CN111923554B - Composite material with high flexibility and mechanical property and preparation method and application thereof - Google Patents

Composite material with high flexibility and mechanical property and preparation method and application thereof Download PDF

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CN111923554B
CN111923554B CN202010832154.2A CN202010832154A CN111923554B CN 111923554 B CN111923554 B CN 111923554B CN 202010832154 A CN202010832154 A CN 202010832154A CN 111923554 B CN111923554 B CN 111923554B
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carbon fiber
fiber cloth
composite material
tpu
graphene oxide
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CN111923554A (en
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史振宇
段宁民
王继来
张成鹏
王兆辉
袭建人
杨晓涛
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Shandong University
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Shandong University
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/047—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D06M13/5135—Unsaturated compounds containing silicon atoms
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/02—Coating on the layer surface on 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2457/00—Electrical equipment
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/18—Aircraft
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention provides a composite material with high flexibility and mechanical property, a preparation method and application thereof, and belongs to the field of composite material preparation. The composite material is prepared by performing surface modification on carbon fiber cloth, spraying graphene oxide on the carbon fiber cloth, and stacking the carbon fiber cloth and a TPU plate layer by layer. According to the invention, the silane coupling agent and graphene oxide molecules are utilized to treat the surface of the carbon fiber, so that the combination of the carbon fiber cloth and TPU resin can be effectively improved, and the mechanical property of the carbon fiber cloth is further enhanced. The prepared carbon fiber cloth/graphene oxide/TPU composite material has good flexibility, can still recover after being bent, folded and the like for many times, and has good flexibility. The preparation method has the advantages of simple operation, environmental protection, low price cost and the like, and has the prospect of large-scale industrial production.

Description

Composite material with high flexibility and mechanical property and preparation method and application thereof
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a composite material with high flexibility and mechanical properties, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Carbon fiber reinforced Composites (CFRP) are one of the most advanced composite materials at present. The carbon fiber reinforced resin matrix Composite (CFRP) has a series of outstanding performances such as light weight, corrosion resistance, high specific strength and the like, and is widely applied to aerospace, military products, automobile industry and the like. For example, carbon fiber composites have accounted for about 60% of the weight of the helicopter type-9 self-developed by china. The application of composite materials is involved in the aspects of some small and simple structural components such as a rudder, the rear edge of an elevator wing, a pressure cabin wall plate, a cargo cabin floor sandwich structure panel, a wing fairing and the like on an aviation aircraft.
The preparation method of the common carbon fiber composite material at present comprises the following steps: (1) and combining the chopped carbon fibers with resin to prepare the carbon fiber composite material. (2) The chopped carbon fibers are subjected to physical and chemical treatment, so that the surfaces of the chopped carbon fibers are modified, and then the chopped carbon fibers are combined with resin to prepare the carbon fiber composite material with composite characteristics. Both processes are generally carried out to prepare composites by melt blending. The inventor finds that the melt blending method faces two problems, namely, the condition of low carbon fiber content can lead to no obvious improvement of the performance of the composite material; secondly, the carbon fiber is agglomerated in the resin under the condition of high carbon fiber content, so that the performance of the composite material is poor.
Graphene oxide is used as an important derivative of graphene-based materials, and although the oxidation process destroys the highly conjugated structure of graphene, the graphene oxide still maintains special surface properties and a layered structure. The introduction of the oxygen-containing group not only enables the graphene oxide to have chemical stability, but also provides a surface modification active site and a larger specific surface area for synthesizing the graphene-based/graphene oxide-based material. The graphene oxide is used as a precursor and a support carrier for synthesizing the graphene-based composite material, and is easy to functionalize and high in controllability. In the process of compounding with metal, metal oxide, high molecular polymer and other materials, the material can be dispersed and attached effectively in large specific surface area to prevent agglomeration. The graphene oxide also shows excellent physical, chemical, optical and electrical properties, and due to the coexistence structure of various oxygen-containing functional groups on the basal plane and the edge of the graphene sheet layer skeleton, the conductivity and band gap of the graphene oxide can be adjusted by regulating the type and the number of the contained oxygen-containing functional groups, so that the graphene oxide has great application in the photoelectric field, the solar cell field and the biological field.
Disclosure of Invention
In order to overcome the problems, the invention provides a composite material with high flexibility and mechanical properties, and a preparation method and application thereof. According to the invention, the surface of the carbon fiber cloth is modified by a silane coupling agent, so that a large number of active groups exist on the surface of the carbon fiber cloth, graphene oxide is deposited on the modified carbon fiber cloth by a spraying treatment method, and finally a TPU (thermoplastic polyurethane) plate and the carbon fiber cloth on which the graphene oxide is deposited are prepared at a high temperature in a layer-by-layer stacking manner, so that the multilayer carbon fiber cloth/graphene oxide/TPU composite material with high flexibility and mechanical properties is obtained. The invention has the advantages of environmental protection, high universality, good economy and the like, and the prepared composite material has good flexibility and excellent mechanical property, thereby having good value of practical popularization and application.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
in a first aspect of the invention, a multilayer carbon fiber cloth/graphene oxide/TPU composite material with high flexibility and mechanical properties is provided, the composite material is made by stacking carbon fiber cloth and TPU plate layers, and both the upper surface layer and the lower surface layer of the composite material are TPU plates.
The carbon fiber cloth is obtained by modifying the coupling agent and graphene oxide molecules, and the combination of the carbon fiber cloth and TPU resin can be effectively improved through the modification treatment, so that the mechanical property of the carbon fiber cloth is enhanced.
The number of the stacked layers of the carbon fiber cloth and the TPU plate can be adjusted according to actual conditions, so that the composite material of the present invention may include any number of layers of carbon fiber cloth, such as one layer, two layers, three layers, and the like.
In a second aspect of the present invention, there is provided a method for preparing the above composite material, the method comprising: and after the surface modification treatment is carried out on the carbon fiber cloth, the carbon fiber cloth after the surface modification treatment is treated by using graphene oxide, and then the carbon fiber cloth and the TPU plate are stacked layer by layer to obtain the carbon fiber cloth. According to the method, the surface of the carbon fiber cloth is modified by a coupling agent, so that a large number of active groups such as hydroxyl and carboxyl exist on the surface of the carbon fiber cloth, graphene oxide is deposited on the modified carbon fiber cloth by a spraying treatment method, and finally a TPU (thermoplastic polyurethane) plate and the carbon fiber cloth on which the graphene oxide is deposited are prepared at a high temperature in a layer-by-layer stacking manner, so that the multilayer carbon fiber cloth/graphene oxide/TPU composite material with high flexibility and mechanical properties is obtained.
In a third aspect of the present invention, there is provided an application of the composite material and/or the composite material obtained by the preparation method in the manufacture of electronic devices or communication devices.
The beneficial technical effects of one or more technical schemes are as follows:
(1) according to the technical scheme, the silane coupling agent and the graphene oxide molecules are utilized to treat the surface of the carbon fiber, so that the combination of the carbon fiber cloth and the TPU resin can be effectively improved, and the mechanical property of the carbon fiber cloth is further enhanced.
(2) The carbon fiber cloth/graphene oxide/TPU composite material prepared by the technical scheme has good flexibility, can still recover after being bent, folded and the like for many times, and has good flexibility.
(3) The carbon fiber cloth/graphene oxide/TPU composite material prepared by the technical scheme has good mechanical property, wherein the mechanical property of the three-layer composite material can reach 144.1 MPa.
(4) The method used by the technical scheme has the advantages of simple operation, environmental protection and low price and cost, and has a prospect of large-scale industrial production.
(5) The carbon fiber cloth/graphene oxide/TPU composite material prepared by the technical scheme has good mechanical properties and has good application prospects in the aerospace field or the electronic industry.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a fourier infrared spectrum of graphene oxide and a silane coupling agent before and after surface treatment of a carbon fiber cloth in example 1 of the present invention.
Fig. 2 is an X-ray photoelectron energy spectrum of the graphene oxide and the silane coupling agent before and after the surface treatment of the carbon fiber cloth in example 1 of the present invention.
Fig. 3 is a flexibility diagram of the carbon fiber cloth/graphene oxide/TPU composite material in embodiment 1 of the present invention.
Fig. 4 is a graph of the tensile strength of the carbon fiber cloth/graphene oxide/TPU composite material in examples 1 to 3 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. It is to be understood that the scope of the invention is not to be limited to the specific embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention.
As mentioned above, the composite material prepared by the existing melt mixing has the problems of poor performance and the like.
In view of the above, in an exemplary embodiment of the present invention, a multi-layered carbon fiber cloth/graphene oxide/TPU composite material with high flexibility and mechanical properties is provided, the composite material is made by stacking carbon fiber cloth and TPU plate layers, and both the upper surface layer and the lower surface layer of the composite material are TPU plates.
The carbon fiber cloth is obtained by modifying the coupling agent and graphene oxide molecules, and the combination of the carbon fiber cloth and TPU resin can be effectively improved through the modification treatment, so that the mechanical property of the carbon fiber cloth is enhanced.
In yet another embodiment of the present invention, the coupling agent is a silane coupling agent.
The number of the stacked layers of the carbon fiber cloth and the TPU plate can be adjusted according to actual conditions, so that the composite material of the present invention may include any number of layers of carbon fiber cloth, such as one layer, two layers, three layers, and the like.
In another embodiment of the present invention, there is provided a method for preparing the above composite material, the method comprising: and after the surface modification treatment is carried out on the carbon fiber cloth, the carbon fiber cloth after the surface modification treatment is treated by using graphene oxide, and then the carbon fiber cloth and the TPU plate are stacked layer by layer to obtain the carbon fiber cloth. According to the method, the surface of the carbon fiber cloth is modified by a coupling agent, so that a large number of active groups such as hydroxyl and carboxyl exist on the surface of the carbon fiber cloth, graphene oxide is deposited on the modified carbon fiber cloth by a spraying treatment method, and finally a TPU (thermoplastic polyurethane) plate and the carbon fiber cloth on which the graphene oxide is deposited are prepared at a high temperature in a layer-by-layer stacking manner, so that the multilayer carbon fiber cloth/graphene oxide/TPU composite material with high flexibility and mechanical properties is obtained.
The surface modification treatment of the carbon fiber cloth is carried out by using a coupling agent, the type of the coupling agent is not particularly limited, in some embodiments, the coupling agent is a silane coupling agent, such as KH-550, KH-560, KH-570 and KH-580, and the bonding strength of the carbon fibers on the TPU plate is improved by modifying the carbon fiber cloth by using the silane coupling agent.
In another embodiment of the present invention, the surface modification treatment method comprises: placing the carbon fiber cloth in a mixed solution of absolute ethyl alcohol and a silane coupling agent, standing at a high temperature, washing to remove the residual ethyl alcohol and the silane coupling agent on the surface, and drying to obtain the carbon fiber cloth.
In another embodiment of the present invention, the mass ratio of the anhydrous ethanol to the silane coupling agent is 2 to 3:1, preferably 3: 1.
In another embodiment of the present invention, the specific method of high temperature standing is: the mixture is placed at 50-70 ℃ for 6-10 hours, preferably 60 ℃ for 8 hours.
In yet another embodiment of the present invention, the washing may be performed with water (e.g., distilled water);
in another embodiment of the present invention, the drying process specifically comprises: and (3) treating the treated carbon fiber cloth for 7-10 hours (preferably 8 hours) under a vacuum drying condition, and controlling the temperature to be 90-110 ℃ (preferably 100 ℃).
In yet another embodiment of the present invention, the TPU sheet is commercially or self-prepared, and in some embodiments, the TPU sheet is prepared as follows: drying the TPU granules to remove water, then placing the dried TPU granules in a corresponding mould, carrying out hot pressing treatment, and carrying out curing molding to obtain the TPU granules.
In another embodiment of the present invention, the hot pressing conditions are as follows: and (3) treating at 180-200 ℃ for 20-60 minutes, preferably at 190 ℃ for 30 minutes, and pressurizing the TPU particles at the temperature to effectively cure and form the TPU plate.
In another embodiment of the present invention, the carbon fiber cloth treated by graphene oxide comprises the following specific steps: and spraying graphene oxide on the carbon fiber cloth subjected to surface modification treatment, and drying to obtain the graphene oxide-coated carbon fiber cloth. Wherein the drying treatment specifically comprises: vacuum drying treatment is carried out for 6-10 hours at 50-70 ℃, and preferably for 8 hours at 60 ℃.
In another embodiment of the present invention, the spraying treatment specifically comprises: placing the carbon fiber cloth with the modified surface on a platform, and then spraying a spray gun containing a graphene oxide aqueous solution against the carbon fiber cloth; the distance between the spray gun and the modified carbon fiber cloth is 10-20 cm. During the spraying process, the spray gun is moved back and forth 10-15 times at a speed of 2-3cm/s to ensure the integrity and uniformity of the coverage.
In another embodiment of the present invention, the method for preparing the composite material by stacking layers comprises the following steps: stacking the carbon fiber cloth treated by the graphene oxide with the TPU plate layer, wherein the structure is similar to a sandwich, and then carrying out hot-pressing treatment to obtain the carbon fiber cloth.
In another embodiment of the invention, the hot pressing temperature is controlled to be 180-200 ℃, preferably 190 ℃; and the hot pressing time and the pressure are properly adjusted according to the number of stacked layers, so that the carbon fiber cloth/graphene oxide/TPU composite material with different layers is obtained. Therefore, the composite material of the present invention may contain any number of layers of carbon fiber cloth, such as one layer, two layers, three layers, and the like.
In some embodiments, the hot-pressing condition of the layer of carbon fiber cloth/graphene oxide/TPU composite material is 190 ℃, the pressure is 5MPa, and the hot-pressing time is 15 minutes; the hot-pressing condition of the two-layer carbon fiber cloth/graphene oxide/TPU composite material is 190 ℃, the pressure is 8MPa, and the hot-pressing time is 20 minutes; the hot-pressing condition of the three-layer carbon fiber cloth/graphene oxide/TPU composite material is 190 ℃, the pressure is 10MPa, and the hot-pressing time is 30 minutes.
In another embodiment of the present invention, there is provided a use of the composite material and/or the composite material obtained by the preparation method in the manufacture of electronic devices or communication devices.
The technical solution of the present invention will be described below with specific examples. The raw materials used in the following examples were all commercially available and the equipment used was existing. Wherein the tensile strength standard is ASTM D3039/D3039M-00.
Example 1
A preparation method of a layer of carbon fiber cloth/graphene oxide/TPU composite material comprises the following steps:
firstly, placing the carbon fiber cloth in a mixed solution (mass ratio is 3:1) of absolute ethyl alcohol and a silane coupling agent KH-550 in the carbon fiber cloth, placing the carbon fiber cloth in an environment at 60 ℃ for 8 hours, then washing the carbon fiber cloth with distilled water to remove residual ethanol and the silane coupling agent on the surface, washing the carbon fiber cloth for multiple times, and then placing the carbon fiber cloth in a vacuum drying oven at 100 ℃ for drying for 8 hours to obtain the surface-modified carbon fiber cloth.
And secondly, putting the TPU granules into a vacuum drying box at 100 ℃ for drying to remove moisture existing in the TPU granules, then putting the dried TPU granules into a corresponding mould, processing the dried TPU granules on a hot press at 190 ℃ for 30 minutes, and pressing the TPU granules at the temperature to effectively solidify and form the TPU plate.
And thirdly, placing the carbon fiber cloth with the modified surface on a platform, and then carrying out spraying treatment on the carbon fiber cloth by using a spray gun containing the graphene oxide aqueous solution. The distance between the spray gun and the modified carbon fiber cloth is 20 cm. During the spraying process, the gun was moved back and forth 10 times at a speed of about 3cm/s to ensure the integrity and uniformity of the coverage. And (3) drying the sprayed carbon fiber cloth in a vacuum oven at 60 ℃ for 8 hours to obtain the carbon fiber cloth treated by the graphene oxide.
And fourthly, stacking the carbon fiber cloth treated by the graphene oxide and two TPU plate layers, wherein the structure is similar to a sandwich, and then placing the carbon fiber cloth and the TPU plate layers on a hot press to be hot-pressed for 15 minutes at the temperature of 190 ℃ and under the pressure of 5MPa, so that a layer of carbon fiber cloth/graphene oxide/TPU composite material can be prepared.
Fig. 1 is a fourier infrared spectrum before and after the surface treatment of the carbon fiber cloth by the graphene oxide and the silane coupling agent, and fig. 2 is an X-ray photoelectron energy spectrum before and after the surface treatment of the carbon fiber cloth by the graphene oxide and the silane coupling agent, from which it can be seen that the elements on the surface of the carbon fiber cloth after the treatment are obviously changed, which indicates that the graphene oxide and the silane coupling agent are successfully grafted on the surface of the carbon fiber cloth.
Example 2
A preparation method of a two-layer carbon fiber cloth/graphene oxide/TPU composite material comprises the following steps:
firstly, placing the carbon fiber cloth in a mixed solution (mass ratio is 3:1) of absolute ethyl alcohol and a silane coupling agent KH-550 in the carbon fiber cloth, placing the carbon fiber cloth in an environment at 60 ℃ for 8 hours, then washing the carbon fiber cloth with distilled water to remove residual ethanol and the silane coupling agent on the surface, washing the carbon fiber cloth for multiple times, and then placing the carbon fiber cloth in a vacuum drying oven at 100 ℃ for drying for 8 hours to obtain the surface-modified carbon fiber cloth.
And secondly, putting the TPU granules into a vacuum drying box at 100 ℃ for drying to remove moisture existing in the TPU granules, then putting the dried TPU granules into a corresponding mould, processing the dried TPU granules on a hot press at 190 ℃ for 30 minutes, and pressing the TPU granules at the temperature to effectively solidify and form the TPU plate.
And thirdly, placing the carbon fiber cloth with the modified surface on a platform, and then carrying out spraying treatment on the carbon fiber cloth by using a spray gun containing the graphene oxide aqueous solution. The distance between the spray gun and the modified carbon fiber cloth is 20 cm. During the spraying process, the gun was moved back and forth 10 times at a speed of about 3cm/s to ensure the integrity and uniformity of the coverage. And (3) drying the sprayed carbon fiber cloth in a vacuum oven at 60 ℃ for 8 hours to obtain the carbon fiber cloth treated by the graphene oxide.
And fourthly, stacking two carbon fiber cloth treated by graphene oxide and three TPU plate layers, wherein the structure is similar to a sandwich, and then placing the carbon fiber cloth and the TPU plate layers on a hot press to be hot-pressed for 20 minutes at the temperature of 190 ℃ and under the pressure of 8MPa, so that the two-layer carbon fiber cloth/graphene oxide/TPU composite material can be prepared.
Example 3
A preparation method of a three-layer carbon fiber cloth/graphene oxide/TPU composite material comprises the following steps:
firstly, placing the carbon fiber cloth in a mixed solution (mass ratio is 3:1) of absolute ethyl alcohol and a silane coupling agent KH-550 in the carbon fiber cloth, placing the carbon fiber cloth in an environment at 60 ℃ for 8 hours, then washing the carbon fiber cloth with distilled water to remove residual ethanol and the silane coupling agent on the surface, washing the carbon fiber cloth for multiple times, and then placing the carbon fiber cloth in a vacuum drying oven at 100 ℃ for drying for 8 hours to obtain the surface-modified carbon fiber cloth.
And secondly, putting the TPU granules into a vacuum drying box at 100 ℃ for drying to remove moisture existing in the TPU granules, then putting the dried TPU granules into a corresponding mould, processing the dried TPU granules on a hot press at 190 ℃ for 30 minutes, and pressing the TPU granules at the temperature to effectively solidify and form the TPU plate.
And thirdly, placing the carbon fiber cloth with the modified surface on a platform, and then carrying out spraying treatment on the carbon fiber cloth by using a spray gun containing the graphene oxide aqueous solution. The distance between the spray gun and the modified carbon fiber cloth is 20 cm. During the spraying process, the gun was moved back and forth 10 times at a speed of about 3cm/s to ensure the integrity and uniformity of the coverage. And (3) drying the sprayed carbon fiber cloth in a vacuum oven at 60 ℃ for 8 hours to obtain the carbon fiber cloth treated by the graphene oxide.
And fourthly, stacking three carbon fiber cloth treated by graphene oxide and four TPU (thermoplastic polyurethane) plate layers, wherein the structure is similar to a sandwich, and then placing the carbon fiber cloth and the TPU plate layers on a hot press to be hot-pressed for 30 minutes at the temperature of 190 ℃ and under the pressure of 10MPa, so that the three-layer carbon fiber cloth/graphene oxide/TPU composite material can be prepared.
The test result shows that: the tensile strength of the carbon fiber cloth/graphene oxide/TPU composite material at one layer is 71.4MPa, the tensile strength of the carbon fiber cloth/graphene oxide/TPU composite material at the second layer is 102.2MPa, and the tensile strength of the carbon fiber cloth/graphene oxide/TPU composite material at the third layer is 144.1 MPa. In addition, fig. 3 shows a state where a layer of the composite material is subjected to a plurality of bending and folding, illustrating that the composite material prepared by the method used in the present invention has excellent flexibility.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (20)

1. The multilayer carbon fiber cloth/graphene oxide/TPU composite material with high flexibility and mechanical property is characterized in that the composite material is formed by stacking carbon fiber cloth and TPU plate layers, and the upper surface layer and the lower surface layer of the composite material are TPU plates;
the carbon fiber cloth is obtained by modifying a coupling agent and graphene oxide molecules;
the preparation method of the composite material comprises the following steps: after the surface modification treatment is carried out on the carbon fiber cloth, the carbon fiber cloth after the surface modification treatment is treated by graphene oxide, and then the carbon fiber cloth and a TPU plate are stacked layer by layer to obtain the carbon fiber cloth;
the carbon fiber cloth is treated by the graphene oxide, and the treatment method comprises the following specific steps: and spraying graphene oxide on the carbon fiber cloth subjected to surface modification treatment, and drying to obtain the graphene oxide-coated carbon fiber cloth.
2. The composite material of claim 1, wherein the coupling agent is a silane coupling agent.
3. The composite material of claim 2, wherein the coupling agent is KH-550, KH-560, KH-570, or KH-580.
4. The composite material of claim 1, wherein the surface modification treatment is performed by a specific method comprising: placing the carbon fiber cloth in a mixed solution of absolute ethyl alcohol and a silane coupling agent, standing at a high temperature, washing to remove the residual ethyl alcohol and the silane coupling agent on the surface, and drying to obtain the carbon fiber cloth.
5. The composite material according to claim 4, wherein the mass ratio of the anhydrous ethanol to the silane coupling agent is 2-3: 1;
the specific method for standing at high temperature comprises the following steps: standing for 6-10 hours at 50-70 ℃;
the washing is carried out by adopting water;
the drying treatment specifically comprises the following steps: and (3) treating the treated carbon fiber cloth for 7-10 hours under a vacuum drying condition, and controlling the temperature to be 90-110 ℃.
6. The composite material of claim 5, wherein the anhydrous ethanol and silane coupling agent are present in a mass ratio of 3: 1.
7. The composite material of claim 5, wherein the high temperature standing method comprises the following specific steps: the mixture was left at 60 ℃ for 8 hours.
8. The composite material of claim 5, wherein the water is distilled water.
9. The composite material according to claim 5, characterized in that the drying treatment is in particular: and (3) treating the treated carbon fiber cloth for 8 hours under a vacuum drying condition.
10. The composite material of claim 5, wherein the controlled temperature is 100 ℃.
11. The composite material of claim 1, wherein the TPU sheet is made by: drying the TPU granules to remove water, then placing the dried TPU granules in a corresponding mould, carrying out hot pressing treatment, and carrying out curing molding to obtain the TPU granules.
12. The composite material of claim 11, wherein the hot pressing treatment is carried out under the following specific conditions: treating for 20-60 minutes at 180-200 ℃.
13. The composite material of claim 12, wherein the autoclave treatment is carried out under the following specific conditions: the treatment was carried out at 190 ℃ for 30 minutes.
14. The composite material according to claim 11, characterized in that the drying treatment is in particular: vacuum drying at 50-70 deg.c for 6-10 hr.
15. The composite material of claim 14, wherein the vacuum drying process is carried out at 60 ℃ for 8 hours.
16. The composite material according to claim 1, wherein the spraying treatment is in particular: placing the carbon fiber cloth with the modified surface on a platform, and then spraying a spray gun containing a graphene oxide aqueous solution against the carbon fiber cloth; the distance between the spray gun and the modified carbon fiber cloth is 10-20 cm; during the spraying process, the spray gun moves back and forth 10-15 times at the speed of 2-3 cm/s.
17. The composite material of claim 1, wherein the composite material is prepared by stacking layers by the specific steps of: stacking the carbon fiber cloth treated by the graphene oxide with the TPU plate layer, and carrying out hot pressing treatment to obtain the carbon fiber cloth.
18. The composite material of claim 17, wherein the hot pressing temperature is controlled to be 180-200 ℃.
19. The composite material of claim 18, wherein the hot pressing temperature is controlled to 190 ℃.
20. Use of a composite material according to any one of claims 1 to 19 in the manufacture of electronic devices or in the manufacture of communication devices.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108286187A (en) * 2017-12-26 2018-07-17 山东大学 A kind of preparation method of silane coupling agent auxiliary electrophoretic deposition initiated oxidation graphene modified carbon fiber
CN110450488A (en) * 2019-07-31 2019-11-15 山东大学 A kind of preparation method of different stack layer carbon cloth/TPU composite materials with high electromagnetic shielding performance

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108286187A (en) * 2017-12-26 2018-07-17 山东大学 A kind of preparation method of silane coupling agent auxiliary electrophoretic deposition initiated oxidation graphene modified carbon fiber
CN110450488A (en) * 2019-07-31 2019-11-15 山东大学 A kind of preparation method of different stack layer carbon cloth/TPU composite materials with high electromagnetic shielding performance

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