CN115384136A - Composite material applied to electromagnetic shielding and preparation method thereof - Google Patents

Composite material applied to electromagnetic shielding and preparation method thereof Download PDF

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Publication number
CN115384136A
CN115384136A CN202211034808.2A CN202211034808A CN115384136A CN 115384136 A CN115384136 A CN 115384136A CN 202211034808 A CN202211034808 A CN 202211034808A CN 115384136 A CN115384136 A CN 115384136A
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prepreg
carbon fiber
functional layer
composite material
resin
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孙昊
李昊亮
蔡计杰
李婷
朱家强
王滨
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Shanghai Jinfei Carbon Fiber Technology Co ltd
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Shanghai Jinfei Carbon Fiber Technology Co ltd
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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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/047—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/103—Metal fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • 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

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Electromagnetism (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Fluid Mechanics (AREA)
  • Laminated Bodies (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

The invention relates to the technical field of composite materials, and particularly discloses a preparation method of a composite material applied to electromagnetic shielding, which comprises the following steps: soaking the functional layer film into the modified resin matrix to obtain a functional layer prepreg; laying the obtained functional layer prepreg and the fiber prepreg in a laminated manner to obtain a composite laminated prepreg; and carrying out hot-pressing treatment on the obtained composite laminated prepreg to obtain the composite laminated prepreg. The invention combines the light weight and high strength characteristics of the carbon fiber composite material and the excellent conductivity of the functional layer film, realizes the structure/electromagnetic shielding integrated application of the composite material through interface modification, has simple preparation method and simple and convenient operation, is easy to realize large-scale batch production, and has wide application prospect.

Description

Composite material applied to electromagnetic shielding and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method of a composite material applied to electromagnetic shielding.
Background
With the development of aerospace technologies, components such as aircrafts and electronic devices not only need to meet the requirement of light weight, but also have higher requirements on electromagnetic shielding performance of shells and chassis bottom materials due to the increasing integration level and complexity of electronic control units. Therefore, the development of carbon fiber composite materials with light weight, electromagnetic shielding and electromagnetic compatibility has become a key task for developing raw materials in the aerospace field. The carbon fiber composite material has extremely excellent modulus and strength and low density (about 1.8g cm) -3 ) The bearing is widely applied to the field of light weight of structural components and replaces metal structural parts to bear loads. However, due to the insulating property of the resin in the composite material, the traditional carbon fiber material does not have the functions of electromagnetic shielding and electromagnetic compatibility.
At present, the method for improving the conductivity of resin mainly comprises a filler filling method, and specifically comprises the following steps: metal nano powder filler, nano carbon powder filler and the like, and a lamination composite forming method. However, in the aspect of filling the filler, because the dispersibility of the nano powder and the resin matrix is poor, a continuous conductive network cannot be formed in the matrix due to a small amount of filling; and the excessive filling is easy to form agglomeration, so that the mechanical property of the composite material is extremely attenuated, and the conditions of interface fracture, brittle failure and the like are easy to occur, thereby influencing the normal use of the composite material.
For example, in a preparation method for improving the electromagnetic shielding performance of a carbon fiber composite material based on a graphene-filled polymer reported in patent CN 104419107B, the graphene powder is filled with resin to improve the conductivity of the polymer, but the dispersibility of the powder in a polymer matrix is poor, so that the traditional conductive powder filling strategy is very likely to cause the attenuation of the mechanical properties of the composite material; patent 202010522086.X also reports that a conductive additive is mixed into a matrix such as epoxy resin to be compounded with carbon fibers to prepare a prepreg having conductive and electromagnetic shielding properties, but this method still does not effectively solve the problems of dispersibility of powder in the matrix and failure to form a conductive network. Patent 202011283317.2 reports a high-thermal-conductivity carbon fiber composite material with a laminated hybrid structure and a preparation method thereof, conductive copper powder or graphene powder is uniformly sprayed on the surface of carbon fibers by utilizing a spraying process, patent CN 112724687A proposes a method for electroplating or chemically plating a metal layer on the surface of the carbon fibers, so that the problem of dispersibility of the powder on a polymer matrix can be effectively solved, however, whether a compact and continuous conductive layer can be formed by spraying is still examined, and the bonding effect of the coating and the surface of the carbon fibers is weak, so that the coating is easy to fall off in the using process, and the electromagnetic shielding performance is ineffective.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the composite material applied to electromagnetic shielding and the preparation method thereof, the electromagnetic shielding performance of the composite material in the X wave band (8-12 GHz) range can be improved to more than 60dB, the bonding effect between the carbon fiber prepreg and the functional layer is enhanced through interface modification, and the application requirement of integrating the light weight and the electromagnetic shielding function of electronic equipment is met.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a composite material applied to electromagnetic shielding, which at least comprises the following steps:
soaking the functional layer film into the modified resin matrix to obtain a functional layer prepreg;
laying the obtained functional layer prepreg and the fiber prepreg in a laminated manner to obtain a composite laminated prepreg;
and carrying out hot-pressing treatment on the obtained composite laminated prepreg to obtain the composite laminated prepreg.
Preferably, the functional layer film comprises at least one of a graphene film, a carbon nanotube film, a graphite film, and a metal foil/mesh.
Preferably, the modified resin matrix comprises the following components: resin matrix, modifier and assistant.
Preferably, the weight ratio of the modifier to the auxiliary agent is (30-60): (5-20).
Preferably, the resin matrix includes at least one of a phenol resin, an epoxy resin, a polyimide resin, a bismaleimide resin, a polyetheretherketone resin, and the like.
Preferably, the modifier comprises at least one of conductive carbon black, graphene, multi-walled carbon nanotubes and silver nanowires.
Preferably, the auxiliary agent comprises at least one of polyvinyl alcohol, methyl pyrrolidone, polyvinyl pyrrolidone, dimethylformamide and dimethylsulfoxide.
Preferably, the fibrous prepreg comprises a unidirectional prepreg or a bidirectional woven carbon fiber cloth prepreg.
Preferably, the hot-pressing treatment comprises low-temperature curing and high-temperature curing, wherein the low-temperature curing condition is that the temperature is 100-140 ℃, and the curing time is 0.5-1 h; the high-temperature curing condition is that the temperature is 160-220 ℃, and the curing time is 0.5-2 h.
The invention also provides a composite material applied to electromagnetic shielding, which is obtained by the preparation method, and comprises a carbon fiber prepreg, a functional resin layer and a functional layer, wherein the functional layer is positioned between two adjacent layers of the carbon fiber prepreg, the upper surface layer and the lower surface layer of the functional layer are respectively provided with the functional resin layer, and the functional layer is combined with the carbon fiber prepreg through the functional resin layer.
The invention has the beneficial effects that: according to the invention, the carbon fiber prepreg and the functional layer are laminated and laid to prepare the composite material with excellent mechanical strength and electromagnetic shielding effectiveness and integrated structure function, and the interface modification modified high-conductivity functional layer is inserted between the carbon fiber prepreg to enhance the bonding effect between the electromagnetic shielding functional layer and the carbon fiber prepreg, so that the carbon fiber composite material is endowed with an electromagnetic shielding function, and the application requirement of the integration of the light weight and the electromagnetic shielding function of electronic equipment is met.
Drawings
Fig. 1 is a schematic structural view of a composite material for electromagnetic shielding according to the present invention;
fig. 2 is a schematic view of the structure at a in fig. 1.
In the figure, A is a carbon fiber prepreg; b is a functional layer; and C is a functionalized resin layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments and the accompanying drawings. It should be understood that the embodiments described herein are only for illustrating the present invention and are not to be construed as limiting the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preparation method of a composite material applied to electromagnetic shielding, which at least comprises the following steps:
soaking the functional layer film into the modified resin matrix to obtain a functional layer prepreg;
laying the obtained functional layer prepreg and the fiber prepreg in a laminated manner to obtain a composite laminated prepreg;
and carrying out hot-pressing treatment on the obtained composite laminated prepreg to obtain the composite laminated prepreg.
In some embodiments, the functional layer film comprises at least one of a graphene film, a carbon nanotube film, a graphite film, a metal foil/mesh.
In some embodiments, the functional layer film has an average thickness of 0.01 to 0.05mm in a single layer.
Preferably, the functional layer film has a single layer average thickness of 0.025mm, and the functional layer film has a thickness increased to suitably improve the electromagnetic shielding performance, but an excessive thickness increases the weight of the composite material and also decreases the tensile strength and the interlaminar shear strength of the composite material.
In some embodiments, the modified resin matrix comprises the following components: resin matrix, modifier and assistant.
Preferably, the modified resin matrix comprises the following components in percentage by weight: 1 to 40 percent of modifier, 0.1 to 10 percent of auxiliary agent and the balance of resin matrix.
In some embodiments, the weight ratio of modifier to adjuvant is (30 to 60): (5-20).
In some embodiments, the resin matrix comprises at least one of phenolic resin, epoxy resin, polyimide resin, bismaleimide resin, polyetheretherketone resin, and the like.
Preferably, the resin matrix is an epoxy resin.
In some embodiments, the modifier comprises at least one of conductive carbon black, graphene, multi-walled carbon nanotubes, silver nanowires.
In some embodiments, the adjuvant comprises at least one of polyvinyl alcohol, methyl pyrrolidone, polyvinyl pyrrolidone, dimethylformamide, dimethylsulfoxide.
In some embodiments, the specific method of modification of the modified resin matrix comprises the steps of: adding an auxiliary agent into the resin matrix, slowly adding the modifier after the auxiliary agent is uniformly dispersed, and continuously stirring until the mixture is uniformly mixed to obtain the modified resin matrix.
In the research of the applicant, the proportion of the modifier to the auxiliary agent is found to influence the performance of the composite material, and the main reason is that the improper proportion of the modifier to the auxiliary agent can cause the modifier to agglomerate and precipitate in a resin matrix or increase the viscosity of the resin matrix, so that the operational difficulty in the process of compounding the functional layer film and the fiber prepreg is increased, the electrical conductivity of the joint of the functional layer film and the fiber prepreg is also influenced, and the electromagnetic shielding effect is further deteriorated, and the application selects the special modifier and the auxiliary agent, and limits the weight ratio of the modifier to the auxiliary agent to be (30-60): (5-20), the prepared composite material has excellent conductivity and electromagnetic shielding effectiveness, and the processability of the composite material can be ensured to be excellent.
In some embodiments, the fiber prepreg comprises a unidirectional carbon fiber prepreg or a prepreg made of a bidirectional woven carbon fiber cloth.
Preferably, the carbon fibers comprise polyacrylonitrile-based carbon fibers or pitch-based carbon fibers.
The orientation of the carbon fibers and the thickness of the laminate in the present invention can be adjusted according to the mechanical properties of the application scenario, and the manner of stacking includes, but is not limited to, unidirectional lay-up, i.e., lay-up at 0 °, and bidirectional alternate lay-up, e.g., 0 °/° 90 °/0 °/\8230, + 0 °/90 ° or +45 °/-45 °/\8230, +45 °/+45 °, where "+" and "-" denote opposite directions.
In some embodiments, the number of filaments of the carbon fiber is 1k to 24k, the number of layers of the carbon fiber prepreg stack is 5 to 20, the number of layers of the functional layer is not less than 4 to 16, and the thickness of the carbon fiber prepreg is related to the number of filaments of the carbon fiber, for example, the thickness of a 6k carbon fiber prepreg is about 0.2mm, the thickness of a 12k carbon fiber prepreg is about 0.05mm, and the thickness of a 24k carbon fiber prepreg is about 0.1mm.
The outermost layer of the laminated laying structure is carbon fiber prepreg so as to ensure the mechanical property of the composite material.
In some embodiments, the hot pressing treatment comprises low-temperature curing and high-temperature curing, wherein the low-temperature curing is performed at a temperature of 100-140 ℃ for 0.5-1 h; the high-temperature curing condition is that the temperature is 160-220 ℃, and the curing time is 0.5-2 h.
In some embodiments, the rate of temperature increase in the hot pressing process is 10 to 25 ℃ and the pressure is 2 to 10MPa.
Preferably, the heating rate in the hot pressing treatment is 10-20 ℃, and the pressure is 4-10 MPa.
The applicant finds that the condition of the hot pressing treatment influences the quality and the mechanical property of the composite material, the composite material obtained by the integrated temperature hot pressing treatment can form internal stress in the forming process, so that the composite material is high in brittleness, easy to crack and the like, and the tensile property of the composite material is poor due to improper conditions of the temperature rise rate, the temperature and the pressure.
The invention also provides a composite material applied to electromagnetic shielding, which is obtained by the preparation method, and comprises a carbon fiber prepreg, a functional resin layer and a functional layer, wherein the functional layer is positioned between two adjacent layers of the carbon fiber prepreg, the upper surface layer and the lower surface layer of the functional layer are respectively provided with the functional resin layer, and the functional layer is combined with the carbon fiber prepreg through the functional resin layer.
Example 1
The embodiment provides a preparation method of a composite material applied to electromagnetic shielding, which comprises the following steps:
(1) Preparation of modified resin matrix: adding 8 parts by weight of polyvinyl alcohol into 100 parts by weight of epoxy resin, uniformly dispersing, and then adding 30 parts by weight of conductive carbon black powder, uniformly dispersing to obtain a modified resin matrix;
(2) Coating the modified resin matrix obtained in the step (1) on a functional layer film, wherein the coating thickness is 50-100 mu m, so as to obtain a functional layer prepreg;
(3) Preparing a carbon fiber prepreg, wherein the thickness of a single-layer carbon fiber prepreg is 50 microns, and cutting the single-layer carbon fiber prepreg into sizes of 60cm and 60cm;
(4) Taking 5 layers of carbon fiber prepregs, sequentially and alternately arranging and laying the layers according to cutting angles of 0 degree and 90 degrees, laying a layer of functional layer prepreg in two adjacent layers of carbon fiber prepregs to form a composite laminated prepreg, and placing the composite laminated prepreg in a hot-press forming mold;
(5) Placing the composite laminated prepreg obtained in the step (4) and a hot-pressing forming die on a hot press, heating to 120 ℃ at a heating rate of 20 ℃/min, applying pressure of 4MPa after the temperature is stable, and curing for 0.5h;
(6) And (5) after the curing in the step (5) is finished, further heating to 180 ℃, curing for 0.5h at the temperature, cooling, and demoulding to obtain the composite material.
Wherein the epoxy resin is ST001 epoxy resin manufactured by Shanghai Jinfei carbon fiber science and technology corporation.
The functional layer film is a polyimide graphite film with the thickness of 0.025mm.
The carbon fiber prepreg adopts carbon fiber, ST001 epoxy resin is prepreg resin, and the resin content is 24%, and the surface density is 150g/m 2 The carbon fiber prepreg of (1).
Example 2
The embodiment provides a preparation method of a composite material applied to electromagnetic shielding, which comprises the following steps:
(1) Preparation of modified resin matrix: adding 8 parts by weight of polyvinyl alcohol into 100 parts by weight of epoxy resin, uniformly dispersing, and then adding 30 parts by weight of carbon nanotube powder, uniformly dispersing to obtain a modified resin matrix;
(2) Coating the modified resin matrix obtained in the step (1) on a functional layer film, wherein the coating thickness is 50-100 mu m, so as to obtain a functional layer prepreg;
(3) Preparing carbon fiber prepreg, wherein the thickness of the single-layer carbon fiber prepreg is 50 mu m, and cutting the single-layer carbon fiber prepreg into sizes of 60cm and 60cm;
(4) Taking 10 layers of carbon fiber prepregs, sequentially and alternately arranging and laying the layers according to cutting angles of 0 degree and 90 degrees, laying a layer of functional layer prepreg in two adjacent layers of carbon fiber prepregs to form a composite laminated prepreg, and placing the composite laminated prepreg in a hot-press forming mold;
(5) Placing the composite laminated prepreg obtained in the step (4) and a hot-pressing forming die on a hot press, heating to 120 ℃ at a heating rate of 20 ℃/min, applying pressure of 4MPa after the temperature is stable, and curing for 1h;
(6) And (5) after the curing in the step (5) is finished, further heating to 160 ℃, curing for 1.5h at the temperature, cooling, and demoulding to obtain the composite material.
Wherein the epoxy resin is ST001 epoxy resin manufactured by Shanghai Jinfei carbon fiber science and technology corporation.
The functional layer film is a polyimide graphite film with the thickness of 0.025mm.
The carbon fiber prepreg adopts carbon fiber, ST001 epoxy resin is prepreg resin, and the resin content is 24%, and the surface density is 150g/m 2 The carbon fiber prepreg of (1).
Example 3
The embodiment provides a preparation method of a composite material applied to electromagnetic shielding, which comprises the following steps:
(1) Preparation of modified resin matrix: adding 12 parts by weight of polyvinyl alcohol into 100 parts by weight of epoxy resin, uniformly dispersing, and then adding 40 parts by weight of graphene powder, uniformly dispersing to obtain a modified resin matrix;
(2) Coating the modified resin matrix obtained in the step (1) on a functional layer film, wherein the coating thickness is 50-100 mu m, so as to obtain a functional layer prepreg;
(3) Preparing a carbon fiber prepreg, wherein the thickness of a single-layer carbon fiber prepreg is 50 microns, and cutting the single-layer carbon fiber prepreg into sizes of 60cm and 60cm;
(4) Taking 15 layers of carbon fiber prepregs, sequentially and alternately arranging and laying the layers according to cutting angles of 0-degree and 90-degree, laying a layer of functional layer prepreg in two adjacent layers of carbon fiber prepregs to form a composite laminated prepreg, and placing the composite laminated prepreg in a hot-press forming mold;
(5) Placing the composite laminated prepreg obtained in the step (4) and a hot-pressing forming die on a hot press, heating to 100 ℃ at a heating rate of 20 ℃/min, applying pressure of 6MPa after the temperature is stable, and curing for 1h;
(6) And (5) after the curing in the step (5) is finished, further heating to 140 ℃, curing for 2 hours at the temperature, cooling, and demolding to obtain the composite material.
Wherein the epoxy resin is ST001 epoxy resin manufactured by Shanghai Jinfei carbon fiber science and technology corporation.
The functional layer film is a conductive graphene film, and the thickness of the functional layer film is 0.025mm.
The carbon fiber prepreg adopts carbon fiber, ST001 epoxy resin is prepreg resin, and the resin content is 24%, and the surface density is 150g/m 2 The carbon fiber prepreg of (1).
Example 4
The embodiment provides a preparation method of a composite material applied to electromagnetic shielding, which comprises the following steps:
(1) Preparation of modified resin matrix: adding 18 parts by weight of polyvinyl alcohol into 100 parts by weight of epoxy resin, uniformly dispersing, and then adding 30 parts by weight of graphene powder, uniformly dispersing to obtain a modified resin matrix;
(2) Coating the modified resin matrix obtained in the step (1) on a functional layer film, wherein the coating thickness is 50-100 mu m, so as to obtain a functional layer prepreg;
(3) Preparing a carbon fiber prepreg, wherein the thickness of a single-layer carbon fiber prepreg is 50 microns, and cutting the single-layer carbon fiber prepreg into sizes of 60cm and 60cm;
(4) Taking 15 layers of carbon fiber prepregs, sequentially and alternately arranging and laying the layers according to cutting angles of 0-degree and 90-degree, laying a layer of functional layer prepreg in two adjacent layers of carbon fiber prepregs to form a composite laminated prepreg, and placing the composite laminated prepreg in a hot-press forming mold;
(5) Placing the composite laminated prepreg obtained in the step (4) and a hot-pressing forming die on a hot press, heating to 140 ℃ at a heating rate of 20 ℃/min, applying pressure of 6MPa after the temperature is stable, and curing for 1h;
(6) And (5) after the curing in the step (5) is finished, further heating to 160 ℃, curing for 2 hours at the temperature, cooling, and demolding to obtain the composite material.
Wherein the epoxy resin is ST001 epoxy resin manufactured by Shanghai Jinfei carbon fiber science and technology corporation.
The functional layer film is a conductive graphene film, and the thickness of the functional layer film is 0.025mm.
The carbon fiber prepreg adopts carbon fiber, ST001 epoxy resin is prepreg resin, and the resin content is 24%, and the surface density is 150g/m 2 The carbon fiber prepreg of (1).
Example 5
The embodiment provides a preparation method of a composite material applied to electromagnetic shielding, which comprises the following steps:
(1) Preparation of modified resin matrix: adding 5 parts by weight of methyl pyrrolidone into 100 parts by weight of epoxy resin, uniformly dispersing, and then adding 40 parts by weight of silver nanowires, and uniformly dispersing to obtain a modified resin matrix;
(2) Coating the modified resin matrix obtained in the step (1) on a functional layer film, wherein the coating thickness is 50-100 mu m, so as to obtain a functional layer prepreg;
(3) Preparing a carbon fiber prepreg, wherein the thickness of a single-layer carbon fiber prepreg is 20 microns, and cutting the single-layer carbon fiber prepreg into sizes of 60cm and 60cm;
(4) Taking 15 layers of carbon fiber prepregs, sequentially and alternately arranging and laying the layers according to cutting angles of 0 degree and 90 degrees, laying a layer of functional layer prepreg in two adjacent layers of carbon fiber prepregs to form a composite laminated prepreg, and placing the composite laminated prepreg in a hot-press forming mold;
(5) Placing the composite laminated prepreg obtained in the step (4) and a hot-pressing forming die on a hot press, heating to 120 ℃ at a heating rate of 10 ℃/min, applying pressure of 4MPa after the temperature is stable, and curing for 0.8h;
(6) And (5) after the curing in the step (5) is finished, further heating to 140 ℃, curing for 1h at the temperature, cooling, and demolding to obtain the composite material.
Wherein the epoxy resin is ST001 epoxy resin manufactured by Shanghai Jinfei carbon fiber science and technology corporation, the diameter of the silver nanowire is 50nm, and the concentration is 20mg/mL.
The functional layer film is a copper foil with the thickness of 0.05mm.
The carbon fiber prepreg adopts carbon fiber, and ST001 epoxy resin is used for prepregResin prepared to have a resin content of 24% and an areal density of 150g/m 2 The carbon fiber prepreg of (1).
Example 6
The embodiment provides a preparation method of a composite material applied to electromagnetic shielding, which comprises the following steps:
(1) Preparation of modified resin matrix: adding 15 parts by weight of dimethyl sulfoxide into 100 parts by weight of epoxy resin, uniformly dispersing, and then adding 50 parts by weight of conductive carbon black powder, uniformly dispersing to obtain a modified resin matrix;
(2) Coating the modified resin matrix obtained in the step (1) on a functional layer film, wherein the coating thickness is 50-100 mu m, so as to obtain a functional layer prepreg;
(3) Preparing a carbon fiber prepreg, wherein the thickness of a single-layer carbon fiber prepreg is 100 microns, and cutting the single-layer carbon fiber prepreg into sizes of 60cm and 60cm;
(4) Taking 10 layers of carbon fiber prepregs, sequentially and alternately arranging and laying the layers according to cutting angles of 0 degree and 90 degrees, laying a layer of functional layer prepreg in two adjacent layers of carbon fiber prepregs to form a composite laminated prepreg, and placing the composite laminated prepreg in a hot-press forming mold;
(5) Placing the composite laminated prepreg obtained in the step (4) and a hot-pressing forming die on a hot press, heating to 140 ℃ at a heating rate of 10 ℃/min, applying pressure of 6MPa after the temperature is stable, and curing for 0.5h;
(6) And (5) after the curing in the step (5) is finished, further heating to 200 ℃, curing for 1 hour at the temperature, cooling, and demoulding to obtain the composite material.
Wherein the epoxy resin is ST001 epoxy resin manufactured by Shanghai Jinfei carbon fiber science and technology corporation.
The functional layer film is a copper mesh with the thickness of 50 mu m.
The carbon fiber prepreg adopts carbon fiber, ST001 epoxy resin is prepreg resin, and the resin content is 24%, and the surface density is 150g/m 2 The carbon fiber prepreg of (1).
Example 7
The embodiment provides a preparation method of a composite material applied to electromagnetic shielding, which comprises the following steps:
(1) Preparation of modified resin matrix: adding 10 parts by weight of dimethylformamide into 100 parts by weight of epoxy resin, uniformly dispersing, and then adding 60 parts by weight of graphene powder, and uniformly dispersing to obtain a modified resin matrix;
(2) Coating the modified resin matrix obtained in the step (1) on a functional layer film, wherein the coating thickness is 50-100 mu m, so as to obtain a functional layer prepreg;
(3) Preparing a carbon fiber prepreg, wherein the thickness of a single-layer carbon fiber prepreg is 100 microns, and cutting the single-layer carbon fiber prepreg into sizes of 60cm and 60cm;
(4) Taking 10 layers of carbon fiber prepregs, sequentially and alternately arranging and laying the layers according to cutting angles of +45 degrees and-45 degrees, laying a layer of functional layer prepreg in two adjacent layers of carbon fiber prepregs to form a composite laminated prepreg, and placing the composite laminated prepreg in a hot-press forming mold;
(5) Placing the composite laminated prepreg obtained in the step (4) and a hot-pressing forming die on a hot press, heating to 140 ℃ at a heating rate of 10 ℃/min, applying pressure of 6MPa after the temperature is stable, and curing for 0.5h;
(6) And (5) after the curing in the step (5) is finished, further heating to 200 ℃, curing for 1h at the temperature, cooling, and demolding to obtain the composite material.
Wherein the epoxy resin is ST001 epoxy resin manufactured by Shanghai Jinfei carbon fiber science and technology corporation.
The functional layer film is a conductive graphene film, and the thickness of the functional layer film is 0.025mm.
The carbon fiber prepreg adopts carbon fiber, ST001 epoxy resin is prepreg resin, and the resin content is 24%, and the surface density is 150g/m 2 The carbon fiber prepreg of (1).
Example 8
The embodiment provides a preparation method of a composite material applied to electromagnetic shielding, which comprises the following steps:
(1) Preparation of modified resin matrix: adding 40 parts of graphene powder into 100 parts of epoxy resin by weight parts, and uniformly dispersing to obtain a modified resin matrix;
(2) Coating the modified resin matrix obtained in the step (1) on a functional layer film, wherein the coating thickness is 50-100 mu m, so as to obtain a functional layer prepreg;
(3) Preparing carbon fiber prepreg, wherein the thickness of the single-layer carbon fiber prepreg is 50 mu m, and cutting the single-layer carbon fiber prepreg into sizes of 60cm and 60cm;
(4) Taking 20 layers of carbon fiber prepregs, sequentially and alternately arranging and laying the 20 layers of carbon fiber prepregs according to cutting angles of 0-degree and 90-degree, laying a layer of functional layer prepreg in two adjacent layers of carbon fiber prepregs to form a composite laminated prepreg, and placing the composite laminated prepreg in a hot-pressing forming die;
(5) Placing the composite laminated prepreg obtained in the step (4) and a hot-pressing forming die on a hot press, heating to 100 ℃ at a heating rate of 20 ℃/min, applying pressure of 10MPa after the temperature is stable, and curing for 0.5h;
(6) And (5) after the curing in the step (5) is finished, further heating to 220 ℃, curing for 1.5h at the temperature, cooling, and demoulding to obtain the composite material.
Wherein the epoxy resin is ST001 epoxy resin manufactured by Shanghai Jinfei carbon fiber science and technology corporation.
The functional layer film is a conductive graphene film, and the thickness of the functional layer film is 0.025mm.
The carbon fiber prepreg adopts carbon fiber, ST001 epoxy resin is prepreg resin, and the resin content is 24%, and the surface density is 150g/m 2 The carbon fiber prepreg of (1).
Example 9
The embodiment provides a preparation method of a composite material applied to electromagnetic shielding, which comprises the following steps:
(1) Preparation of modified resin matrix: adding 8 parts of dimethylformamide into 100 parts of epoxy resin by weight parts, uniformly dispersing, and then adding 40 parts of graphene powder, uniformly dispersing to obtain a modified resin matrix;
(2) Coating the modified resin matrix obtained in the step (1) on a functional layer film, wherein the coating thickness is 50-100 mu m, so as to obtain a functional layer prepreg;
(3) Preparing a carbon fiber prepreg, wherein the thickness of a single-layer carbon fiber prepreg is 100 microns, and cutting the single-layer carbon fiber prepreg into sizes of 60cm and 60cm;
(4) Taking 20 layers of carbon fiber prepregs, sequentially and alternately arranging and laying the layers according to cutting angles of +45 degrees and-45 degrees, laying a layer of functional layer prepreg in two adjacent layers of carbon fiber prepregs to form a composite laminated prepreg, and placing the composite laminated prepreg in a hot-press forming mold;
(5) Placing the composite laminated prepreg obtained in the step (4) and a hot-pressing forming die on a hot press, heating to 140 ℃ at a heating rate of 20 ℃/min, applying pressure of 10MPa after the temperature is stable, and curing for 0.5h;
(6) And (5) after the curing in the step (5) is finished, further heating to 180 ℃, curing for 1.5h at the temperature, cooling, and demoulding to obtain the composite material.
Wherein the epoxy resin is ST001 epoxy resin manufactured by Shanghai Jinfei carbon fiber science and technology corporation.
The functional layer film is a conductive graphene film, and the thickness of the functional layer film is 0.025mm.
The carbon fiber prepreg adopts carbon fiber, ST001 epoxy resin is prepreg resin, and the resin content is 24%, and the surface density is 150g/m 2 The carbon fiber prepreg of (1).
Example 10
The embodiment provides a preparation method of a composite material applied to electromagnetic shielding, which comprises the following steps:
(1) Preparing a carbon fiber prepreg, wherein the thickness of a single-layer carbon fiber prepreg is 50 microns, and cutting the single-layer carbon fiber prepreg into sizes of 60cm and 60cm;
(2) Taking 5 layers of carbon fiber prepregs, sequentially and alternately arranging and laying the layers according to cutting angles of 0 degree and 90 degrees to form a composite laminated prepreg, and placing the composite laminated prepreg in a hot-press forming die;
(3) Placing the composite laminated prepreg obtained in the step (2) and a hot-pressing forming die on a hot press, heating to 100 ℃ at a heating rate of 20 ℃/min, applying pressure of 4MPa after the temperature is stable, and curing for 0.5h;
(4) And (5) after the curing in the step (5) is finished, further heating to 160 ℃, curing for 0.5 hour at the temperature, cooling, and demoulding to obtain the composite material.
The carbon fiber prepreg adopts carbon fiber, ST001 epoxy resin is prepreg resin, and the resin content is 24%, and the surface density is 150g/m 2 The carbon fiber prepreg of (1).
Example 11
Referring to fig. 1 and 2, the present embodiment provides a composite material for electromagnetic shielding, obtained according to the preparation method of embodiment 4, and the composite material includes a carbon fiber prepreg a, a functional resin layer B, and a functional layer C, where the functional layer B is located between two adjacent layers of the carbon fiber prepreg a, the upper and lower surface layers of the functional layer B are respectively provided with a functional resin layer C, and the functional layer B is bonded to the carbon fiber prepreg a through the functional resin layer C.
Performance testing
The composites prepared in examples 1-10 were tested for the following properties:
1. tensile strength
The test was carried out according to ASTM D3039, with the results shown in Table 1.
2. Electromagnetic shielding effectiveness
The test was carried out according to the shielded room method defined in GJB 6190-2008 standard, and the results are shown in Table 1.
TABLE 1
Figure BDA0003818506550000121
Figure BDA0003818506550000131
In summary, the functional layer modified by interface modification and the carbon fiber prepreg are integrated to form the carbon fiber composite material, so that the electromagnetic shielding performance of the carbon fiber composite material can be effectively improved, the mechanical performance of the final composite material product fluctuates with different forming processes, but no obvious attenuation occurs, the structural function is still better, the electromagnetic shielding performance is remarkably improved to more than 60dB and can exceed 80dB, and the application requirements in the field of electromagnetic shielding at present can be met.
It should be noted that the above mentioned embodiments are only preferred embodiments of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by the present specification, or any other related technical fields directly or indirectly, are included in the scope of the present invention.

Claims (10)

1. The preparation method of the composite material applied to electromagnetic shielding is characterized by at least comprising the following steps:
soaking the functional layer film into the modified resin matrix to obtain a functional layer prepreg;
laying the obtained functional layer prepreg and the fiber prepreg in a laminated manner to obtain a composite laminated prepreg;
and carrying out hot-pressing treatment on the obtained composite laminated prepreg to obtain the composite laminated prepreg.
2. The method of claim 1, wherein the functional layer film comprises at least one of a graphene film, a carbon nanotube film, a graphite film, and a metal foil/mesh.
3. The method of claim 1, wherein the modified resin matrix comprises the following components: resin matrix, modifier and assistant.
4. The method for preparing a composite material for electromagnetic shielding according to claim 3, wherein the weight ratio of the modifier to the additive is (30-60): (5-20).
5. The method of claim 3, wherein the resin matrix comprises at least one of phenolic resin, epoxy resin, polyimide resin, bismaleimide resin, polyetheretherketone resin, and the like.
6. The method of claim 4, wherein the modifier comprises at least one of conductive carbon black, graphene, multi-walled carbon nanotubes, and silver nanowires.
7. The method of claim 4, wherein the auxiliary comprises at least one of polyvinyl alcohol, methyl pyrrolidone, polyvinyl pyrrolidone, dimethylformamide, and dimethylsulfoxide.
8. The method of claim 1, wherein the fiber prepreg comprises a unidirectional carbon fiber prepreg or a prepreg made of a bidirectional woven carbon fiber cloth.
9. The method for preparing a composite material for electromagnetic shielding according to claim 1, wherein the hot pressing comprises low temperature curing and high temperature curing, the low temperature curing is performed at a temperature of 100-140 ℃ for a time of 0.5-1 h; the high-temperature curing condition is that the temperature is 160-220 ℃, and the curing time is 0.5-2 h.
10. The composite material for electromagnetic shielding, prepared by the preparation method according to any one of claims 1 to 9, comprises a carbon fiber prepreg, a functional resin layer and a functional layer, wherein the functional layer is positioned between two adjacent layers of the carbon fiber prepreg, the upper surface layer and the lower surface layer of the functional layer are respectively provided with the functional resin layer, and the functional layer is combined with the carbon fiber prepreg through the functional resin layer.
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CN117082796A (en) * 2023-10-16 2023-11-17 歌尔股份有限公司 Electronic device, composite shell and preparation method thereof

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CN108410136A (en) * 2018-05-02 2018-08-17 北京大学 Novel high heat conduction graphene or graphite film/carbon fibre composite preparation method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108410136A (en) * 2018-05-02 2018-08-17 北京大学 Novel high heat conduction graphene or graphite film/carbon fibre composite preparation method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117082796A (en) * 2023-10-16 2023-11-17 歌尔股份有限公司 Electronic device, composite shell and preparation method thereof
CN117082796B (en) * 2023-10-16 2024-03-12 歌尔股份有限公司 Electronic device, composite shell and preparation method thereof

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