CN111116992B - Modified carbon fiber, preparation method and application - Google Patents
Modified carbon fiber, preparation method and application Download PDFInfo
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- CN111116992B CN111116992B CN201911383063.9A CN201911383063A CN111116992B CN 111116992 B CN111116992 B CN 111116992B CN 201911383063 A CN201911383063 A CN 201911383063A CN 111116992 B CN111116992 B CN 111116992B
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Abstract
The invention belongs to the technical field of electromagnetic shielding, and particularly relates to a modified carbon fiber, a preparation method and application thereof. The modified carbon fiber provided by the invention is prepared according to the following steps: a) dipping the dopamine modified carbon fiber into a solution containing a substance A to obtain a substance A-dopamine modified carbon fiber; b) under the alkaline condition, mixing and reacting the substance A-dopamine modified carbon fiber with dopamine modified filler in a liquid phase to obtain filler modified carbon fiber; c) and carbonizing the filler modified carbon fiber to obtain the modified carbon fiber. The invention solves the problems of poor dispersibility and easy agglomeration of the small-scale filler in the modified material, and the filler in the provided modified carbon fiber is uniformly dispersed and has excellent electromagnetic shielding performance; the resin composite material prepared from the modified carbon fiber has good electromagnetic shielding performance and mechanical strength.
Description
Technical Field
The invention belongs to the technical field of electromagnetic shielding, and particularly relates to a modified carbon fiber, a preparation method and application thereof.
Background
The Carbon Fiber (CF) is a special fiber composed of carbon elements, has the characteristics of high temperature resistance, friction resistance, electric conduction, heat conduction, corrosion resistance and the like, is fibrous and soft in appearance, and can be processed into various fabrics. The carbon fiber is mainly used as a reinforcing material to be compounded with resin, metal, ceramic, carbon and the like to manufacture an advanced composite material.
In recent years, carbon fiber reinforced resin matrix composite materials are more and more widely applied in the field of electromagnetic shielding, and in order to improve the market competitiveness of the carbon fiber reinforced resin matrix composite materials, a certain amount of functional filler, such as a wave absorbing agent, a reinforcing filler and the like, is usually additionally added into the composite materials. At present, functional fillers are generally directly added into a resin base material for compounding, but most of the functional fillers are small in size and easy to agglomerate, so that the functional fillers are difficult to disperse uniformly in the resin base material, the electromagnetic shielding performance of the material is unstable, and the mechanical property of the composite material is reduced due to the fact that the functional fillers are not uniformly dispersed in the resin base material, so that the practical application of the composite material is seriously influenced.
Disclosure of Invention
In view of the above, the present invention aims to provide a modified carbon fiber, a preparation method and an application thereof. The modified carbon fiber provided by the invention solves the problems of poor dispersibility and easy agglomeration of small-scale fillers in modified materials, and the fillers in the modified carbon fiber are uniformly dispersed and have excellent electromagnetic shielding performance; the resin composite material prepared from the modified carbon fiber has good electromagnetic shielding performance and mechanical strength.
The invention provides modified carbon fiber, which is prepared by mixing and reacting dopamine modified carbon fiber with a substance A and a dopamine modified filler in sequence and then carbonizing;
the substance A is a compound and/or a polymer containing active amino;
the dopamine modified filler comprises dopamine modified magnetic particles and/or dopamine modified carbon nano-materials.
Preferably, the dopamine-modified magnetic particles comprise one or more of dopamine-modified ferroferric oxide particles, dopamine-modified nickel particles, dopamine-modified cobalt particles and dopamine-modified cobalt ferrite particles;
the dopamine modified carbon nano material comprises dopamine modified carbon nano tubes and/or dopamine modified graphene.
Preferably, the substance A comprises one or more of aliphatic amine, alicyclic amine, polyethyleneimine, polyamide-amine and polyacrylamide.
The invention provides a preparation method of modified carbon fibers, which comprises the following steps:
a) dipping the dopamine modified carbon fiber into a solution containing a substance A for chemical reaction to obtain a substance A-dopamine modified carbon fiber;
the substance A is a compound or polymer containing active amino, and comprises one or more of aliphatic amine, alicyclic amine, polyethyleneimine, polyamide-amine and polyacrylamide;
b) under the alkaline condition, mixing the substance A-dopamine modified carbon fiber and dopamine modified filler in a liquid phase for reaction to obtain a substance B (dopamine modified filler-substance A-dopamine modified fiber);
the dopamine modified filler comprises dopamine modified magnetic particles and/or dopamine modified carbon nano-materials;
c) and carbonizing the substance B to obtain the modified carbon fiber.
Preferably, the dopamine modified carbon fiber is prepared according to the following steps:
mixing a carbon fiber material with dopamine in a liquid phase under an alkaline condition; taking out the carbon fiber material from the liquid phase after a period of time, and drying to obtain dopamine modified carbon fiber;
the dopamine modified filler is prepared according to the following steps:
mixing a filler with dopamine in a liquid phase under alkaline conditions; and taking out the filler from the liquid phase after a period of time, and drying to obtain the dopamine modified filler.
Preferably, in the step a), the concentration of the substance A is 1-5 mg/mL; the dipping time is 1-48 h.
Preferably, step b) specifically comprises:
b1) dipping the substance A-dopamine modified fiber into an alkaline buffer solution containing dopamine modified filler for reaction to obtain a substance B (dopamine modified filler-substance A-dopamine modified fiber);
b2) taking out the substance B from the liquid phase, and drying to obtain filler modified carbon fiber;
in the step b1), the concentration of the dopamine modified filler in the alkaline buffer solution containing the dopamine modified filler is (0.5-2) mg/mL; the dipping time is 0.5-48 h.
Preferably, in the step c), the temperature of the carbonization treatment is 900-1200 ℃; the carbonization treatment time is 60-300 min.
The invention also provides a composite material which comprises the modified carbon fiber. For example, the composite material comprises modified carbon fibers, resin and a curing agent, wherein the modified carbon fibers are the modified carbon fibers or the modified carbon fibers prepared by the preparation method in the technical scheme.
The invention also provides an electromagnetic shielding material which comprises the modified fiber.
The invention provides a preparation method of a composite material, which comprises the following steps:
and mixing the modified carbon fiber, the resin and the curing agent, and curing to obtain the composite material, wherein the modified carbon fiber is the modified carbon fiber prepared by the technical scheme or the modified carbon fiber prepared by the preparation method of the technical scheme.
The invention utilizes Dopamine (DA) to carry out surface modification on the filler, so that the filler is uniformly dispersed in a liquid phase and is not agglomerated; then the filler is efficiently and uniformly grafted on the surface of the carbon fiber by utilizing the Schiff base reaction principle; and finally, carrying out high-temperature carbonization treatment on the carbon fiber with the surface grafted with the filler by utilizing the principle that polydopamine is carbonized at high temperature to form a graphene-like layer structure, wherein the polydopamine on the surfaces of the carbon fiber and the filler is converted into graphene-like layer carbide with excellent conductivity in the process, so that the surface of the carbon fiber can be firmly coated with the filler to form an integral structure, the surface conductivity of the carbon fiber can be obviously improved, various loss mechanisms are formed on electromagnetic waves, and the electromagnetic shielding performance of the finally obtained modified carbon fiber is further enhanced. In addition, when the modified carbon fiber prepared by the invention is subsequently adopted to prepare the resin composite material, the filler uniformly distributed on the surface of the modified carbon fiber can be uniformly distributed in the resin matrix along with the carbon fiber, so that the problem of filler agglomeration can not exist, and the filler distributed on the surface of the modified carbon fiber can also enhance the roughness of the surface of the material, so that the mechanical locking action between the carbon fiber and the epoxy resin is enhanced, the interface performance between the carbon fiber and the epoxy resin is improved, and the mechanical property of the finally prepared resin composite material is enhanced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a flow chart of a process for preparing a modified carbon fiber/resin composite material according to example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides modified carbon fiber, which is prepared by mixing and reacting dopamine modified carbon fiber with a substance A and a dopamine modified filler in sequence and then carbonizing;
the substance A is a compound or polymer containing active amino groups, and the active amino groups comprise amino and/or imino;
the dopamine modified filler comprises dopamine modified magnetic particles and/or dopamine modified carbon nano-materials.
The modified carbon fiber provided by the invention is prepared by mixing and reacting dopamine modified carbon fiber with a substance A and a dopamine modified filler in sequence and then carbonizing the mixture. The dopamine modified carbon fiber is composed of a carbon fiber material and polydopamine attached to the surface of the carbon fiber material, the carbon fiber material can be selected from a desized fiber fabric, and the polydopamine can be formed by self-polymerization of dopamine under an alkaline condition. In some embodiments provided herein, the dopamine modified carbon fiber can be prepared by the following steps:
mixing a carbon fiber material with dopamine in a liquid phase under an alkaline condition; and taking out the carbon fiber material from the liquid phase after a period of time, and drying to obtain the dopamine modified carbon fiber.
In the preparation steps of the dopamine modified carbon fiber provided by the above embodiment of the present invention, firstly, the carbon fiber material and dopamine are mixed in a liquid phase under an alkaline condition; the pH value of the alkaline condition is preferably 8-10, and specifically can be 8, 8.5, 9, 9.5 or 10; the specific process of mixing preferably comprises: the carbon fiber material is immersed into an alkaline buffer solution containing dopamine, and the dopamine is subjected to self-polymerization reaction under alkaline conditions and attached to the surface of the carbon fiber material. Wherein, the alkaline buffer solution is preferably Tris-HCl buffer solution; the concentration of the dopamine in the alkaline buffer solution is preferably (0.5-3) mg/mL, and specifically can be 0.5mg/mL, 1mg/mL, 1.5mg/mL, 2mg/mL, 2.5mg/mL or 3 mg/mL; the dipping temperature is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the soaking time is preferably 12-48 h, and specifically can be 12h, 18h, 24h, 30h, 36h, 42h or 48 h.
In the preparation step of the dopamine modified carbon fiber provided by the above embodiment of the present invention, the drying mode is preferably drying, and the drying temperature is preferably 80 to 100 ℃, and specifically may be 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃. In the present invention, the carbon fiber material taken out of the liquid phase is preferably washed with water before drying.
In the modified carbon fiber provided by the invention, the dopamine modified carbon fiber is preferably mixed and reacted with the substance A according to the following steps:
and (3) soaking the dopamine modified carbon fiber into a solution containing the substance A, and carrying out Schiff base reaction on polydopamine on the dopamine modified carbon fiber and an active amino group in the substance A to obtain the modified carbon fiber bonded with the substance A. The substance A is a compound or polymer containing active amino, the active amino comprises amino and/or imino, preferably one or more of aliphatic amine, alicyclic amine, polyethyleneimine, polyamide-amine and polyacrylamide, and the more the active amino in the substance A, the more the electromagnetic shielding performance and the mechanical performance of the modified fiber and the composite material can be effectively improved. The concentration of the substance A in the solution is preferably 1-5 mg/mL, and specifically can be 1mg/mL, 1.5mg/mL, 2mg/mL, 2.5mg/mL, 3mg/mL, 3.5mg/mL, 4mg/mL, 4.5mg/mL or 5 mg/mL; the dipping temperature is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the soaking time is preferably 1-5 h, and specifically can be 1h, 2h, 3h, 4h, 4.5h or 5 h.
In the modified carbon fiber provided by the invention, the dopamine modified filler comprises dopamine modified magnetic particles and/or dopamine modified carbon nano-materials. The dopamine modified magnetic particles comprise but are not limited to one or more of dopamine modified ferroferric oxide particles, dopamine modified nickel particles, dopamine modified cobalt particles and dopamine modified cobalt ferrite particles, and the particle size of the dopamine modified magnetic particles is preferably in a nanometer level; the dopamine modified carbon nanomaterial comprises, but is not limited to, dopamine modified carbon nanotubes and/or dopamine modified graphene. In the invention, the use of the dopamine modified magnetic particles can obviously improve the magnetic permeability of the modified carbon fiber, and the use of the dopamine modified carbon nano-material can further improve the electric conductivity and the mechanical strength of the modified carbon fiber.
In the modified carbon fiber provided by the invention, the dopamine modified filler consists of a filler and polydopamine attached to the surface of the filler, and the filler comprises magnetic particles and/or carbon nano-materials; the magnetic particles include but are not limited to one or more of ferroferric oxide particles, nickel particles, cobalt particles and cobalt ferrite particles, and the particle size of the magnetic particles is preferably nanometer-scale; the carbon nanomaterials include, but are not limited to, multi-carbon nanotubes and/or graphene; the polydopamine can be prepared by self-polymerization of dopamine under alkaline conditions. In one embodiment provided by the present invention, the dopamine modified filler can be prepared according to the following steps:
mixing a filler with dopamine in a liquid phase under alkaline conditions; and taking out the filler from the liquid phase after a period of time, and drying to obtain the dopamine modified filler.
In the preparation steps of the dopamine modified filler provided by the above embodiment of the present invention, firstly, the filler and dopamine are mixed in a liquid phase under an alkaline condition; the pH value of the alkaline condition is preferably 8-10, and specifically can be 8, 8.5, 9, 9.5 or 10; the specific process of mixing preferably comprises: the filler is immersed in an alkaline buffer containing dopamine which undergoes a self-polymerization reaction under alkaline conditions and adheres to the filler surface. Wherein, the alkaline buffer solution is preferably Tris-HCl buffer solution; the concentration of the dopamine in the alkaline buffer solution is preferably (0.5-3) mg/mL, and specifically can be 0.5mg/mL, 1mg/mL, 1.5mg/mL, 2mg/mL, 2.5mg/mL or 3 mg/mL; the concentration of the filler in the alkaline buffer solution is preferably (0.5-3) mg/mL, and specifically can be 0.5mg/mL, 1mg/mL, 1.5mg/mL, 2mg/mL, 2.5mg/mL or 3 mg/mL; in the process of immersing the filler, the temperature of the mixed system is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the immersion time is preferably 12-48 h, and specifically can be 12h, 18h, 24h, 30h, 36h, 42h or 48 h. In the invention, in the process of immersing the filler, ultrasound and stirring are preferably carried out, specifically, ultrasound is firstly carried out for 30-60 min, and then stirring is carried out until the filler is taken out.
In the preparation step of the dopamine modified filler provided by the above embodiment of the present invention, the drying mode is preferably drying, and the drying temperature is preferably 80 to 100 ℃, and specifically may be 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃. In the present invention, the filler taken out of the liquid phase is preferably washed with water before drying.
In the modified carbon fiber provided by the invention, the substance A-dopamine modified carbon fiber is preferably mixed and reacted with dopamine modified filler according to the following steps:
dipping the substance A-dopamine modified carbon fiber into an alkaline buffer solution containing dopamine modified filler, and carrying out Schiff base reaction on the substance A-dopamine modified carbon fiber and polydopamine on the dopamine modified filler so as to introduce the filler to the surface of the carbon fiber; and then taking out the carbon fiber after the reaction from the liquid phase to obtain a substance B, and drying to obtain the filler modified carbon fiber. The pH value of the alkaline buffer solution is preferably 8-10, specifically 8, 8.5, 9, 9.5 or 10, and the alkaline buffer solution is preferably Tris-HCl buffer solution; the concentration of the dopamine modified filler in the alkaline buffer solution containing the dopamine modified filler is preferably (0.5-2) mg/mL, and specifically can be 0.5mg/mL, 1mg/mL, 1.5mg/mL or 2 mg/mL; the dipping time is preferably 0.5-3 h, and specifically can be 0.5h, 1h, 1.5h, 2h, 2.5h or 3 h; the drying mode is preferably drying, and the drying temperature is preferably 80-100 ℃, and specifically can be 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃.
In the modified carbon fiber provided by the invention, the carbonization treatment temperature is preferably 900-1200 ℃, and specifically can be 900 ℃, 950 ℃, 980 ℃, 1000 ℃, 1050 ℃, 1100 ℃ or 1200 ℃ and the like; the carbonization treatment time is preferably 60-300 min, and specifically can be 60min, 80min, 120min, 150min, 200min, 250min or 300 min. In the invention, polydopamine adhered to the carbon fibers can form a graphene layer-like structure layer after high-temperature carbonization, so that the surface of the carbon fibers is firmly coated with the filler, the filler and the carbon fibers form an integral structure, and the conductivity of the surface of the carbon fibers is improved.
In the modified carbon fiber provided by the invention, the preferred surface density of the modified carbon fiber is 200-500 g/m2Specifically, it may be 200g/m2、250g/m2、300g/m2、350g/m2、400g/m2、450g/m2Or 500g/m2。
The modified carbon fiber provided by the invention has the advantages that the filler is efficiently and uniformly grafted on the surface of the carbon fiber by utilizing the Schiff base reaction principle; and then, the carbon fiber with the filler grafted on the surface is subjected to high-temperature carbonization treatment by utilizing the principle that polydopamine is subjected to high-temperature carbonization to form a graphene-like layer structure, and the polydopamine on the surface of the carbon fiber is converted into graphene-like carbide with excellent conductivity in the process, so that the filler and the carbon fiber can be firmly coated on the surface of the carbon fiber to form an integral structure, and the surface conductivity of the carbon fiber can be obviously improved, so that the electromagnetic shielding performance and the mechanical performance of the modified carbon fiber provided by the invention are further enhanced.
In addition, when the modified carbon fiber provided by the invention is subsequently adopted to prepare the resin composite material, the filler uniformly distributed on the surface of the modified carbon fiber can be uniformly distributed in the resin matrix along with the carbon fiber, so that the problem of filler agglomeration can not exist, and the filler distributed on the surface of the modified carbon fiber can also enhance the roughness of the surface of the material, so that the mechanical locking action between the carbon fiber and the epoxy resin is enhanced, the interface performance between the carbon fiber and the epoxy resin is improved, and the mechanical property of the finally prepared resin composite material is enhanced.
The experimental results show that: the shielding effectiveness of the modified carbon fiber/resin composite material prepared by the modified carbon fiber provided by the invention is more than 40dB (the maximum value of 8.2-12.4 GHz), the tensile strength is more than 910MPa, the bending strength is more than 1065MPa, and the interlaminar shear strength is more than or equal to 60 MPa.
The invention also provides a preparation method of the modified carbon fiber, which comprises the following steps:
a) dipping the dopamine modified carbon fiber into a solution containing a substance A to obtain a substance A-dopamine modified carbon fiber;
the substance A is a compound or polymer containing active amino;
b) under the alkaline condition, mixing and reacting the substance A-dopamine modified carbon fiber with dopamine modified filler in a liquid phase to obtain filler modified carbon fiber;
the dopamine modified filler comprises dopamine modified magnetic particles and/or dopamine modified carbon nano-materials;
c) and carbonizing the filler modified carbon fiber to obtain the modified carbon fiber.
According to the preparation method of the modified carbon fiber, the dopamine modified carbon fiber is provided firstly, the dopamine modified carbon fiber is composed of a carbon fiber material and polydopamine attached to the surface of the carbon fiber material, the carbon fiber material can be selected from a desized carbon fiber fabric, and the polydopamine can be formed by self-polymerization of dopamine under an alkaline condition. In some embodiments provided herein, the dopamine modified carbon fiber can be prepared by:
mixing a carbon fiber material with dopamine in a liquid phase under an alkaline condition; and taking out the carbon fiber material from the liquid phase after a period of time, and drying to obtain the dopamine modified carbon fiber.
In the preparation steps of the dopamine modified carbon fiber provided by the above embodiment of the present invention, firstly, the carbon fiber material and dopamine are mixed in a liquid phase under an alkaline condition; the pH value of the alkaline condition is preferably 8-10, and specifically can be 8, 8.5, 9, 9.5 or 10; the specific process of mixing preferably comprises: the carbon fiber material is immersed into an alkaline buffer solution containing dopamine, and the dopamine is subjected to self-polymerization reaction under alkaline conditions and attached to the surface of the carbon fiber material. Wherein, the alkaline buffer solution is preferably Tris-HCl buffer solution; the concentration of the dopamine in the alkaline buffer solution is preferably (0.5-3) mg/mL, and specifically can be 0.5mg/mL, 1mg/mL, 1.5mg/mL, 2mg/mL, 2.5mg/mL or 3 mg/mL; the dipping temperature is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the soaking time is preferably 12-48 h, and specifically can be 12h, 18h, 24h, 30h, 36h, 42h or 48 h.
In the preparation step of the dopamine modified carbon fiber provided by the above embodiment of the present invention, the drying mode is preferably drying, and the drying temperature is preferably 80 to 100 ℃, and specifically may be 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃. In the present invention, the carbon fiber material taken out of the liquid phase is preferably washed with water before drying.
And (3) soaking the dopamine modified carbon fiber into a solution containing the substance A, and carrying out Schiff base reaction on polydopamine on the dopamine modified carbon fiber and an active amino group in the substance A to obtain the modified carbon fiber bonded with the substance A. The substance A is a compound or polymer containing active amino, the active amino comprises amino and/or imino, preferably one or more of aliphatic amine, alicyclic amine, polyethyleneimine, polyamide-amine and polyacrylamide, and the more the active amino in the substance A, the more the electromagnetic shielding performance and the mechanical performance of the modified fiber and the composite material can be effectively improved. The concentration of the substance A in the solution is preferably 1-5 mg/mL, and specifically can be 1mg/mL, 1.5mg/mL, 2mg/mL, 2.5mg/mL, 3mg/mL, 3.5mg/mL, 4mg/mL, 4.5mg/mL or 5 mg/mL; the dipping temperature is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the soaking time is preferably 1-5 h, and specifically can be 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5 h.
In the preparation method of the modified carbon fiber provided by the invention, the substance A-dopamine modified fiber and dopamine modified filler are mixed and reacted in a liquid phase under an alkaline condition to obtain the filler modified carbon fiber. The dopamine modified filler is composed of a filler and polydopamine attached to the surface of the filler, the filler comprises magnetic particles and/or carbon nano materials, and the polydopamine can be formed by self-polymerization of dopamine under an alkaline condition. In the invention, the dopamine modified filler can be prepared according to the following steps:
mixing a filler with dopamine in a liquid phase under alkaline conditions; and taking out the filler from the liquid phase after a period of time, and drying to obtain the dopamine modified carbon fiber.
In the step of preparing the dopamine modified filler provided by the invention, firstly, the filler and dopamine are mixed in a liquid phase under an alkaline condition; the pH value of the alkaline condition is preferably 8-10, and specifically can be 8, 8.5, 9, 9.5 or 10; the specific process of mixing preferably comprises: the filler is immersed into an alkaline buffer solution containing dopamine, and the dopamine undergoes self-polymerization reaction under alkaline conditions and is attached to the surface of the filler. Wherein, the alkaline buffer solution is preferably Tris-HCl buffer solution; the concentration of the dopamine in the alkaline buffer solution is preferably (0.5-3) mg/mL, and specifically can be 0.5mg/mL, 1mg/mL, 1.5mg/mL, 2mg/mL, 2.5mg/mL or 3 mg/mL; the concentration of the filler in the alkaline buffer solution is preferably (0.5-3) mg/mL, and specifically can be 0.5mg/mL, 1mg/mL, 1.5mg/mL, 2mg/mL, 2.5mg/mL or 3 mg/mL; in the process of immersing the filler, the temperature of the mixed system is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the immersion time is preferably 12-48 h, and specifically can be 12h, 18h, 24h, 30h, 36h, 42h or 48 h. In the invention, in the process of immersing the filler, ultrasound and stirring are preferably carried out, specifically, ultrasound is firstly carried out for 30-60 min, and then stirring is carried out until the filler is taken out.
In the step of preparing the dopamine modified filler provided by the invention, the drying mode is preferably drying, and the drying temperature is preferably 80-100 ℃, and specifically can be 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃. In the present invention, the filler taken out of the liquid phase is preferably washed with water before drying.
In the preparation method of the modified carbon fiber provided by the present invention, the specific preparation steps of the filler modified carbon fiber preferably include:
b1) dipping the substance A-dopamine modified carbon fiber into an alkaline buffer solution containing dopamine modified filler for reaction to obtain a reaction product;
b2) and taking out the reaction product from the liquid phase, and drying to obtain the filler modified carbon fiber.
In the preparation step of the filler modified carbon fiber provided by the invention, in step b1), the pH value of the alkaline buffer solution is preferably 8-10, specifically 8, 8.5, 9, 9.5 or 10, and the alkaline buffer solution is preferably Tris-HCl buffer solution; the concentration of the dopamine modified filler in the alkaline buffer solution containing the dopamine modified filler is preferably (0.5-2) mg/mL, and specifically can be 0.5mg/mL, 1mg/mL, 1.5mg/mL or 2 mg/mL; the soaking time is preferably 0.5-3 h, and specifically can be 0.5h, 1h, 1.5h, 2h, 2.5h or 3 h. In the dipping process, the substance A-dopamine modified carbon fiber and polydopamine on the dopamine modified filler are subjected to Schiff base reaction, so that the filler is introduced to the surface of the carbon fiber.
In the preparation step of the filler modified carbon fiber provided by the invention, in the step b2), the drying mode is preferably drying, and the drying temperature is preferably 80-100 ℃, and specifically may be 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃.
In the preparation method of the modified carbon fiber provided by the invention, after the filler modified carbon fiber is obtained, the filler modified carbon fiber is carbonized. Wherein the carbonization treatment temperature is preferably 950-1050 ℃, and specifically can be 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃, 1000 ℃, 1010 ℃, 1020 ℃, 1030 ℃, 1040 ℃ or 1050 ℃; the carbonization time is preferably 120-150min, and specifically can be 120min, 125min, 130min, 135min, 140min, 145min or 150 min. In the carbonization treatment process, polydopamine adhered to the carbon fibers forms a graphene-like layer structure after high-temperature carbonization, so that the surface of the carbon fibers is firmly coated with the filler, and the conductivity of the surface of the carbon fibers is improved. And finally, obtaining the modified carbon fiber provided by the invention after the carbonization treatment.
The invention utilizes Dopamine (DA) to carry out surface modification on the filler, so that the filler can be uniformly dispersed in a liquid phase and is not agglomerated; then the filler is efficiently and uniformly grafted on the surface of the carbon fiber by utilizing the Schiff base reaction principle; and finally, carrying out high-temperature carbonization treatment on the carbon fiber with the surface grafted with the filler by utilizing the principle that polydopamine is subjected to high-temperature carbonization to form a graphene-like layer structure, wherein the polydopamine on the surface of the carbon fiber is converted into graphene-like carbide with excellent conductivity in the process, so that the filler can be firmly coated on the surface of the carbon fiber, the conductivity of the surface of the carbon fiber can be obviously improved, and the electromagnetic shielding performance of the finally obtained modified carbon fiber is further enhanced.
In addition, when the modified carbon fiber prepared by the invention is subsequently adopted to prepare the resin composite material, the filler uniformly distributed on the surface of the modified carbon fiber can be uniformly distributed in the resin matrix along with the carbon fiber, so that the problem of filler agglomeration can not exist, and the filler distributed on the surface of the modified carbon fiber can also enhance the roughness of the surface of the material, so that the mechanical locking action between the carbon fiber and the epoxy resin is enhanced, the interface performance between the carbon fiber and the epoxy resin is improved, and the mechanical property of the finally prepared resin composite material is enhanced.
The invention also provides a composite material which comprises the modified carbon fiber, epoxy resin and a curing agent, wherein the modified carbon fiber is the modified carbon fiber in the technical scheme or the modified carbon fiber prepared by the method in the technical scheme.
The composite material provided by the invention comprises the modified carbon fiber, resin and a curing agent. The modified carbon fiber is preferably a modified carbon fiber fabric layer, and the surface density of the modified carbon fiber fabric layer is preferably 200-500 g/m2Specifically, it may be 200g/m2、250g/m2、300g/m2、350g/m2、400g/m2、450g/m2Or 500g/m2(ii) a The resin is preferably an epoxy resin; the mass ratio of the modified carbon fibers to the epoxy resin is preferably (2-6): 6, specifically 2:6, 2.5:6, 3:6, 3.5:6, 4:6, 4.5:6, 5:6, 5.5:6 or 5: 6; the mass ratio of the epoxy resin to the curing agent is preferably (2-4): 1, specifically 2:1, 2.5:1, 3:1, 3.5:1 or 4: 1.
The modified carbon fiber provided by the technical scheme of the invention is added into the composite material provided by the invention, so that the composite material has good electromagnetic shielding performance and mechanical strength. The experimental results show that: the shielding effectiveness of the composite material provided by the invention is more than 40dB (the maximum value of 8.2-12.4 GHz), the tensile strength is more than 910MPa, the bending strength is more than 1065MPa, and the interlaminar shear strength is more than or equal to 60 MPa.
The invention also provides a preparation method of the composite material, which comprises the following steps:
mixing the modified carbon fiber, resin and a curing agent, and curing to obtain a composite material;
the modified carbon fiber is the modified carbon fiber in the technical scheme or the modified carbon fiber prepared by the method in the technical scheme.
In the preparation method of the composite material provided by the invention, the modified carbon fiber, the resin and the curing agent are directly mixed and then cured to obtain the composite material. Wherein the curing temperature is preferably 80-100 ℃, and specifically can be 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃; the curing time is preferably 8-12 h, and specifically can be 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h or 12 h. In the present invention, a specific process for preparing the composite material may employ a VARTM molding process.
For the sake of clarity, the following examples are given in detail.
Example 1
The composite material is prepared according to the flow shown in fig. 1, and specifically comprises the following steps:
(1) adding Dopamine (DA) into a Tris-HCl buffer solution with the pH value of 8.5 to prepare a DA/Tris-HCl buffer solution with the DA concentration of 1mg/mL, and uniformly stirring; then dipping the desized carbon fiber fabric (CF) in DA/Tris-HCl buffer solution for 12h at room temperature; and then washing the carbon fiber with deionized water for three times and drying the carbon fiber at 80-100 ℃ to obtain the dopamine modified carbon fiber (DA-CF).
(2) DA-CF is added into a 1mg/mL polyethyleneimine solution, and the solution is immersed for 2 hours at room temperature to obtain polyethyleneimine modified carbon fibers (PEI-CF).
(3) Adding Dopamine (DA) into a Tris-HCl buffer solution with the pH value of 8.5 to prepare a DA/Tris-HCl buffer solution with the DA concentration of 1mg/mL, and uniformly stirring; then adding the ferroferric oxide nano particles into DA/Tris-HCl buffer solution at room temperature to prepare Fe3O4Mixed solution with concentration of 1mg/mL, ultrasonic at 200W and 3%After 0min, magnetically stirring the mixed solution at room temperature for 12 h; finally centrifugally washing by deionized water and drying at 80 ℃ to prepare dopamine modified ferroferric oxide (DA-Fe)3O4)。
(4) DA-Fe3O4Dispersing in Tris-HCl buffer solution with pH value of 8.5 to prepare DA-Fe3O4A suspension at a concentration of 1 mg/mL; then, PEI-CF is dipped in the suspension for 1h, the product is fished out and dried at the temperature of 80 ℃, and ferroferric oxide modified carbon fiber (Fe) is obtained3O4-CF)。
(5) Mixing Fe3O4carbonizing-CF in a muffle furnace at 950 ℃ for 120-150min to obtain carbonized ferroferric oxide modified carbon fiber (Fe)3O4-C-CF)。
(6) Preparation of carbon fiber/epoxy resin composite material by VARTM (vacuum vapor deposition) molding process, wherein Fe3O4The areal density of the-C-CF is 300g/m210 carbon fiber layers, epoxy resin and Fe3O4The mass ratio of-C to CF is 4:6, the ratio of epoxy resin (E51) to curing agent (trimethylethylenediamine) is 3:1, and the curing temperature of the composite material is 80 ℃/5 h.
Example 2
(1) Adding Dopamine (DA) into a Tris-HCl buffer solution with the pH value of 8.5 to prepare a DA/Tris-HCl buffer solution with the DA concentration of 2mg/mL, and uniformly stirring; then dipping the desized carbon fiber fabric (CF) in DA/Tris-HCl buffer solution for 24-36h at room temperature; and then washing the carbon fiber with deionized water for three times and drying the carbon fiber at 80-100 ℃ to obtain the dopamine modified carbon fiber (DA-CF).
(2) DA-CF is added into a polyethyleneimine solution of 2mg/mL, and the solution is immersed for 1-2h at room temperature to obtain polyethyleneimine modified carbon fibers (PEI-CF).
(3) Adding Dopamine (DA) into a Tris-HCl buffer solution with the pH value of 8.5 to prepare a DA/Tris-HCl buffer solution with the DA concentration of 2mg/mL, and uniformly stirring; adding the nickel nanoparticles into DA/Tris-HCl buffer solution at room temperature to prepare mixed solution with the Ni concentration of 1mg/mL, performing ultrasonic treatment at 200W for 60min, and magnetically stirring the mixed solution at room temperature for 24 h; and finally, centrifugally washing by deionized water and drying at 80 ℃ to prepare the dopamine modified nickel powder (DA-Ni).
(4) Dispersing DA-Ni in Tris-HCl buffer solution with the pH value of 8.5 to prepare suspension with the concentration of DA-Ni of 1 mg/mL; and then, soaking the PEI-CF in the suspension for 1-2h, taking out the product, and drying at 80 ℃ to obtain the nickel modified carbon fiber (Ni-CF).
(5) And carbonizing the Ni-CF in a muffle furnace at 1050 ℃ for 120min to obtain the carbonized nickel modified carbon fiber (Ni-C-CF).
(6) The preparation of the carbon fiber/epoxy resin composite material is carried out by utilizing a VARTM (vacuum assisted transfer molding) forming process, wherein the surface density of Ni-C-CF is 300g/m210 carbon fiber layers, epoxy resin and Fe3O4The mass ratio of-C to CF is 4:6, the ratio of epoxy resin (E51) to curing agent (trimethylethylenediamine) is 3:1, and the curing temperature of the composite material is 80 ℃/5 h.
Example 3
(1) Adding Dopamine (DA) into a Tris-HCl buffer solution with the pH value of 8.5 to prepare a DA/Tris-HCl buffer solution with the DA concentration of 2mg/mL, and uniformly stirring; then dipping the desized carbon fiber fabric (CF) in DA/Tris-HCl buffer solution for 24 hours at room temperature; and then washing the carbon fiber with deionized water for three times and drying the carbon fiber at 80-100 ℃ to obtain the dopamine modified carbon fiber (DA-CF).
(2) DA-CF is added into a polyethyleneimine solution of 2mg/mL, and the solution is immersed for 1-2h at room temperature to obtain polyethyleneimine modified carbon fibers (PEI-CF).
(3) Adding Dopamine (DA) into a Tris-HCl buffer solution with the pH value of 8.5 to prepare a DA/Tris-HCl buffer solution with the DA concentration of 2mg/mL, and uniformly stirring; then adding the cobalt nanoparticles into DA/Tris-HCl buffer solution at room temperature to prepare mixed solution with the Co concentration of 1mg/mL, carrying out ultrasonic treatment at 200W for 60-90min, and then carrying out magnetic stirring on the mixed solution at room temperature for 36 h; and finally, centrifugally washing by deionized water and drying at 80 ℃ to obtain the dopamine modified cobalt powder (DA-Co).
(4) Dispersing DA-Co in Tris-HCl buffer solution with the pH value of 8.5 to prepare suspension with the concentration of DA-Co being 1 mg/mL; and then, soaking the PEI-CF in the suspension for 2h, taking out the product, and drying at 80 ℃ to obtain the cobalt powder modified carbon fiber (Co-CF).
(5) And carbonizing the Co-CF in a muffle furnace at 10000 ℃ for 120min to obtain the carbonized cobalt powder modified carbon fiber (Co-C-CF).
(6) The preparation of the carbon fiber/epoxy resin composite material is carried out by utilizing a VARTM (vacuum assisted transfer molding) forming process, wherein the areal density of Co-C-CF is 300g/m2The number of carbon fiber laying layers is 10, the mass ratio of epoxy resin to Co-C-CF is 4:6, the ratio of epoxy resin (E51) to curing agent (trimethylethylenediamine) is 3:1, and the curing temperature of the composite material is 80 ℃/5 h.
Example 4
(1) Adding Dopamine (DA) into a Tris-HCl buffer solution with the pH value of 8.5 to prepare a DA/Tris-HCl buffer solution with the DA concentration of 2mg/mL, and uniformly stirring; then dipping the desized carbon fiber fabric (CF) in DA/Tris-HCl buffer solution for 24-36h at room temperature; then washing with deionized water for three times and drying at 80 ℃ to obtain the dopamine modified carbon fiber (DA-CF).
(2) DA-CF is added into a polyethyleneimine solution of 2mg/mL, and the solution is immersed for 2 hours at room temperature to obtain polyethyleneimine modified carbon fibers (PEI-CF).
(3) Adding Dopamine (DA) into a Tris-HCl buffer solution with the pH value of 8.5 to prepare a DA/Tris-HCl buffer solution with the DA concentration of 2mg/mL, and uniformly stirring; then adding the nano cobalt ferrite particles into DA/Tris-HCl buffer solution at room temperature to prepare CoFe2O4Carrying out ultrasonic treatment on the mixed solution with the concentration of 1mg/mL for 30min at 200W, and then magnetically stirring the mixed solution at room temperature for 24 h; finally centrifugally washing by deionized water and drying at 80 ℃ to prepare the dopamine modified nano cobalt ferrite particles (DA-CoFe)2O4)。
(4) DA-CoFe2O4Dispersing in Tris-HCl buffer solution with pH value of 8.5 to prepare DA-CoFe2O41mg/mL suspension, then soaking PEI-CF in the suspension for 1h, taking out the product, and drying at 80 ℃ to obtain the cobalt ferrite modified carbon fiber (CoFe)2O4-CF)。
(5) Mixing CoFe2O4carbonizing-CF in a muffle furnace at 950 ℃ for 120min to obtain carbonized cobalt ferrite modified carbon fiber(CoFe2O4-C-CF)。
(6) Preparing carbon fiber/epoxy resin composite material by using VARTM (vacuum assisted transfer molding) process, wherein CoFe2O4The areal density of the-C-CF is 300g/m210 carbon fiber layers, epoxy resin and CoFe2O4The mass ratio of-C to CF is 4:6, the ratio of epoxy resin (E51) to curing agent (trimethylethylenediamine) is 3:1, and the curing temperature of the composite material is 80 ℃/5 h.
Example 5
(1) Adding Dopamine (DA) into a Tris-HCl buffer solution with the pH value of 8.5 to prepare a DA/Tris-HCl buffer solution with the DA concentration of 2mg/mL, and uniformly stirring; then dipping the desized carbon fiber fabric (CF) in DA/Tris-HCl buffer solution for 24 hours at room temperature; then washing with deionized water for three times and drying at 80 ℃ to obtain the dopamine modified carbon fiber (DA-CF).
(2) DA-CF is added into a polyethyleneimine solution of 2mg/mL, and the solution is immersed for 1h at room temperature to obtain polyethyleneimine modified carbon fibers (PEI-CF).
(3) Adding Dopamine (DA) into a Tris-HCl buffer solution with the pH value of 8.5 to prepare a DA/Tris-HCl buffer solution with the DA concentration of 2mg/mL, and uniformly stirring; adding graphene into DA/Tris-HCl buffer solution at room temperature to prepare mixed solution with the G concentration of 1mg/mlL, performing ultrasonic treatment at 200W for 30min, and magnetically stirring the mixed solution at room temperature for 12 h; and carrying out suction filtration, washing and drying to obtain the dopamine modified graphene (DA-G).
(4) Dispersing DA-G in Tris-HCl buffer solution with the pH value of 8.5 to prepare suspension with the concentration of DA-G being 1 mg/mL; and then, soaking PEI-CF in the suspension for 1h by 60W ultrasound, taking out the product, and drying at 80 ℃ to obtain the graphene modified carbon fiber (G-CF).
(5) Carbonizing the G-CF in a muffle furnace at 1050 ℃ for 150min to obtain carbonized graphene modified carbon fibers (G-C-CF).
(6) The preparation of the carbon fiber/epoxy resin composite material is carried out by utilizing a VARTM (vacuum assisted transfer molding) forming process, wherein the areal density of G-C-CF is 300G/m2The number of carbon fiber laying layers is 10, the mass ratio of epoxy resin to G-C-CF is 4:6, and epoxy resin (E51) is mixed with epoxy resinThe proportion of the curing agent (trimethylethylenediamine) is 3:1, and the curing temperature of the composite material is 80 ℃/5 h.
Performance testing
The composite materials prepared in examples 1 to 5 were respectively processed into test sample strips, and the electromagnetic shielding performance and the mechanical strength were tested, and the results are shown in table 1:
TABLE 1 composite electromagnetic shielding performance and mechanical strength test results
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A modified carbon fiber is prepared by mixing and reacting dopamine modified carbon fiber with a substance A and a dopamine modified filler in sequence, and then carbonizing;
the substance A is a compound and/or a polymer containing active amino;
the dopamine modified filler comprises dopamine modified magnetic particles and/or dopamine modified carbon nano-materials;
and in the carbonization process, polydopamine on the surfaces of the carbon fibers and the filler is converted into graphene-like layer carbide.
2. The modified carbon fiber of claim 1, wherein the dopamine-modified magnetic particles comprise one or more of dopamine-modified ferroferric oxide particles, dopamine-modified nickel particles, dopamine-modified cobalt particles, and dopamine-modified cobalt ferrite particles;
the dopamine modified carbon nano material comprises dopamine modified carbon nano tubes and/or dopamine modified graphene.
3. The modified carbon fiber according to claim 1, wherein the substance a comprises one or more of aliphatic amine, alicyclic amine, polyethyleneimine, polyamide, polyamidoamine, and polyacrylamide.
4. A preparation method of modified carbon fiber comprises the following steps:
a) dipping the dopamine modified carbon fiber into a solution containing a substance A for chemical reaction to obtain a substance A-dopamine modified carbon fiber;
the substance A is a compound and/or a polymer containing active amino, and comprises one or more of aliphatic amine, alicyclic amine, polyethyleneimine, polyamide-amine and polyacrylamide;
b) under the alkaline condition, mixing the substance A-dopamine modified carbon fiber and dopamine modified filler in a liquid phase for reaction to obtain a substance B;
the dopamine modified filler comprises dopamine modified magnetic particles and/or dopamine modified carbon nano-materials;
c) carbonizing the substance B to obtain modified carbon fibers;
and in the carbonization process, polydopamine on the surfaces of the carbon fibers and the filler is converted into graphene-like layer carbide.
5. The preparation method according to claim 4, wherein the dopamine-modified carbon fiber is prepared by the following steps:
mixing a carbon fiber material with dopamine in a liquid phase under an alkaline condition; taking out the carbon fiber material from the liquid phase after a period of time, and drying to obtain dopamine modified carbon fiber;
the dopamine modified filler is prepared according to the following steps:
mixing a filler with dopamine in a liquid phase under alkaline conditions; and taking out the filler from the liquid phase after a period of time, and drying to obtain the dopamine modified filler.
6. The preparation method according to claim 4, wherein in the step a), the concentration of the substance A is 1-5 mg/mL; the dipping time is 1-48 h.
7. The method according to claim 4, wherein step b) comprises in particular:
b1) dipping the substance A-dopamine modified carbon fiber into an alkaline buffer solution containing dopamine modified filler for reaction to obtain a substance B;
b2) taking the substance B out of the liquid phase and drying;
in the step b1), the concentration of the dopamine modified filler in the alkaline buffer solution containing the dopamine modified filler is (0.5-2) mg/mL; the dipping time is 0.5-48 h.
8. The preparation method according to claim 4, wherein in the step c), the temperature of the carbonization treatment is 900 to 1200 ℃; the carbonization treatment time is 60-300 min.
9. A composite material comprising the modified carbon fiber according to any one of claims 1 to 3 or the modified carbon fiber produced by the production method according to any one of claims 4 to 8.
10. An electromagnetic shielding material, comprising the modified carbon fiber according to any one of claims 1 to 3 or the modified carbon fiber obtained by the production method according to any one of claims 4 to 8.
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