CN112280077A - Prepreg with electromagnetic shielding function and preparation method thereof - Google Patents
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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Abstract
The invention belongs to the technical field of functional composite materials, and particularly relates to a prepreg with an electromagnetic shielding function and a preparation method thereof, wherein the preparation method comprises the following specific steps: and uniformly mixing the resin matrix with the toughening agent and the nano filler, and then compounding the resin matrix with the fiber layer and the electromagnetic shielding layer through a hot-melt method prepreg process to obtain the electromagnetic shielding prepreg. The prepreg has the characteristics of excellent manufacturability, stable electromagnetic shielding performance, high shielding effect and good mechanical property. The electromagnetic shielding composite material product prepared by the prepreg has the characteristics of reliable shielding effect and no process influence, and can be used for preparing composite material products with electromagnetic shielding functions.
Description
Technical Field
The invention belongs to the technical field of functional composite materials, and particularly relates to a prepreg with an electromagnetic shielding function and a preparation method thereof.
Background
The electromagnetic radiation brings great challenges to the use safety of equipment and the safety of human bodies, and the electromagnetic radiation is prevented or becomes an important assessment index for equipment development by utilizing the electromagnetic radiation. With the improvement of the requirement of light weight, the usage amount of the resin-based composite material is continuously increased, but at present, the method for endowing the resin-based composite material with electromagnetic wave characteristics generally comprises the steps of spraying the electromagnetic material on the outer surface or additionally arranging an electromagnetic wave protection device. The method is simple, but has high cost and low reliability, and can not exert the advantage of designability of the composite material. The electromagnetic wave material is arranged in the composite material, which is an ideal design scheme, but at present, because the recognition level of the electromagnetic wave characteristic of the composite material is uneven, the performance of the composite material can be influenced when the electromagnetic wave characteristic material (such as a wave absorber) and the electromagnetic shielding material (such as a shielding copper net) are arranged in the composite material, and secondly, because the construction of the materials is different from that of the composite material, the construction is limited by the level of constructors, and the quality controllability of the composite material structural member prepared by the method is poor.
Disclosure of Invention
In order to solve the technical problems, the invention provides a prepreg with an electromagnetic shielding function and a preparation method thereof, and the prepreg with the excellent electromagnetic shielding function, mechanical property and process property is obtained by utilizing a nano material, a wave-transmitting resin matrix and fibers, and the preparation method of the prepreg is provided.
The invention is realized in such a way that the prepreg with the electromagnetic shielding function comprises the following components in parts by weight:
40-50 parts of pre-impregnated resin mixture
49-59 parts of fiber layer
1-10 parts of shielding layer
The prepreg resin mixture comprises the following components in parts by weight:
60-97 parts of resin matrix
2-30 parts of toughening agent
1-10 parts of nano filler.
Preferably, the resin matrix is a wave-transparent resin that can be used to prepare prepregs by a hot-melt process.
More preferably, the resin matrix is one of epoxy resin, cyanate resin, bismaleimide resin and phthalonitrile resin.
Preferably, the toughening agent is one or more of rubber containing hydroxyl and epoxy groups, a toughening agent containing a core-shell structure, thermoplastic particles and an aliphatic compound containing active groups.
More preferably, the nano filler has an inorganic particle structure with a particle size of 10-500 nm.
Further preferably, the nanofiller is one of a carbon nanotube, a graphene sheet, and silicon carbide.
Preferably, the fiber layer is one or more of glass fiber, carbon fiber and aramid fiber; the shielding layer is one or more of a copper net, a nickel net, an iron net, a stainless steel net, a carbon nano film and a graphene film with ductility.
The invention also provides a method for preparing the prepreg with the electromagnetic shielding function, which comprises the following steps:
1) drying the resin matrix, the toughening agent, the nano filler, the fiber layer and the shielding layer at the drying temperature of 60-110 ℃ for 1-10 hours;
2) heating a resin matrix to a molten state, and uniformly mixing the resin matrix with a toughening agent and a nano filler according to a proportion to obtain a pre-impregnated resin mixture;
3) regularly arranging fiber layers on a yarn guide system of a pre-soaking machine;
4) attaching the fiber layer arranged in the step 3) on at least one surface of the shielding layer to obtain a reinforced material mixture;
5) compounding the pre-impregnated resin mixture obtained in the step 2) with the reinforced material mixture obtained in the step 4) through a pre-impregnating machine to obtain the electromagnetic shielding pre-impregnated material, wherein the compounding hot melting temperature is 60-150 ℃, and the hot melting pressure is 0.1-2 MPa.
Preferably, in the step 4), fiber layers are respectively applied to two surfaces of the shielding layer, and a prepreg resin mixture is compounded on the outer surfaces of the two fiber layers to form a five-layer prepreg with an electromagnetic shielding function.
Compared with the prior art, the invention has the advantages that:
1) the shielding performance is excellent, and the prepreg can be used for preparing a product with shielding effectiveness larger than 40 dB;
2) the mechanical property is excellent, the interlaminar performance of the composite material prepared by the prepreg is excellent, and the interlaminar shear strength is more than 40 MPa;
3) the process performance is excellent, the prepreg has the same process performance as the conventional prepreg, can be directly used together with the conventional prepreg, and is suitable for an autoclave process, a vacuum forming process and a hand lay-up process;
4) the quality stability is high, and the composite material product prepared by the prepreg has stable shielding performance and is not influenced by the construction process.
Drawings
Fig. 1 shows a prepreg having an electromagnetic shielding function in a five-layer structure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Examples 1,
The preparation method of the prepreg with the electromagnetic shielding function comprises the following steps:
1) drying each component of a dicyandiamide epoxy resin system, unidirectional D glass fiber yarn, a toughening agent CMP-410, carbon nano tubes (F-CNT) and a nickel screen SN354-300 (with the hole pitch of 0.8mm) for 9 hours at 60 ℃;
2) uniformly mixing each component of the dicyandiamide epoxy resin system in the step 1), heating to a molten state, and uniformly mixing with CMP-410 and carbon nanotubes (F-CNT) to obtain a pre-impregnated resin mixture;
3) regularly arranging the unidirectional D glass fiber yarns in the step 1) on a yarn guide system of a pre-soaking machine;
4) adhering the unidirectional D glass fiber yarns obtained in the step 3) to two sides of the nickel screen obtained in the step 1) to obtain a reinforced material mixture;
5) and (3) performing one-step hot melting on the pre-impregnated resin mixture obtained in the step 2) by using a one-step hot melting pre-impregnator and compounding the pre-impregnated resin mixture on the upper surface and the lower surface of the reinforced material mixture obtained in the step 4) to obtain the electromagnetic shielding pre-impregnated material, wherein the pre-impregnating temperature is 80 ℃, and the hot melting pressure is 0.1 MPa.
The test result of the composite material performance is as follows:
table 1 unidirectional sheets of prepreg obtained in example 1
| Test items | Measured value | Test standard |
| 0 degree tensile modulus/GPa | 31 | GB/T3354-2014 |
| 0 degree tensile strength/MPa | 930 | GB/T3354-2014 |
| 0 DEG compressive modulus/GPa | 31 | GB/T3856-2005 |
| 0 degree compressive strength/MPa | 600 | GB/T3856-2005 |
| Tensile modulus at 90 DEG/GPa | 9.7 | GB/T3354-2014 |
| Tensile strength at 90 DEG/MPa | 31 | GB/T3354-2014 |
| Interlaminar shear strength/MPa | 56 | JC/T773-1996 |
| Fiber volume content/%) | 61 | GB3355-2005 |
| Degree of cure/%) | 97 | GB2576-2005 |
| Void fraction/%) | 1.0 | JC/T287-2010 |
| Shielding effectiveness (30MHZ)/dB | 45 | GJB6190 |
Examples 2,
1) Drying cyanate resin, T800 carbon fiber yarn, toughening agent SA-2000, carbon nano tube (F-CNT) and carbon nano tube film (thickness is 0.5mm) for 2 hours at 100 ℃;
2) heating the cyanate ester resin in the step 1) to a molten state, and uniformly mixing the cyanate ester resin with a toughening agent SA-2000 and carbon nanotubes (F-CNT) to obtain a pre-impregnated resin mixture;
3) regularly arranging the T800 carbon fibers in the step 1) on a yarn guide system of a pre-soaking machine;
4) pasting the T800 carbon fibers in the step 3) on two sides of the carbon nanotube film in the step 1) to obtain a reinforced material mixture;
5) compounding the pre-impregnated resin mixture obtained in the step 2) on two surfaces of the reinforced material mixture obtained in the step 4) through a one-step hot melting pre-impregnation machine to obtain an electromagnetic shielding pre-impregnated material, wherein the pre-impregnation temperature is 100 ℃, and the hot melting pressure is 2 MPa;
the performance detection result of the composite prepreg is as follows:
table 2 properties of prepregs made in example 2
| Performance of | Index (I) | Test standard |
| Mass fraction/% of resin | 45±3 | JC/T 780-1996 |
| Volatile matter mass fraction/%) | ≤1 | JC/T 780-1996 |
| Monolayer thickness/mm | 0.15 | Calculation method |
| Spreadability | Superior food | Experiment of |
| Conformability | Superior food | Experiment of |
Table 3 prepreg unidirectional sheets prepared in example 2
Examples 3,
1) Drying bismaleimide resin, T700 carbon fiber 3K plain cloth, a toughening agent SA-2000, aminated graphene XF005-4 and a carbon nanotube film (with the thickness of 0.5mm) at 900 ℃ for 5 hours;
2) heating the bismaleimide resin obtained in the step 1) to a molten state, and uniformly mixing the bismaleimide resin with a toughening agent SA-2000 and aminated graphene to obtain a pre-impregnated resin mixture;
3) regularly arranging the T700 carbon fiber cloth in the step 1) on a yarn guide system of a pre-dipping machine;
4) pasting the two sides of the carbon nanotube film in the step 1) on the two sides of the T700 carbon fiber cloth in the step 3) to obtain a reinforced material mixture;
5) and (3) compounding the pre-impregnated resin mixture obtained in the step 2) on two surfaces of the reinforced material mixture obtained in the step 4) through a one-step hot melting pre-impregnation machine to obtain the electromagnetic shielding pre-impregnated material. The presoaking temperature is 120 ℃, and the hot melting pressure is 1MPa
And (3) prepreg performance detection results:
table 4 properties of prepregs made in example 3
| Performance of | Index (I) | Test standard |
| Mass fraction/% of resin | 45±3 | JC/T 780-1996 |
| Volatile matter mass fraction/%) | ≤1 | JC/T 780-1996 |
| Monolayer thickness/mm | 0.2 | Calculation method |
| Spreadability | Superior food | Experiment of |
| Conformability | Superior food | Experiment of |
By using the method of the invention, various combinations can be carried out on the shielding layer 1, the fiber layers 2 and the pre-impregnated resin mixture layers 3, for example, referring to fig. 1, the fiber layers 2 can be adhered on the upper and lower sides of the shielding layer 1, and the pre-impregnated resin mixture layers 3 are compounded on the outer layers of the upper and lower fiber layers 2, so as to achieve different electromagnetic shielding effects. In principle, the shielding effect on the reflection of waves is achieved by the degree of compactness of the arrangement of the prepreg resin mixture.
Claims (9)
1. The prepreg with the electromagnetic shielding function is characterized by comprising the following components in parts by weight:
40-50 parts of pre-impregnated resin mixture
49-59 parts of fiber layer
1-10 parts of shielding layer
The prepreg resin mixture comprises the following components in parts by weight:
60-97 parts of resin matrix
2-30 parts of toughening agent
1-10 parts of nano filler.
2. The prepreg having an electromagnetic shielding function according to claim 1, wherein the resin matrix is a wave-transmitting resin which can be prepared by a hot-melt method.
3. The prepreg with electromagnetic shielding function according to claim 2, wherein the resin matrix is one of epoxy resin, cyanate ester resin, bismaleimide resin and phthalonitrile resin.
4. The prepreg with the electromagnetic shielding function according to claim 1, wherein the toughening agent is one or more of a rubber containing hydroxyl and epoxy groups, a toughening agent containing a core-shell structure, thermoplastic particles and an aliphatic compound containing active groups.
5. The prepreg with the electromagnetic shielding function according to claim 1, wherein the nano filler is an inorganic particle structure with a particle size of 10-500 nm.
6. The prepreg with electromagnetic shielding function of claim 5, wherein the nano filler is one of carbon nanotube, graphene sheet, and silicon carbide.
7. The prepreg with the electromagnetic shielding function according to claim 1, wherein the fiber layer is one or more of glass fiber, carbon fiber and aramid fiber; the shielding layer is one or more of a copper net, a nickel net, an iron net, a stainless steel net, a carbon nano film and a graphene film with ductility.
8. A method for preparing the prepreg with electromagnetic shielding function according to claim 1, comprising the steps of:
1) drying the resin matrix, the toughening agent, the nano filler, the fiber layer and the shielding layer at the drying temperature of 60-110 ℃ for 1-10 hours;
2) heating a resin matrix to a molten state, and uniformly mixing the resin matrix with a toughening agent and a nano filler according to a proportion to obtain a pre-impregnated resin mixture;
3) regularly arranging fiber layers on a yarn guide system of a pre-soaking machine;
4) attaching the fiber layer arranged in the step 3) on at least one surface of the shielding layer to obtain a reinforced material mixture;
5) compounding the pre-impregnated resin mixture obtained in the step 2) with the reinforced material mixture obtained in the step 4) through a pre-impregnating machine to obtain the electromagnetic shielding pre-impregnated material, wherein the compounding hot melting temperature is 60-150 ℃, and the hot melting pressure is 0.1-2 MPa.
9. The method for preparing the prepreg with the electromagnetic shielding function according to claim 8, wherein in the step 4), the fiber layers are respectively applied to both sides of the shielding layer, and the prepreg resin mixture is compounded on the outer surfaces of the two fiber layers to form the prepreg with the electromagnetic shielding function in a five-layer structure.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358253A (en) * | 2019-07-04 | 2019-10-22 | 武汉楚辰新材料科技有限公司 | For producing the composite material and preparation method of railway signal tank unit housings |
| CN115401960A (en) * | 2022-09-01 | 2022-11-29 | 哈尔滨玻璃钢研究院有限公司 | Resin-based composite material with high electromagnetic shielding efficiency and forming method and application thereof |
| CN115464941A (en) * | 2022-09-15 | 2022-12-13 | 上海伽材新材料科技有限公司 | Preparation method of carbon fiber/graphene composite electromagnetic shielding prepreg |
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| US20120135655A1 (en) * | 2010-11-29 | 2012-05-31 | Hyundai Motor Company | Thermoplastic composite for stiffener and method for preparing same |
| CN103171173A (en) * | 2013-03-14 | 2013-06-26 | 中国人民解放军国防科学技术大学 | Carbon fiber electromagnetic wave absorbing material and preparation method thereof |
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| US20120135655A1 (en) * | 2010-11-29 | 2012-05-31 | Hyundai Motor Company | Thermoplastic composite for stiffener and method for preparing same |
| CN103171173A (en) * | 2013-03-14 | 2013-06-26 | 中国人民解放军国防科学技术大学 | Carbon fiber electromagnetic wave absorbing material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358253A (en) * | 2019-07-04 | 2019-10-22 | 武汉楚辰新材料科技有限公司 | For producing the composite material and preparation method of railway signal tank unit housings |
| CN115401960A (en) * | 2022-09-01 | 2022-11-29 | 哈尔滨玻璃钢研究院有限公司 | Resin-based composite material with high electromagnetic shielding efficiency and forming method and application thereof |
| CN115464941A (en) * | 2022-09-15 | 2022-12-13 | 上海伽材新材料科技有限公司 | Preparation method of carbon fiber/graphene composite electromagnetic shielding prepreg |
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