CN114379167A - Interlayer modified carbon fiber composite material and preparation method and application thereof - Google Patents

Interlayer modified carbon fiber composite material and preparation method and application thereof Download PDF

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Publication number
CN114379167A
CN114379167A CN202210233556.XA CN202210233556A CN114379167A CN 114379167 A CN114379167 A CN 114379167A CN 202210233556 A CN202210233556 A CN 202210233556A CN 114379167 A CN114379167 A CN 114379167A
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carbon fiber
carbon fibers
composite material
chopped
fiber prepreg
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沈忱
高峰
张晖
张忠
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National Center for Nanosccience and Technology China
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National Center for Nanosccience and Technology China
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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
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • 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
    • B32B2262/106—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
    • B32B2307/202—Conductive
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive

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Abstract

The invention provides an interlayer modified carbon fiber composite material and a preparation method and application thereof. The interlayer modified carbon fiber composite material based on the vertical orientation chopped carbon fibers provided by the invention has excellent interlayer mechanical properties (interlayer toughness is obviously improved), and the conductivity and heat conductivity in the thickness direction are also greatly improved. In addition, the preparation method has the advantages of simple preparation process, mild conditions, no need of complex equipment and obvious advantages in large-scale preparation.

Description

Interlayer modified carbon fiber composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of composite material science, relates to an interlayer modified carbon fiber composite material, a preparation method and application thereof, and particularly relates to an interlayer modified carbon fiber composite material based on vertical oriented chopped carbon fibers, and a preparation method and application thereof.
Background
Carbon fiber composite materials are widely used due to their excellent properties, such as: high strength, high modulus, fatigue property, light weight, heat resistance, corrosion resistance and good designability. At present, the method is widely applied to the fields of aerospace, electronic communication, medical appliances, sports goods and the like. However, carbon fiber composite boards are generally of a laminated structure, wherein the intermediate layer is not fiber-reinforced, and only the epoxy matrix is used for bonding and load transfer, so that the toughness between the layers is weak, and the layers are more easily separated particularly under impact load, which also limits the application of the carbon fiber/epoxy composite material. Meanwhile, the single resin matrix between layers also causes the poor electric and heat conduction performance of the carbon fiber composite material in the Z direction (thickness direction). Therefore, the improvement of the interlayer performance of the carbon fiber reinforced composite material has great scientific significance and practical value.
The interlaminar properties (such as mechanical, electrical, and thermal properties) of the carbon fiber composite material are not excellent and need to be improved, and there are many methods for improving the interlaminar properties of the carbon fiber composite material, such as improving the interlaminar properties of the carbon fiber composite material by improving the toughness of the matrix resin. However, modification of the matrix, etc., may cause loss of other non-interlayer properties or impair its processability, and the molding process is more complicated. CN107459820A discloses a preparation method of a micro-nano particle synergistic interlayer toughened bismaleimide carbon fiber composite material, which is characterized in that a solid-liquid composite low-viscosity resin system is obtained by a 'multiphase compounding' method, thermoplastic micro-particles and core-shell nano-particles are dispersed in a liquid toughening agent formed by combining an allyl compound and epoxy resin, bismaleimide micro-powder is added for uniform premixing, the mixture is physically blended on a three-roll grinder, and the micro-nano particles are uniformly dispersed by virtue of shearing and diffusion, so that the toughened bismaleimide resin system is obtained. And (3) coating the bismaleimide resin system, then performing hot-pressing, pre-dipping and compounding with a carbon fiber reinforcement, and finally performing die pressing to obtain the interlaminar toughened composite material. Although the interlayer performance of the carbon fiber composite material is improved, the process is complex, and the performance in the layer is changed. In the prior art, the surface of the fiber is modified to enhance the bonding effect with the matrix resin, but the improvement performance is limited, the process is complex and difficult to control. In the prior art, micro-nano particles are used for improving interlayer toughness, for example, CN104945852A discloses a micro-nano particle interlayer toughening technology, in which a mixed solution of inorganic particles as micro-nano particles is first uniformly sprayed on fibers, and then compounded with thermosetting resin to obtain a micro-nano particle interlayer toughened composite material. In the prior art, carbon nano-material carbon nanotubes are used for interlayer modification, for example, CN110117409A reports a method for toughening a composite interlayer by using multi-wall carbon nanotubes, but the improved interlayer toughness performance is limited, and no discussion is given on the electric and thermal conductivity in the thickness direction. In view of the above examples, none of the examples can simultaneously achieve the improvement of the mechanical, electrical and thermal properties between the carbon fiber composite layers.
Therefore, in the art, it is desirable to develop an interlayer modified carbon fiber composite material, which has improved interlayer mechanical, electrical and thermal properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an interlayer modified carbon fiber composite material, a preparation method and application thereof, in particular to an interlayer modified carbon fiber composite material based on vertical orientation chopped carbon fibers, a preparation method and application thereof. The interlayer modified carbon fiber composite material has excellent interlayer mechanical property, and the interlayer comprehensive properties (such as electric conductivity and heat conductivity in the thickness direction) of the interlayer modified carbon fiber composite material are also obviously improved. The preparation method is simple, low in cost and high in operability. The method has wide application prospect in the field of resin-based carbon fiber composite material interlayer modification.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an interlaminar modified carbon fiber composite material prepared by vertically orienting chopped carbon fibers on a carbon fiber prepreg.
In the invention, the interlayer modified carbon fiber composite material prepared by vertically orienting the chopped carbon fibers on the carbon fiber prepreg has excellent interlayer mechanical property, and the conductivity and the heat conductivity in the thickness direction are also obviously improved.
In the invention, the interlayer modified carbon fiber composite material comprises a laminated plate formed by pressing carbon fiber prepreg and chopped carbon fibers vertically distributed in an interlayer orientation mode.
In the present invention, the vertical orientation refers to an orientation in the thickness direction of the carbon fiber prepreg.
Preferably, the raw material for preparing the carbon fiber prepreg includes continuous carbon fibers (for example, may be selected from T700 model of dongli corporation), a resin matrix, and a curing agent.
Preferably, the resin matrix comprises any one of epoxy resin, bismaleimide resin, cyanate ester resin or polyimide resin or a combination of at least two of the above.
Preferably, the curing agent comprises an anhydride-based curing agent.
The carbon fiber prepreg used in the present invention may be prepared by a method known in the art, or may be purchased as it is. The continuous carbon fibers in the carbon fiber prepreg can be arranged in a single direction or in multiple directions.
Preferably, the chopped carbon fibers comprise pitch-based carbon fibers and/or polyacrylonitrile-based carbon fibers, and also can be modified pitch-based carbon fibers or modified polyacrylonitrile-based carbon fibers.
Preferably, the chopped carbon fibers have a length of 100-150 μm, such as 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, or the like. When the length of the chopped carbon fibers is too large, the interlayer thickness of the interlayer modified carbon fiber composite material may be too large, and the performance per unit thickness may be reduced although the overall performance may be improved.
Chopped carbon fibers of suitable length can be obtained by mechanical vibratory screening, as follows:
placing the cut chopped carbon fibers in a mechanical vibrating screen, wherein the mesh number of the screen is as follows from top to bottom: 50 meshes, 100 meshes, 200 meshes and 300 meshes, and mechanically vibrating and screening for 1-3 h. The length of the carbon fibers on each mesh screen is close, for example, the length of the carbon fibers on a 100 mesh screen is substantially uniform, the length of the carbon fibers on a 200 mesh screen is substantially uniform, and the length of the carbon fibers on a 300 mesh screen is substantially uniform. After the screening, the fibers of 300 meshes were taken and counted by an optical microscope to have a length of about 100-150 μm.
Preferably, the chopped carbon fibers have a diameter of 6-10 μm, such as 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm, and the like.
In a second aspect, the present invention provides a method for preparing the interlayer modified carbon fiber composite material according to the first aspect, the method comprising the steps of:
(1) preheating the carbon fiber prepreg, and vertically attaching the chopped carbon fibers to one surface of the carbon fiber prepreg to obtain the carbon fiber prepreg attached with the vertically oriented chopped carbon fibers;
(2) repeating the step (1) to obtain a plurality of carbon fiber prepregs attached with the vertically oriented chopped carbon fibers;
(3) and (3) stacking a plurality of carbon fiber prepregs attached with the vertical-orientation chopped carbon fibers obtained in the step (2), enabling the surfaces attached with the chopped carbon fibers to face upwards, laying one carbon fiber prepreg which is not attached with the chopped carbon fibers on the uppermost surface, transferring the carbon fiber prepreg into a mold, prepressing, heating, and curing to obtain the interlayer modified carbon fiber composite material.
In the invention, the carbon fiber prepreg is preheated in the step (1), so that the resin matrix of the carbon fiber prepreg is in a viscous semi-cured state, which is beneficial to the adhesion of the subsequent chopped carbon fibers, and the preheating can be carried out in an oven.
In the present invention, the plurality of sheets in the step (2) means at least two sheets, and it is needless to say that only one sheet of the carbon fiber prepreg to which the vertically oriented chopped carbon fibers are attached may be obtained without repeating the step (1). The number of the sheets in the step (3) is not limited, and the number of the sheets can be determined according to the product requirements. When a plurality of carbon fiber prepregs attached with the vertically oriented chopped carbon fibers are stacked, the stacking direction of the carbon fiber prepregs can be arranged in a unidirectional mode (namely, continuous carbon fibers of the plurality of carbon fiber prepregs are all arranged in the same direction), or the carbon fiber prepregs can be arranged in a multidirectional mode (for example, the continuous carbon fibers of the carbon fiber prepregs are arranged in a crossed mode), and the arrangement mode can be determined according to the actual application of the product.
In the invention, in the step (3), the prepreg obtained in the step (2) is laid layer by layer with the side with the vertically oriented chopped carbon fibers facing upwards. Ensuring that the uppermost layer is prepreg without vertically oriented chopped carbon fibers. For example, the total number of plies is 24, then the lower 23 plies are all the prepregs with the vertically oriented chopped carbon fibers bundled in the step (2), and only the 24 th ply is the prepreg without the vertically oriented chopped carbon fibers attached.
The preparation method disclosed by the invention is simple, mild in condition, free of high-temperature condition, capable of being prepared at room temperature, free of modification and introduction of other substances, free of complex equipment, low in cost, high in operability and remarkable in large-scale preparation.
Preferably, the temperature of said preheating of step (1) is 60 ℃ to 80 ℃, such as 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, etc.
Preferably, the preheating time in step (1) is 10min-30min, such as 10min, 15min, 20min, 25min or 30 min.
Preferably, the step (1) of vertically attaching the chopped carbon fibers to one surface of the carbon fiber prepreg specifically includes the following steps: fixing the preheated carbon fiber prepreg on an upper polar plate of a high-voltage electrostatic device, dispersing the short carbon fibers on a lower polar plate of the high-voltage electrostatic device, turning on a power switch of the high-voltage electrostatic device, enabling the short carbon fibers to fly to the upper polar plate under the action of a high-voltage electrostatic field, vertically orienting in the electric field, and vertically penetrating into a resin matrix of the carbon fiber prepreg.
Preferably, the means of securing comprises securing with tape.
Preferably, the means of dispersion comprises mechanical shock dispersion.
Preferably, the voltage of the high voltage electrostatic device is 5-20kV, such as 5kV, 8kV, 10kV, 13kV, 15kV, 18kV or 20kV, etc., and the energization time is 10-30s, such as 10s, 15s, 20s, 25s or 30s, etc., during which the chopped carbon fibers can be completely impregnated at one side of the carbon fiber prepreg.
Preferably, the distance between the upper plate and the lower plate of the high-voltage electrostatic device is 5-15cm, such as 5cm, 6cm, 7cm, 8cm, 9cm, 10cm, 11cm, 12cm, 13cm, 14cm or 15 cm.
Preferably, the electric field intensity of the high-voltage electrostatic field is 1-3kV/cm, such as 1kV/cm, 1.5kV/cm, 2kV/cm, 2.5kV/cm, or 3kV/cm, etc.
In the invention, by controlling the voltage of the high-voltage electrostatic device and the distance between the polar plates, the chopped carbon fibers are polarized on the lower polar plate, obtain a certain initial speed, accelerate to fly to the substrate under the action of an electric field force, penetrate into the resin matrix of the preheated carbon fiber prepreg and maintain the vertical orientation characteristic.
Preferably, the mold in step (3) is a preheated mold, and the preheated temperature is 50 ℃ to 150 ℃, such as 50 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 130 ℃ or 150 ℃ and the like.
Preferably, the temperature of the pre-pressing in the step (3) is 50 ℃ to 90 ℃, such as 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃ and the like, the time of the pre-pressing is 30 to 60min, such as 30min, 40min, 50min or 60min and the like, and the pressure of the pre-pressing is 0.5 to 1.5MPa, such as 0.5MPa, 1.0MPa or 1.5MPa and the like.
Preferably, the temperature rise in step (3) is to 120-150 ℃, such as 120 ℃, 130 ℃, 140 ℃ or 150 ℃ and the like.
Preferably, the temperature for curing in step (3) is 120-150 ℃, such as 120 ℃, 130 ℃, 140 ℃ or 150 ℃, etc.
Preferably, the pressure for curing in step (3) is 2-5MPa, such as 2MPa, 3MPa, 4MPa or 5 MPa.
Preferably, the curing time in step (3) is 2-5h, such as 2h, 3h, 4h or 5 h.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) preheating a carbon fiber prepreg at 60-80 ℃ for 10-30 min, fixing the preheated carbon fiber prepreg on an upper polar plate of a high-voltage electrostatic device, dispersing short carbon fibers on a lower polar plate of the high-voltage electrostatic device, turning on a power switch of the high-voltage electrostatic device, enabling the short carbon fibers to fly to the upper polar plate under the action of a high-voltage electrostatic field, vertically orienting in the electric field, and vertically penetrating into a resin matrix of the carbon fiber prepreg to obtain the carbon fiber prepreg attached with the vertically oriented short carbon fibers; wherein the electric field intensity of the high-voltage electrostatic field is 1-3kV/cm, and the electrifying time is 10-30 s;
(2) repeating the step (1) to obtain a plurality of carbon fiber prepregs attached with the vertically oriented chopped carbon fibers;
(3) and (3) stacking a plurality of carbon fiber prepregs attached with the vertical-orientation chopped carbon fibers obtained in the step (2), wherein one surface attached with the chopped carbon fibers faces upwards, then laying one carbon fiber prepreg which is not attached with the chopped carbon fibers on the uppermost surface, then transferring the carbon fiber prepreg into a preheated mold, prepressing for 30-60min at 50-90 ℃ and 0.5-1.5MPa, heating to 120-150 ℃, and curing for 2-5h at 120-150 ℃ and 2-5MPa to obtain the interlayer modified carbon fiber composite material.
In a third aspect, the present invention provides the use of the interlaminar modified carbon fiber composite of the first aspect in a multifunctional composite product.
Compared with the prior art, the invention has the following beneficial effects:
(1) the interlayer modified carbon fiber composite material based on the vertical orientation chopped carbon fibers provided by the invention has excellent interlayer mechanical properties (interlayer I-shaped fracture toughness is improved by 91.6%), and the conductivity in the thickness direction (the conductivity in the thickness direction is improved by 4 orders of magnitude) and the heat conductivity (the heat conductivity in the thickness direction is improved by 36%) are also greatly improved.
(2) The preparation method disclosed by the invention is simple, mild in condition, free of high-temperature condition, capable of being prepared at room temperature, free of modification and introduction of other substances, free of complex equipment, low in cost, high in operability and remarkable in large-scale preparation.
Drawings
Fig. 1 is a schematic partial structure diagram of an interlayer modified carbon fiber composite material provided in example 1, wherein 1 is a carbon fiber prepreg arranged unidirectionally; 2-interlayer vertically oriented chopped carbon fibers, which are sandwiched between two layers of carbon fiber prepregs; 3-epoxy matrix.
Fig. 2 is a scanning electron microscope image of a cross section of the interlayer modified carbon fiber composite material provided in example 1.
Fig. 3 is a local scanning electron microscope image of the cross section of the interlayer modified carbon fiber composite material provided in example 1, in which the chopped carbon fibers are vertically oriented.
Fig. 4 is a scanning electron microscope image of a cross section of the carbon fiber composite material provided in comparative example 1.
Fig. 5 is a graph showing comparative test results of type I fracture toughness of the interlayer modified carbon fiber composite provided in example 1 and the carbon fiber composite provided in comparative example 1.
Fig. 6 is a graph showing the results of comparative tests of electrical conductivity in the Z direction (thickness direction) of the interlayer modified carbon fiber composite material provided in example 1 and the carbon fiber composite material provided in comparative example 1.
Fig. 7 is a graph showing the results of comparative tests of thermal conductivity in the Z direction (thickness direction) of the interlayer modified carbon fiber composite material provided in example 1 and the carbon fiber composite material provided in comparative example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The interlayer modified carbon fiber composite material is prepared by vertically orienting chopped carbon fibers on a carbon fiber prepreg, and a schematic partial structure diagram of the interlayer modified carbon fiber composite material is shown in fig. 1, and comprises a carbon fiber prepreg 1 which is arranged in a unidirectional manner, vertically oriented interlayer chopped carbon fibers 2, an epoxy matrix 3 sandwiched between two layers of the carbon fiber prepreg.
Wherein the carbon fiber prepreg is purchased from Hippo materials science and technology Limited and has the brand number of EP 700; the chopped carbon fiber is polyacrylonitrile-based carbon fiber, the length of the carbon fiber is about 100-150 mu m, and the diameter of the carbon fiber is 7 mu m.
In this embodiment, the polyacrylonitrile-based carbon fiber with the length of about 100-150 μm is obtained by mechanical vibration screening, which specifically comprises the following steps:
placing the cut polyacrylonitrile-based chopped carbon fibers in a mechanical vibrating screen, wherein the mesh number of the screen is as follows from top to bottom: 50 meshes, 100 meshes, 200 meshes and 300 meshes, and mechanically vibrating and screening for 2 hours. The polyacrylonitrile-based carbon fibers on each mesh screen are approximately the same length, for example, the polyacrylonitrile-based carbon fibers on a 100 mesh screen are approximately the same length, the polyacrylonitrile-based carbon fibers on a 200 mesh screen are approximately the same length, and the polyacrylonitrile-based carbon fibers on a 300 mesh screen are approximately the same length. After the screening is finished, taking 300-mesh polyacrylonitrile-based short-cut carbon fibers, and counting the length of the polyacrylonitrile-based short-cut carbon fibers by using an optical microscope, wherein the length of the polyacrylonitrile-based short-cut carbon fibers is about 100-150 mu m.
The interlayer modified carbon fiber composite material is prepared by the following method:
(1) placing the carbon fiber prepreg in a 60 ℃ oven for preheating for 20min to enable epoxy glue of the prepreg to be in a viscous semi-cured state, fixing the preheated carbon fiber prepreg on an upper polar plate of a high-voltage electrostatic device by using an adhesive tape, dispersing chopped carbon fibers on a lower polar plate of the high-voltage electrostatic device in a mechanical vibration mode, adjusting the distance between the polar plates to be 10cm, turning on a power switch of the high-voltage electrostatic device, adjusting the voltage to be 20kV, turning off a power supply after powering on for 10s, and vertically orienting, flying and inserting the polyacrylonitrile-based chopped carbon fibers into the epoxy glue of the prepreg due to the polarization effect of an electric field to obtain the carbon fiber prepreg attached with the vertically oriented chopped carbon fibers;
(2) repeating the step (1) to obtain 23 carbon fiber prepregs attached with the vertically oriented chopped carbon fibers;
(3) placing the die into a 50 ℃ oven for preheating, placing 23 pieces of carbon fiber prepreg attached with vertical orientation chopped carbon fibers obtained in the step (2) in a stacking mode, enabling the surfaces attached with the chopped carbon fibers to face upwards and be arranged in a unidirectional mode, then laying one piece of carbon fiber prepreg without the attached chopped carbon fibers on the uppermost surface, transferring the carbon fiber prepreg into the preheated die, placing the die on a press, keeping the temperature at 80 ℃ and the pressure at 1MPa for prepressing for 30min, heating to 150 ℃ after the prepressing to 2.5MPa, unloading the pressure, repeating the steps for three times, removing air between layers, and then curing for 3h at 150 ℃ and 2.5MPa to obtain the interlayer modified carbon fiber composite material.
The microscopic morphology of the cross section of the interlayer modified carbon fiber composite material provided by the embodiment is characterized by using a scanning electron microscope, and as can be seen from fig. 2 and 3, the interlayer chopped carbon fiber has a good vertical orientation characteristic in an epoxy matrix.
Example 2
This example differs from example 1 only in that the chopped carbon fibers used are pitch-based chopped carbon fibers. The other conditions were the same as in example 1.
Example 3
This example differs from example 1 only in that in step (1) the carbon fiber prepreg was placed in a 70 ℃ oven for preheating for 20 min. The other conditions were the same as in example 1.
Example 4
This example differs from example 1 only in that the inter-plate distance of the high voltage electrostatic device in step (1) is 8 cm. The other conditions were the same as in example 1.
Example 5
This example differs from example 1 only in that the voltage of the high voltage electrostatic device in step (1) was 10 kV. The other conditions were the same as in example 1.
Example 6
This example differs from example 1 only in that the pre-pressing time in step (3) was 60 min. The other conditions were the same as in example 1.
Example 7
This example is different from example 1 only in that the thermosetting temperature in step (3) is 130 ℃ and the other conditions are the same as example 1.
Comparative example 1
This comparative example differs from example 1 only in that, 24 carbon fiber prepregs were laid directly on top of one another without introducing vertically oriented chopped carbon fibers as reinforcement between the carbon fiber prepreg layers, i.e., without an interlaminar reinforcing phase. The other conditions were the same as in example 1.
The scanning electron microscope image of the cross section of the carbon fiber composite material provided by the comparative example is shown in fig. 4, and it can be seen that only the epoxy glue between the layers does not have the vertically oriented chopped carbon fiber reinforced phase.
Comparative example 2
This comparative example differs from example 1 only in that the carbon fiber prepreg was not subjected to a preheating treatment in step (1), i.e., the carbon fiber prepreg was directly placed in a high-pressure electrostatic device. The other conditions were the same as in example 1.
Comparative example 3
This comparative example is different from example 1 only in that the voltage of the high-voltage electrostatic device in step (1) was 2kV, and the other conditions were the same as example 1.
Comparative example 4
The comparative example is different from example 1 only in that the preliminary press treatment is not performed in step (3), and the temperature and pressure are directly raised to cure. The other conditions were the same as in example 1.
In order to test the interlaminar toughening performance of the carbon fiber composite materials in the examples and the comparative examples, the interlaminar toughening performance of the test samples is tested by using the GB 1446-83 standard. In one end of the sampleAnd laying a polytetrafluoroethylene plastic film or a film equivalent to the polytetrafluoroethylene plastic film on the surface to obtain the prefabricated crack. The sample was loaded in a displacement-controlled manner at a loading rate of 1 mm/min. And (4) unloading after the crack expands by about 20mm, and unloading after the crack expands by about 10mm each time until the crack length reaches about 100 mm. Recording the crack length, the crack propagation critical load corresponding to the highest point on the loaded load-loading point displacement curve and the loading point displacement, and calculating according to a formula to obtain the I-type interlaminar fracture toughness GIC. Five samples were tested and averaged.
The type I fracture toughness test results of example 1 and comparative example 1 are shown in fig. 5, and it can be seen that the type I fracture toughness of example 1 is improved by 91.6% and is significantly improved after vertically oriented chopped carbon fibers are added as a reinforcing phase between layers.
In comparative example 2, the carbon fiber prepreg is not preheated in advance, the epoxy glue in the prepreg is high in viscosity and does not show fluidity, so that the chopped carbon fibers vertically oriented in an electric field cannot penetrate into the carbon fiber prepreg, and the interlayer performance of the carbon fiber composite material is not improved.
In comparative example 3, when the chopped carbon fibers are oriented in the electric field, 2kV is selected as the oriented voltage, too small voltage makes the orientation of the chopped carbon fibers in the electric field not good, and meanwhile, the kinetic energy of the chopped carbon fibers obtained in the electric field is limited due to the small electric field intensity, and the chopped carbon fibers cannot be well pricked into the epoxy glue of the prepreg, so that the effect of improving the interlayer performance obtained by the chopped carbon fibers is limited.
In comparative example 4, during hot-pressing layer operation, pre-pressing operation was not performed, and a small amount of air was present between the obtained carbon fiber composite material layers, so that defects existed between the cured composite material layers, and the performance between the composite material layers was damaged.
The conductivity properties in the thickness direction of the samples of examples and comparative examples were measured using the Keithley-DMM7510 semiconductor characteristics analysis system, and the conductivity test results of examples 1 and comparative examples 1 are shown in fig. 6, from which it can be seen that the conductivity in the thickness direction of examples 1 is improved by 4 orders of magnitude compared to comparative examples 1.
The thermal diffusion coefficient D in the thickness direction of the samples in examples and comparative examples was measured in a nitrogen atmosphere by a laser flash method, and the specific heat capacity C was measured by combining a physical property test systemPUsing the formula K ═ ρ CPAnd D, calculating to obtain the thermal conductivity K, wherein rho is the density of the sample. The results of the thermal conductivity test of example 1 and comparative example 1 are shown in fig. 7, and it can be seen that the thermal conductivity of example 1 is improved by 36% compared to comparative example 1.
The results of the experimental conditions in examples 2 to 7 of the present application were substantially the same as those in example 1, except that the change in the experimental conditions did not substantially affect the properties of the test specimens.
Therefore, the interlayer I-shaped fracture toughness of the interlayer modified carbon fiber composite material based on the vertical-orientation chopped carbon fibers is improved by 91.6%, the interlayer toughness is obviously enhanced, meanwhile, the carbon fiber composite material has more excellent electric and heat conduction performance in the thickness direction, after the vertical-orientation chopped carbon fibers are introduced into the interlayer, the electric conductivity in the thickness direction is improved by four orders of magnitude, and the heat conductivity in the thickness direction is improved by 36%. The interlayer modified carbon fiber composite material based on the vertical orientation chopped carbon fibers is simple in preparation method, low in cost and good in operability, and can be prepared at room temperature.
The applicant states that the invention is illustrated by the above examples to the interlayer modified carbon fiber composite material of the invention, the preparation method and the application thereof, but the invention is not limited to the above examples, that is, the invention is not meant to be implemented only by relying on the above examples. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (10)

1. An interlayer modified carbon fiber composite material is characterized in that the interlayer modified carbon fiber composite material is prepared by vertically orienting short carbon fibers on a carbon fiber prepreg.
2. The interlaminar modified carbon fiber composite of claim 1, wherein the chopped carbon fibers comprise pitch-based carbon fibers and/or polyacrylonitrile-based carbon fibers.
3. The interlaminar modified carbon fiber composite material as claimed in claim 1 or 2, wherein the length of the chopped carbon fibers is 100-150 μm;
preferably, the chopped carbon fibers have a diameter of 6 to 10 μm.
4. The method for producing the interlaminar modified carbon fiber composite material according to any one of claims 1 to 3, characterized in that the production method comprises the steps of:
(1) preheating the carbon fiber prepreg, and vertically attaching the chopped carbon fibers to one surface of the carbon fiber prepreg to obtain the carbon fiber prepreg attached with the vertically oriented chopped carbon fibers;
(2) repeating the step (1) to obtain a plurality of carbon fiber prepregs attached with the vertically oriented chopped carbon fibers;
(3) and (3) stacking a plurality of carbon fiber prepregs attached with the vertical-orientation chopped carbon fibers obtained in the step (2), enabling the surfaces attached with the chopped carbon fibers to face upwards, laying one carbon fiber prepreg which is not attached with the chopped carbon fibers on the uppermost surface, transferring the carbon fiber prepreg into a mold, prepressing, heating, and curing to obtain the interlayer modified carbon fiber composite material.
5. The method for preparing the catalyst according to claim 4, wherein the temperature of the preheating in the step (1) is 60-80 ℃;
preferably, the preheating time in the step (1) is 10min-30 min.
6. The preparation method according to claim 4 or 5, wherein the step (1) of vertically attaching the chopped carbon fibers to one surface of the carbon fiber prepreg specifically comprises the following steps: fixing the preheated carbon fiber prepreg on an upper polar plate of a high-voltage electrostatic device, dispersing short carbon fibers on a lower polar plate of the high-voltage electrostatic device, turning on a power switch of the high-voltage electrostatic device, enabling the short carbon fibers to fly to the upper polar plate under the action of a high-voltage electrostatic field, vertically orienting in the electric field, and vertically penetrating into a resin matrix of the carbon fiber prepreg;
preferably, the fixing comprises fixing with an adhesive tape;
preferably, the means of dispersion comprises mechanical shock dispersion;
preferably, the voltage of the high-voltage electrostatic device is 5-20kV, and the electrifying time is 10-30 s;
preferably, the distance between the upper polar plate and the lower polar plate of the high-voltage electrostatic device is 5-15 cm;
preferably, the electric field intensity of the high-voltage electrostatic field is 1-3 kV/cm.
7. The method according to any one of claims 4 to 6, wherein the mold of step (3) is a preheated mold, and the preheated temperature is 50 ℃ to 150 ℃;
preferably, the temperature of the prepressing in the step (3) is 50-90 ℃, the prepressing time is 30-60min, and the prepressing pressure is 0.5-1.5 MPa.
8. The method according to any one of claims 4-7, wherein the temperature increase in step (3) is to 120-150 ℃;
preferably, the temperature for curing in step (3) is 120-150 ℃;
preferably, the pressure for curing in the step (3) is 2-5 MPa;
preferably, the curing time of step (3) is 2-5 h.
9. The method according to any one of claims 4 to 8, characterized in that it comprises the steps of:
(1) preheating a carbon fiber prepreg at 60-80 ℃ for 10-30 min, fixing the preheated carbon fiber prepreg on an upper polar plate of a high-voltage electrostatic device, dispersing short carbon fibers on a lower polar plate of the high-voltage electrostatic device, turning on a power switch of the high-voltage electrostatic device, enabling the short carbon fibers to fly to the upper polar plate under the action of a high-voltage electrostatic field, vertically orienting in the electric field, and vertically penetrating into a resin matrix of the carbon fiber prepreg to obtain the carbon fiber prepreg attached with the vertically oriented short carbon fibers; wherein the electric field intensity of the high-voltage electrostatic field is 1-3kV/cm, and the electrifying time is 10-30 s;
(2) repeating the step (1) to obtain a plurality of carbon fiber prepregs attached with the vertically oriented chopped carbon fibers;
(3) and (3) stacking a plurality of carbon fiber prepregs attached with the vertical-orientation chopped carbon fibers obtained in the step (2), wherein one surface attached with the chopped carbon fibers faces upwards, then laying one carbon fiber prepreg which is not attached with the chopped carbon fibers on the uppermost surface, then transferring the carbon fiber prepreg into a preheated mold, prepressing for 30-60min at 50-90 ℃ and 0.5-1.5MPa, heating to 120-150 ℃, and curing for 2-5h at 120-150 ℃ and 2-5MPa to obtain the interlayer modified carbon fiber composite material.
10. Use of the interlaminar modified carbon fiber composite of any one of claims 1 to 3 in a multifunctional composite product.
CN202210233556.XA 2022-03-10 2022-03-10 Interlayer modified carbon fiber composite material and preparation method and application thereof Pending CN114379167A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115302809A (en) * 2022-07-27 2022-11-08 浙江大学 Fiber high-energy implantation equipment and method

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Publication number Priority date Publication date Assignee Title
CN103987764A (en) * 2011-12-26 2014-08-13 东丽株式会社 Carbon fiber base, prepreg, and carbon-fiber-reinforced composite material
CN107323025A (en) * 2017-08-02 2017-11-07 北京航空航天大学 Vertical orientated composite of a kind of interlayer high heat conduction fine hair and preparation method thereof
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

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
CN103987764A (en) * 2011-12-26 2014-08-13 东丽株式会社 Carbon fiber base, prepreg, and carbon-fiber-reinforced composite material
CN107323025A (en) * 2017-08-02 2017-11-07 北京航空航天大学 Vertical orientated composite of a kind of interlayer high heat conduction fine hair and preparation method thereof
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
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CN115302809A (en) * 2022-07-27 2022-11-08 浙江大学 Fiber high-energy implantation equipment and method

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