carbon foam material serving as a filling material in the carbon nanotube honeycomb core structure, wherein the carbon foam material has a porous structure consisting of a three-dimensional network space structure; and (c) a second step of,
and encapsulating the carbon nano tube composite film serving as the honeycomb plate on the top surface and the bottom surface of the carbon nano tube honeycomb core structure to obtain the carbon foam filled carbon nano tube honeycomb electromagnetic shielding material.
In some embodiments, the method of making comprises: and preparing the carbon nano tube film at least by adopting a floating catalytic chemical vapor deposition method.
The carbon nanotube film is not substitutable as a honeycomb core material, the carbon nanotube has excellent performances of high conductivity, high modulus, high strength, low density, high temperature resistance and the like, and if other materials are selected as the honeycomb core, the material structure is easy to be unstable and easy to decompose during carbonization. The light weight and excellent conductivity of carbon nanotubes determine the excellent electromagnetic shielding performance of the carbon nanotubes as honeycomb core and panel materials.
In some embodiments, the method of making comprises: and connecting the plurality of carbon nanotube films by adopting an adhesive, soaking the carbon nanotube films in a setting resin, taking out the carbon nanotube films, and curing and setting the carbon nanotube films to obtain the carbon nanotube honeycomb core structure.
In some more specific embodiments, the preparation method specifically comprises:
folding each carbon nanotube film, wherein the distances between adjacent folds are equal;
coating adhesive on each carbon nanotube film at intervals, wherein the width of the formed adhesive tape is the distance between adjacent creases, and the distance between adjacent adhesive tapes is 3 times of the width of the adhesive tape;
sequentially laminating the plurality of carbon nanotube films coated with the adhesive in a staggered manner, so that the adhesive tape of each carbon nanotube film is positioned between the adjacent adhesive tapes of the adjacent carbon nanotube film, sequentially laminating, cutting and stretching to form a carbon nanotube honeycomb core structure with a regular hexagonal through hole structure; and the number of the first and second groups,
and soaking the carbon nano tube honeycomb core structure in a setting resin, taking out the carbon nano tube honeycomb core structure, removing the redundant setting resin, and then curing and setting the carbon nano tube honeycomb core structure in an oven to obtain the hard carbon nano tube honeycomb core structure.
Furthermore, the adhesive used for adhering the carbon nanotube film in the present invention may be epoxy AB adhesive, paste instant adhesive, etc., or may be other adhesives, which is not limited herein.
Further, the size of the through hole structure of the carbon nanotube honeycomb core structure can be adjusted and controlled according to the distance between adjacent creases.
Further, the resin used for shaping the carbon nanotube honeycomb core structure in the present invention may be any one or a combination of two or more of phenol resin, epoxy resin, bismaleimide resin, and the like, and may be other resins, which is not limited herein.
In some embodiments, the method of making comprises: filling a uniform mixing system containing foaming raw materials, water and a foaming agent into a through hole structure of the carbon nano tube honeycomb core structure, steaming and taking out, and then heating and carbonizing in a protective atmosphere to obtain the carbon nano tube honeycomb core structure filled with the carbon foam material.
Furthermore, the porosity of the carbon foam material is 59% -69%, and the density is 0.22-0.32 g/cm 3 。
Further, the preparation method specifically comprises the following steps: heating to 120-140 ℃ at the speed of 2-4 ℃/min in protective atmosphere, preserving heat for 30-40 min, heating to 790-810 ℃ at the speed of 4-6 ℃/min, preserving heat for 100-120 min, and carbonizing.
Due to the characteristics of porosity and low density of the foam, the carbon foam material with a unique structure can be prepared after high-temperature carbonization treatment, the internal three-dimensional network space structure of the carbon foam material enables the carbon foam material to have better electric conductivity, and meanwhile, the porous structure enables electromagnetic waves to be reflected and dissipated in pores for many times, so that more excellent electromagnetic shielding efficiency is shown.
Further, the protective atmosphere includes an inert atmosphere, preferably an argon atmosphere, but is not limited thereto.
Further, the homogeneous mixing system further includes a functional filler, and the functional filler includes magnetic particles, preferably any one or a combination of two or more of mixed magnetic bodies such as iron, cobalt, nickel, and the like, so as to increase the electromagnetic shielding effectiveness, but is not limited thereto. The carbon foam filled carbon nanotube honeycomb composite material prepared by the invention has excellent electromagnetic shielding performance, and the electromagnetic shielding performance of the honeycomb plate can be further improved by adding a certain amount of magnetic particle fillers.
In some embodiments, the foaming raw material may be any one or a combination of two or more of biomass raw materials such as flour, potato starch, corn starch and the like, and may also be other biomass starch. Further, the foaming raw material can be replaced by phenolic resin with higher carbon residue rate.
Further, the foaming agent may be an inorganic foaming agent, an organic foaming agent, or the like or a mixture thereof, and is preferably yeast, but not limited thereto.
In some embodiments, the method of making comprises:
compounding the carbon nanotube film with polymer to form a carbon nanotube composite film;
and connecting the carbon nano tube composite film to the top surface and the bottom surface of the carbon nano tube honeycomb core structure by adopting a binder to obtain the carbon foam filled carbon nano tube honeycomb electromagnetic shielding material.
Further, the preparation method comprises the following steps: and soaking the carbon nano tube film in a high molecular solution to form the carbon nano tube composite film.
Further, the carbon nanotube composite film as the panel may be compounded with a polymer such as PVA, TPU, PI, or the like.
Further, the polymer includes any one or a combination of two or more of PVA, TPU, PI, and the like, but is not limited thereto.
Further, the content of the polymer in the polymer solution is 1 to 1.5wt%.
As a typical embodiment of the present invention, the method for preparing the carbon foam filled carbon nanotube honeycomb electromagnetic shielding material specifically comprises the following steps:
firstly, connecting carbon nanotube films by using quick-drying glue to prepare a carbon nanotube honeycomb core structure, spreading and soaking the carbon nanotube films in phenolic resin, taking out the carbon nanotube films, draining the excess resin, and putting the carbon nanotube films into an oven for curing to obtain the hard carbon nanotube honeycomb core structure. Mixing flour, water and yeast, stirring, fermenting, kneading, exhausting, filling in the prepared carbon nanotube honeycomb core structure, steaming, taking out, putting into a furnace, and heating under the protection of argon gas for carbonization. And adhering the carbon nano tube composite film soaked in the PVA solution on the upper surface and the lower surface of the carbon nano tube honeycomb core structure by using glue to serve as panels, thereby preparing the carbon foam filled carbon nano tube honeycomb electromagnetic shielding material. The electromagnetic shielding cellular board prepared by the method has low density and low cost, and the filling material fully utilizes renewable resources widely existing in the nature and is environment-friendly. The cellular board prepared by the method fully utilizes the structural porosity and excellent conductivity of the material, so that the cellular board has excellent electromagnetic shielding performance.
Another aspect of an embodiment of the present invention also provides a carbon foam filled carbon nanotube honeycomb electromagnetic shielding material prepared by the foregoing method, including:
the carbon nano tube honeycomb core structure is characterized in that a carbon foam material is filled in a through hole structure of the carbon nano tube honeycomb core structure, the carbon foam material has a porous structure consisting of a three-dimensional network space structure, the porosity of the carbon foam material is 59% -69%, and the density of the carbon foam material is 0.22-0.32 g/cm 3 (ii) a And the number of the first and second groups,
the carbon nano tube composite films are packaged on the top surface and the bottom surface of the carbon nano tube honeycomb core structure;
the carbon foam filled carbon nanotube honeycomb electromagnetic shielding material has the following electromagnetic shielding effectiveness at the wave band of 8.2-12.4 GHz: 50-90 dB.
Further, the carbon nanotube honeycomb core structure is further filled with a functional filler, and the functional filler includes magnetic particles, preferably any one or a combination of two or more of mixed magnetic bodies such as iron, cobalt, nickel, and the like, so as to increase the electromagnetic shielding effectiveness, but is not limited thereto. The carbon foam filled carbon nanotube honeycomb composite material prepared by the invention has excellent electromagnetic shielding performance, and the electromagnetic shielding performance of the honeycomb plate can be further improved by adding a certain amount of magnetic particle fillers.
The invention also provides an application of the carbon foam filled carbon nanotube honeycomb electromagnetic shielding material in preparation of a novel electromagnetic protection material.
In conclusion, the invention adopts the biomass raw material to foam and carbonize to obtain the carbon foam material as the honeycomb core filling material, and the carbon nanotube film with extremely light weight as the honeycomb core and the panel, thereby reducing the density of the honeycomb panel, preparing the material with excellent electromagnetic shielding efficiency and realizing the preparation of the novel electromagnetic protection material; moreover, the preparation process is simple, the cost is low, the batch production can be expanded, and the commercialization is realized.
The invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
Embodiment 1 as shown in fig. 1, a method for preparing a carbon foam filled carbon nanotube honeycomb electromagnetic shielding material comprises the following specific technical steps:
1) Carbon Nanotube (CNT) thin film: the carbon nano tube film is prepared by a floating catalytic chemical vapor deposition method. (Suzhou Jiedi nanotechnology Co., ltd.)
2) Carbon nanotube honeycomb core structure: as shown in fig. 2, each carbon nanotube film is folded, and the distances between the folded creases are equal; gluing each carbon nanotube film at intervals, wherein the width of each adhesive tape is the distance between two creases, the distance between adjacent adhesive tapes is the width of the adhesive tape which is 3 times, laminating a plurality of glued carbon nanotube films in a staggered manner, arranging the adhesive tape of a second carbon nanotube film in the middle of the adjacent adhesive tape of a first carbon nanotube film, arranging the adhesive tape of a third carbon nanotube film in the middle of the adjacent adhesive tape of the second carbon nanotube film, laminating, and cutting according to the height of the carbon nanotube honeycomb core structure. And pulling the carbon nanotube honeycomb core structure open to enable the through hole structure to be in a regular hexagon shape, soaking the phenolic resin liquid, taking out the phenolic resin liquid, draining the redundant resin, and putting the phenolic resin liquid into an oven for shaping.
3) Carbon foam filled honeycomb core: mixing and stirring a certain amount of flour, water and yeast, well mixing and fermenting, uniformly kneading and exhausting, filling into the prepared honeycomb core, steaming, taking out, putting into a furnace, heating to 120-140 ℃ at the speed of 2-4 ℃/min under the protection of argon, preserving heat for 30-40 min, heating to 790-810 ℃ at the speed of 4-6 ℃/min, and preserving heat for 100-120 min, thereby preparing the carbon foam filled carbon nano tube honeycomb core structure.
4) And (3) honeycomb plate packaging: soaking the carbon nano tube film in 1-1.5 wt% of PVA aqueous solution, taking out and drying, fixing the carbon nano tube film on two sides of the carbon nano tube honeycomb core structure by using glue, and finally preparing the carbon foam filled carbon nano tube honeycomb electromagnetic shielding material, wherein the structure can be shown in figure 3.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and sections in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the invention.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or order in which certain actions are performed is not critical, so long as the present teachings remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (13)

1. A preparation method of a carbon foam filled carbon nanotube honeycomb electromagnetic shielding material is characterized by comprising the following steps:
providing a carbon nanotube film;
folding each carbon nanotube film, wherein the distances between adjacent folds are equal;
coating adhesive on each carbon nanotube film at intervals, wherein the width of the formed adhesive tape is the distance between adjacent creases, and the distance between adjacent adhesive tapes is 3 times of the width of the adhesive tape;
sequentially laminating the plurality of carbon nanotube films coated with the adhesive in a staggered manner, so that the adhesive tape of each carbon nanotube film is positioned between the adjacent adhesive tapes of the adjacent carbon nanotube film, sequentially laminating, cutting and stretching to form a carbon nanotube honeycomb core structure with a regular hexagonal through hole structure; and the number of the first and second groups,
soaking the carbon nano tube honeycomb core structure in a setting resin, taking out the carbon nano tube honeycomb core structure, removing the redundant setting resin, and then curing and setting the carbon nano tube honeycomb core structure in an oven to obtain a hard carbon nano tube honeycomb core structure;
filling a uniformly mixed system containing foaming raw materials, water and foaming agent into a through hole structure of the carbon nano tube honeycomb core structure, steaming and taking out, then heating to 120-140 ℃ at the speed of 2-4 ℃/min in protective atmosphere, preserving heat for 30-40 min, heating to 790-810 ℃ at the speed of 4-6 ℃/min, preserving heat for 100-120 min, heating and carbonizing to obtain the carbon nano tube honeycomb core structure filled with the carbon foam material; the porosity of the carbon foam material is 59-69%, and the density is 0.22-0.32 g/cm 3 (ii) a And the number of the first and second groups,
soaking the carbon nanotube film in a high molecular solution; the polymer comprises any one or the combination of more than two of PVA, TPU and PI; the content of the macromolecule in the macromolecule solution is 1-1.5 wt%, and a carbon nano tube composite film is formed;
connecting the carbon nano tube composite film to the top surface and the bottom surface of the carbon nano tube honeycomb core structure by adopting a binder to obtain a carbon foam filled carbon nano tube honeycomb electromagnetic shielding material;
the carbon foam filled carbon nanotube honeycomb electromagnetic shielding material has the following electromagnetic shielding effectiveness at the wave band of 8.2-12.4 GHz: 50-90 dB.
2. The production method according to claim 1, characterized by comprising: and preparing the carbon nano tube film at least by adopting a floating catalytic chemical vapor deposition method.
3. The production method according to claim 1, characterized in that: the adhesive comprises epoxy resin AB adhesive and/or paste instant adhesive.
4. The method of claim 1, wherein: the setting resin comprises any one or the combination of more than two of phenolic resin, epoxy resin and bismaleimide resin.
5. The method according to claim 1, characterized in that the protective atmosphere is an argon atmosphere.
6. The method of claim 1, wherein: the homogeneous mixing system also comprises a functional filling body.
7. The method of claim 1, wherein: the foaming raw material comprises a biomass raw material, and the biomass raw material comprises any one or a combination of more than two of flour, potato starch and corn starch.
8. The method of claim 1, wherein: the foaming agent is yeast.
9. The method of claim 6, wherein: the functional filler includes magnetic particles.
10. The method of claim 9, wherein: the magnetic particles are any one or the combination of more than two of iron, cobalt and nickel.
11. The carbon foam filled carbon nanotube honeycomb electromagnetic shielding material prepared by the method of any one of claims 1-10, comprising:
the carbon nanotube honeycomb core structure is characterized in that a carbon foam material is filled in a through hole structure of the carbon nanotube honeycomb core structure, the carbon foam material has a porous structure formed by a three-dimensional network space structure, the porosity of the carbon foam material is 59-69%, and the density of the carbon foam material is 0.22-0.32 g/cm 3 (ii) a And，
the carbon nano tube composite films are packaged on the top surface and the bottom surface of the carbon nano tube honeycomb core structure;
the carbon foam filled carbon nanotube honeycomb electromagnetic shielding material has the following electromagnetic shielding effectiveness at the wave band of 8.2-12.4 GHz: 50-90 dB.
12. The carbon foam-filled carbon nanotube honeycomb electromagnetic shielding material of claim 11, wherein: the carbon nano tube honeycomb core structure is also filled with a functional filling body, the functional filling body comprises magnetic particles, and the magnetic particles are any one or the combination of more than two of iron, cobalt and nickel.
13. Use of the carbon foam filled carbon nanotube honeycomb electromagnetic shielding material of any one of claims 11-12 in the preparation of electromagnetic shielding materials.
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