CN112476846B - High-thermal-conductivity carbon fiber prepreg and preparation method thereof - Google Patents
High-thermal-conductivity carbon fiber prepreg and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
- B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
- B29B15/125—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex by dipping
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2481/06—Polysulfones; Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
Abstract
The invention discloses a high-thermal-conductivity carbon fiber prepreg and a preparation method thereof, wherein the high-thermal-conductivity carbon fiber prepreg comprises a nanofiber film, a high-thermal-conductivity carbon fiber bundle A and a high-thermal-conductivity carbon fiber bundle B, wherein the high-thermal-conductivity carbon fiber bundle A and the high-thermal-conductivity carbon fiber bundle B are alternately arranged at intervals; the nano fiber membranes are sequentially and alternately inserted between the high-heat-conductivity carbon fiber bundles A and the high-heat-conductivity carbon fiber bundles B; one sides of the high-thermal-conductivity carbon fiber bundles A and the high-thermal-conductivity carbon fiber bundles B far away from the nanofiber membrane are impregnated with hot melt resin. According to the invention, the carbon fiber prepreg loaded with the nanofiber membrane is prepared by arranging the fiber yarn bundles in a staggered manner and hot-pressing and dipping twice, so that on one hand, the yarn breakage rate in the yarn guiding process is reduced, and the performance and preparation efficiency of the prepreg and the in-plane performance of the high-thermal-conductivity composite material prepared from the high-thermal-conductivity carbon fiber prepreg are improved; on the other hand, the interlaminar shear performance of the high-thermal-conductivity composite material prepared from the high-thermal-conductivity carbon fiber prepreg is improved by introducing the nanofiber membrane and arranging the nanofiber membrane in the prepreg in the thickness direction.
Description
Technical Field
The invention relates to a preparation method of a special carbon fiber prepreg, and particularly relates to a high-thermal-conductivity carbon fiber prepreg and a preparation method thereof.
Background
At present, a hot melting method is mainly adopted in a method for preparing a high-thermal-conductivity carbon fiber prepreg, namely, a resin film is firstly prepared, and then the prepreg is prepared through the technical processes of yarn arrangement, gum dipping, hot pressing, cooling, film covering, rolling and the like. However, the preparation process of the high-thermal-conductivity carbon fiber prepreg is different from that of common carbon fibers, and one of the processes is that due to the inherent high modulus characteristic of the high-thermal-conductivity carbon fibers, the fiber has poor manufacturability in the yarn arranging process, high yarn breakage rate and low preparation efficiency, the prepreg with good performance cannot be obtained, and various mechanical and thermal properties of the composite material are directly influenced. Secondly, the graphitization degree of the high-heat-conductivity carbon fiber is high, and the physical and chemical states of the surface of the fiber are difficult to improve through surface treatment, so that the inertia of the surface of the fiber is strong, the combination with resin is poor, the performance of the obtained composite material layer is weak, and the use requirement cannot be well met.
Disclosure of Invention
In order to solve the problems, the invention adopts the following technical scheme:
a high-thermal-conductivity carbon fiber prepreg comprises a nanofiber membrane, a high-thermal-conductivity carbon fiber bundle A and a high-thermal-conductivity carbon fiber bundle B, wherein the high-thermal-conductivity carbon fiber bundle A and the high-thermal-conductivity carbon fiber bundle B are alternately arranged at intervals; the nano fiber membranes are sequentially and alternately inserted between the high-heat-conductivity carbon fiber bundle A and the high-heat-conductivity carbon fiber bundle B; and hot melt resin is impregnated on one sides of the high-thermal-conductivity carbon fiber bundles A and the high-thermal-conductivity carbon fiber bundles B far away from the nanofiber membrane.
A preparation method of a high-thermal-conductivity carbon fiber prepreg comprises the following steps:
s10, preparing a high-thermal-conductivity carbon fiber prepreg A: arranging high-thermal-conductivity carbon fiber bundles A in a clearance mode, laying a resin film and a nanofiber film on two sides of the high-thermal-conductivity carbon fiber bundles A, and impregnating the resin film and the nanofiber film by using an impregnation line of a hot-melt pre-impregnator to obtain a high-thermal-conductivity carbon fiber prepreg A;
s20, preparing a high-thermal-conductivity carbon fiber prepreg B: arranging high-thermal-conductivity carbon fiber bundles B corresponding to gaps among the high-thermal-conductivity carbon fiber bundles A, laying a resin film on one side of the high-thermal-conductivity carbon fiber bundles B, and impregnating the resin film by using an impregnation line of a hot-melt prepreg machine to prepare a high-thermal-conductivity carbon fiber prepreg B;
s30, respectively placing the high-thermal-conductivity carbon fiber prepreg A and the high-thermal-conductivity carbon fiber prepreg B on a prepreg unreeling device, wherein the corresponding prepreg roll placing direction is consistent with the winding direction; and the high-thermal-conductivity carbon fiber prepreg B is arranged corresponding to the reserved gap of the high-thermal-conductivity carbon fiber prepreg A, and the high-thermal-conductivity carbon fiber prepreg is prepared through the working procedures of hot pressing, cooling, laminating and rolling.
Further, the width of the high-thermal-conductivity carbon fiber prepreg is 100-1000 mm, the fiber surface density is 50-250 gsm, and the gel content is 20-40%.
Further, gaps among the high-thermal-conductivity carbon fiber bundles A forming the high-thermal-conductivity carbon fiber prepreg A are uniformly distributed; and gaps among the high-thermal-conductivity carbon fiber bundles B corresponding to the high-thermal-conductivity carbon fiber bundles A, which form the high-thermal-conductivity carbon fiber prepreg B, are uniformly distributed.
Further, the high thermal conductivity carbon fiber prepreg a and the high thermal conductivity carbon fiber prepreg B can be replaced with each other, and any one of the prepregs is loaded with the nanofiber film.
Further, the high-thermal-conductivity carbon fibers forming the high-thermal-conductivity carbon fiber bundle A comprise mesophase pitch-based carbon fibers, the specification of the fiber bundle is 1K-3K, the linear density is 200-800 g/km, and the axial thermal conductivity is 400W/m.K-1000W/m.K.
Further, the nanofiber membrane is one of a nylon nanofiber membrane, a polyetherimide nanofiber membrane, a polysulfone nanofiber membrane, a polyethersulfone nanofiber membrane or a polyetherketone nanofiber membrane.
Further, the nanofiber membrane has the surface density of 1-10 gsm and the thickness of 5-30 microns.
Has the beneficial effects that:
according to the high-thermal-conductivity carbon fiber prepreg and the preparation method thereof, the carbon fiber prepreg loaded with the nanofiber membrane is prepared by hot-pressing impregnation twice through staggered arrangement of fiber yarn bundles, on one hand, the yarn breakage rate in the yarn leading process is reduced, and the performance and the preparation efficiency of the prepreg and the in-plane performance of a high-thermal-conductivity composite material prepared from the high-thermal-conductivity carbon fiber prepreg are improved; on the other hand, the interlaminar shear performance of the high-thermal-conductivity composite material prepared from the high-thermal-conductivity carbon fiber prepreg is improved by introducing the nanofiber membrane and arranging the nanofiber membrane in the prepreg in the thickness direction. In addition, the preparation process of the high-thermal-conductivity carbon fiber prepreg is controllable, the material selection range is wide, the designability is strong, and the preparation method is suitable for preparing various high-thermal-conductivity carbon fiber resin matrix composite materials.
Drawings
FIG. 1 is a schematic view of arrangement positions of fiber yarns of a high thermal conductivity carbon fiber bundle A in a dividing comb
FIG. 2 is a schematic view showing the arrangement position of the fiber yarn of the carbon fiber bundle B with high thermal conductivity in the dividing comb
FIG. 3 is a schematic structural diagram of a high thermal conductivity carbon fiber prepreg
FIG. 4 is a comparison table of in-plane thermal conductivity of composite tested by GB/T22588-2008 and interlaminar shear strength of composite tested by JC/T773-2010
Wherein, 1, carbon fiber bundle A with high thermal conductivity; 2. a high thermal conductivity carbon fiber bundle B; 3. separating silk and combing; 4. a nanofiber membrane; 5. high heat conduction carbon fiber prepreg A; 6. and (3) high-thermal-conductivity carbon fiber prepreg B.
Detailed Description
Example 1
A preparation method of a high-thermal-conductivity carbon fiber prepreg comprises the following steps:
selecting an epoxy resin film with the surface density of 30gsm and a nylon nanofiber film with the surface density of 4.5gsm, respectively placing the epoxy resin film and the nylon nanofiber film on an unwinding mechanism, installing a 1K high-thermal-conductivity carbon fiber 60 shaft with the linear density of 250g/km and the thermal conductivity of 500W/m.K on a creel, and preparing a unidirectional high-thermal-conductivity carbon fiber prepreg A with uniformly distributed gaps by adopting a prepreg impregnating machine; preparing a unidirectional high-thermal-conductivity carbon fiber prepreg B containing uniformly distributed gaps by impregnating an epoxy resin film with the surface density of 30gsm and 60-axis high-thermal-conductivity carbon fibers of the same type through a prepreg machine; and then respectively placing the high-thermal-conductivity carbon fiber prepreg A and the high-thermal-conductivity carbon fiber prepreg B on a prepreg unreeling device, wherein the placing direction of a prepreg roll is consistent with the winding direction, and preparing the high-thermal-conductivity carbon fiber prepreg with the width of 300mm, the fiber surface density of 100gsm and the gel content of 36.5 +/-3% through the hot pressing, cooling, laminating and winding processes of a prepreg machine.
Example 2
A preparation method of a high-thermal-conductivity carbon fiber prepreg comprises the following steps:
selecting a cyanate ester resin film with the surface density of 25gsm and a polysulfone nanofiber film with the surface density of 3gsm, respectively placing the cyanate ester resin film and the polysulfone nanofiber film on an unwinding mechanism, installing a 2K high-thermal-conductivity carbon fiber 75 shaft with the linear density of 500g/km and the thermal conductivity of 620W/m.K on a creel, and preparing a unidirectional high-thermal-conductivity carbon fiber prepreg A with uniformly distributed gaps by adopting a prepreg impregnation machine; preparing a unidirectional high-thermal-conductivity carbon fiber prepreg B containing uniformly distributed gaps by impregnating an epoxy resin film with the surface density of 25gsm and 75-axis high-thermal-conductivity carbon fibers of the same type through a prepreg machine; and then respectively placing the high-thermal-conductivity carbon fiber prepreg A and the high-thermal-conductivity carbon fiber prepreg B on a prepreg unreeling device, wherein the placing direction of a prepreg roll is consistent with the winding direction, and preparing the high-thermal-conductivity carbon fiber prepreg with the width of 500mm, the fiber surface density of 150gsm and the gel content of 24.6 +/-3% through the hot pressing, cooling, laminating and winding processes of a prepreg machine.
Comparative example 1
Two rolls of epoxy resin films with the area density of 30gsm are selected to be respectively placed on an unwinding mechanism of a pre-soaking machine, a shaft of the 1K high-heat-conductivity carbon fiber 120 with the linear density of 250g/km and the heat conductivity of 500W/m.K is installed on a creel, the pre-soaking process adopts double-sided resin film gum dipping, and the high-heat-conductivity carbon fiber pre-soaking material with the width of 300mm, the fiber area density of 100gsm and the gum content of 37.5 +/-3% is prepared through the processes of hot pressing, cooling, laminating and winding of the pre-soaking machine.
Comparative example 2
Selecting two rolls of cyanate ester resin films with the area density of 25gsm, respectively placing the cyanate ester resin films on an unwinding mechanism of a pre-soaking machine, installing 150 shafts of 2K high-heat-conductivity carbon fibers with the linear density of 500g/km and the heat conductivity of 620W/m.K on a creel, dipping the two-sided resin films in the pre-soaking process, and preparing the high-heat-conductivity carbon fiber pre-preg with the width of 500mm, the fiber area density of 150gsm and the gel content of 25 +/-3% through hot pressing, cooling, film covering and winding processes of the pre-soaking machine.
The prepregs prepared in the example 1, the example 2, the comparative example 1 and the comparative example 2 are used for preparing a unidirectional high-thermal-conductivity composite material laminated plate, and the interlayer shear strength of the composite material is tested by using JC/T773-2010; the in-plane thermal conductivity of the composite material is tested by GB/T22588-.
Example 3
A high-thermal-conductivity carbon fiber prepreg (as shown in figure 3) comprises a nanofiber membrane 4, high-thermal-conductivity carbon fiber bundles A1 and high-thermal-conductivity carbon fiber bundles B2, wherein the high-thermal-conductivity carbon fiber bundles A1 and the high-thermal-conductivity carbon fiber bundles B2 are alternately arranged at intervals; the nano-fiber membranes 4 are sequentially and alternately inserted between the high-heat-conductivity carbon fiber bundle A1 and the high-heat-conductivity carbon fiber bundle B2; the sides of the high thermal conductivity carbon fiber bundle A1 and the high thermal conductivity carbon fiber bundle B2 far away from the nanofiber membrane are impregnated with hot melt resin.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (7)
1. The preparation method of the high-thermal-conductivity carbon fiber prepreg is characterized in that the high-thermal-conductivity carbon fiber prepreg comprises a nanofiber film, a high-thermal-conductivity carbon fiber bundle A and a high-thermal-conductivity carbon fiber bundle B, wherein the high-thermal-conductivity carbon fiber bundle A and the high-thermal-conductivity carbon fiber bundle B are alternately arranged at intervals; the nano fiber membranes are sequentially and alternately inserted between the high-heat-conductivity carbon fiber bundle A and the high-heat-conductivity carbon fiber bundle B; hot melt resin is impregnated on one sides of the high-thermal-conductivity carbon fiber bundles A and the high-thermal-conductivity carbon fiber bundles B far away from the nanofiber membrane; the preparation method comprises the following steps:
s10, preparing a high-thermal-conductivity carbon fiber prepreg A: arranging high-thermal-conductivity carbon fiber bundles A in a clearance mode, laying a resin film and a nanofiber film on two sides of the high-thermal-conductivity carbon fiber bundles A, and impregnating the resin film and the nanofiber film by using an impregnation line of a hot-melt pre-impregnator to obtain a high-thermal-conductivity carbon fiber prepreg A;
s20, preparing a high-thermal-conductivity carbon fiber prepreg B: arranging high-thermal-conductivity carbon fiber bundles B corresponding to gaps among the high-thermal-conductivity carbon fiber bundles A, laying a resin film on one side of the high-thermal-conductivity carbon fiber bundles B, and impregnating the resin film by using an impregnation line of a hot-melt prepreg machine to prepare a high-thermal-conductivity carbon fiber prepreg B;
s30, respectively placing the high-thermal-conductivity carbon fiber prepreg A and the high-thermal-conductivity carbon fiber prepreg B on a prepreg unreeling device, wherein the corresponding prepreg roll placing direction is consistent with the winding direction; and the high-thermal-conductivity carbon fiber prepreg B is arranged corresponding to the reserved gap of the high-thermal-conductivity carbon fiber prepreg A, and the high-thermal-conductivity carbon fiber prepreg is prepared through the working procedures of hot pressing, cooling, laminating and rolling.
2. The preparation method of the high-thermal-conductivity carbon fiber prepreg according to claim 1, wherein the high-thermal-conductivity carbon fiber prepreg has a width of 100-1000 mm, a fiber areal density of 50-250 gsm, and a gel content of 20-40%.
3. The method for preparing the high thermal conductivity carbon fiber prepreg according to claim 1, wherein gaps among the high thermal conductivity carbon fiber bundles A constituting the high thermal conductivity carbon fiber prepreg A are uniformly distributed; and gaps among the high-thermal-conductivity carbon fiber bundles B corresponding to the high-thermal-conductivity carbon fiber bundles A, which form the high-thermal-conductivity carbon fiber prepreg B, are uniformly distributed.
4. The method according to claim 3, wherein the highly thermal conductive carbon fiber prepreg A and the highly thermal conductive carbon fiber prepreg B are replaceable with each other, and either one of the highly thermal conductive carbon fiber prepreg A and the highly thermal conductive carbon fiber prepreg B carries the nanofiber film.
5. The method for preparing the high thermal conductivity carbon fiber prepreg according to claim 4, wherein the high thermal conductivity carbon fibers constituting the high thermal conductivity carbon fiber bundle A comprise mesophase pitch-based carbon fibers, the specification of the fiber bundle is 1K-3K, the linear density is 200-800 g/km, and the axial thermal conductivity is 400W/m-K-1000W/m-K.
6. The method for preparing the carbon fiber prepreg with high thermal conductivity according to claim 1, wherein the nanofiber membrane is one of a nylon nanofiber membrane, a polyetherimide nanofiber membrane, a polysulfone nanofiber membrane, a polyethersulfone nanofiber membrane or a polyetherketone nanofiber membrane.
7. The preparation method of the high-thermal-conductivity carbon fiber prepreg according to claim 1, wherein the nanofiber film has an areal density of 1-10 gsm and a thickness of 5-30 μm.
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| US5836715A (en) * | 1995-11-19 | 1998-11-17 | Clark-Schwebel, Inc. | Structural reinforcement member and method of utilizing the same to reinforce a product |
| FR2962175B1 (en) * | 2010-07-02 | 2012-08-10 | Snecma | AUBE A LONGERON INTEGRATED COMPOSITE |
| CN108248063A (en) * | 2012-01-25 | 2018-07-06 | 赫克赛尔控股有限责任公司 | The improvement of laminate or the improvement about laminate |
| US9802358B2 (en) * | 2012-12-21 | 2017-10-31 | Cytec Industries Inc. | Curable prepregs with surface openings |
| US10562262B2 (en) * | 2018-04-19 | 2020-02-18 | The Boeing Company | Thermoplastic cellular network toughened composites |
| US11584041B2 (en) * | 2018-04-20 | 2023-02-21 | Pella Corporation | Reinforced pultrusion member and method of making |
| 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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Address after: Room 2202, building F1, Lugu Yuyuan, No.27 Wenxuan Road, high tech Development Zone, Changsha City, Hunan Province Patentee after: Hunan Dongying Carbon Materials Technology Co.,Ltd. Patentee after: Hunan Dongying special carbon asphalt material Co.,Ltd. Address before: Room 2202, building F1, Lugu Yuyuan, No.27 Wenxuan Road, high tech Development Zone, Changsha City, Hunan Province Patentee before: HUNAN DONGYING CARBON MATERIAL TECHNOLOGY CO.,LTD. Patentee before: Hunan Dongying special carbon asphalt material Co.,Ltd. |