CN108589267B - Industrial method for continuous modification of carbon fiber surface - Google Patents
Industrial method for continuous modification of carbon fiber surface Download PDFInfo
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- CN108589267B CN108589267B CN201810460689.4A CN201810460689A CN108589267B CN 108589267 B CN108589267 B CN 108589267B CN 201810460689 A CN201810460689 A CN 201810460689A CN 108589267 B CN108589267 B CN 108589267B
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
Abstract
The invention relates to an industrial method for continuously modifying the surface of carbon fiber, which solves the technical problem of the blank technical field of the research and development and application of the carbon fiber modified by using carbon nitride, and provides the industrial method for continuously modifying the surface of the carbon fiber, which comprises the following steps: (1) carbon fiber pretreatment: dipping the carbon fiber precursor which is not coated with the sizing agent in an aqueous solution containing the component A, and then drying to obtain pretreated carbon fiber; the component A is composed of one or more of cyanamide, dicyandiamide, melamine, urea or thiourea; (2) in-situ generation of carbon nitride reinforcement on the surface of carbon fiber: enabling the pretreated carbon fiber obtained in the step (1) to pass through a fluidized bed containing a component B, and generating a carbon nitride reinforcement in situ on the surface of the carbon fiber; the component B is composed of one or more of melamine, urea or thiourea, and the invention can be widely applied to the field of preparation of high-performance composite materials.
Description
Technical Field
The invention relates to the field of preparation of high-performance composite materials, in particular to an industrial method for continuous modification of the surface of carbon fiber.
Background
Carbon Fiber (Carbon Fiber) is a high-strength, high-modulus Fiber material with a Carbon content of more than 95%, and has many excellent properties of elemental Carbon: such as small specific gravity, good heat resistance, small thermal expansion coefficient, large thermal conductivity, good corrosion resistance and electrical conductivity, etc. Meanwhile, the fabric has fiber-like flexibility and can be woven and wound for forming. The carbon fiber has the best performance of high specific strength and high specific modulus, and is an ideal reinforcement for resin matrix composite materials. The carbon fiber reinforced epoxy resin-based composite material is widely applied to the fields of aerospace, national defense weaponry, sports equipment and transportation, can obviously reduce weight, improve effective load and improve overall performance, and is an excellent structural material. But carbon fibers also have inherent disadvantages: the surface is smooth and lacks reactive groups, so that the wettability of the carbon fiber reinforced epoxy resin composite material with epoxy resin is poor, the interface bonding force between the carbon fiber reinforced epoxy resin composite material and the epoxy resin is weak, and the further application of the carbon fiber reinforced epoxy resin composite material is severely limited.
In order to solve the technical problem of poor interface bonding between carbon fibers and an epoxy resin matrix, researchers in the field of interface engineering have developed various carbon fiber surface modification technologies, including: surface coating method (CN102312377A), wet chemical oxidation method (CN102021678A), vapor deposition method (CN104532548A), plasma treatment (CN103696228A), chemical grafting method (CN105063999A), electrochemical oxidation treatment (CN104178790A), high-energy ray radiation treatment (CN105887463A), and surface nanoparticle graft modification method (CN 105690802A). The surface nano particle grafting modification method can enhance the interface combination between the fiber and the matrix by increasing the mechanical locking area and the chemical bonding effect between the carbon fiber and the epoxy resin, and obviously improves the overall performance of the composite material. The commonly used carbon fiber surface nano-reinforcing materials comprise silicon dioxide, titanium dioxide, zinc oxide and the like, no relevant report about the use of carbon nitride modified carbon fiber is found at present, and the invention fills the gap in the technical field of research and development and application of carbon nitride modified carbon fiber.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an industrial method for continuously modifying the surface of carbon fiber, which improves the interfacial property of a carbon fiber composite material by generating a carbon nitride reinforcement in situ on the surface of the carbon fiber.
The technical scheme adopted by the invention for solving the technical problem is as follows: the invention provides an industrialized method for continuously modifying the surface of carbon fiber, which comprises the following steps:
(1) carbon fiber pretreatment
Dipping the carbon fiber precursor which is not coated with the sizing agent in an aqueous solution containing the component A, and then drying to obtain pretreated carbon fiber; the component A is composed of one or more of cyanamide, dicyandiamide, melamine, urea or thiourea;
(2) carbon nitride reinforcement generated on surface of carbon fiber in situ
Enabling the pretreated carbon fiber obtained in the step (1) to pass through a fluidized bed containing a component B, and generating a carbon nitride reinforcement in situ on the surface of the carbon fiber; the component B is composed of one or more of melamine, urea or thiourea.
Preferably, the mass concentration of the cyanamide in the step (1) is 0-775 g/L; the mass concentration of the dicyandiamide is 0-60 g/L; the mass concentration of melamine is 0-10 g/L; the mass concentration of the urea is 0-1100 g/L, and the mass concentration of the thiourea is 0-150 g/L.
Preferably, the aqueous solution in step (1) is a saturated aqueous solution of component a.
Preferably, the temperature of the aqueous solution in the step (1) is 20-50 ℃.
Preferably, the drying temperature in the step (1) is 300-1000 ℃.
Preferably, the time for soaking the aqueous solution in the step (1) is 10-90 s.
Preferably, the mass concentration of the melamine in the step (2) is 0-1 g/cm3(ii) a The mass concentration of the urea is 0-1.1 g/cm3(ii) a The mass concentration of the thiourea is 0-1.2 g/cm3。
Preferably, the temperature in the fluidized bed in the step (2) is 450-650 ℃.
Preferably, the residence time of the pretreated carbon fibers in the step (2) in the vulcanizing bed is 30-120 s.
Preferably, the carbon fiber precursor which is not coated with the sizing agent in the step (1) is dipped in an aqueous solution containing the component A for ultrasonic treatment, and then is dried to obtain the pretreated carbon fiber.
The invention has the beneficial effects that: the invention provides an industrial method for continuously modifying the surface of carbon fiber, which forms a carbon nitride reinforcement body on the surface of the carbon fiber in situ, realizes controllable structure, uniform distribution and controllable loading capacity, increases the surface area and the number of surface active groups of the carbon fiber, regulates and optimizes the specific surface area and the surface reaction activity of the carbon fiber, improves the wettability and the interface combination between the carbon fiber and epoxy resin, solves the technical problem of poor interface combination between the carbon fiber and an epoxy resin matrix in a carbon fiber reinforced epoxy resin composite material, improves the overall performance of the carbon fiber reinforced epoxy resin composite material, and fills the blank in the technical field of research, development and application of the carbon fiber technology modified by using the carbon nitride.
Drawings
FIG. 1 is a schematic structural diagram of in-situ generation of carbon nitride on the surface of a carbon fiber;
FIG. 2 is a reaction mechanism diagram of in-situ generation of carbon nitride on the surface of carbon fiber;
FIG. 3 is a schematic view of an industrial continuous process for in situ generation of carbon nitride on the surface of carbon fiber.
Description of reference numerals: 1. carbon fibers; 2. a carbon fiber pretreatment tank; 3. a tubular drying furnace; 4. a fluidized bed; 5. and a guide roller.
Detailed Description
The invention is further described below in conjunction with the drawings and the specific embodiments to assist in understanding the contents of the invention. The method used in the invention is a conventional method if no special provisions are made; the raw materials and the apparatus used are, unless otherwise specified, conventional commercially available products.
Example 1
The invention provides an industrialized method for continuously modifying the surface of carbon fiber, which comprises the following steps:
(1) carbon fiber pretreatment
Dipping the carbon fiber precursor which is not coated with the sizing agent in the aqueous solution containing the component A for ultrasonic treatment, and then drying to obtain the pretreated carbon fiber. Wherein the component A is cyanamide, and the mass concentration of the component A in the aqueous solution is 775 g/L; the temperature of the aqueous solution is 20 ℃; the drying temperature is 300 ℃, and the drying time is 65 s; the immersion time of the aqueous solution was 20 s.
(2) Carbon nitride reinforcement generated on surface of carbon fiber in situ
And (2) enabling the pretreated carbon fiber obtained in the step (1) to pass through a fluidized bed containing a component B, and generating a carbon nitride reinforcement in situ on the surface of the carbon fiber. Wherein the component B is melamine with the mass concentration of 1g/cm3(ii) a The temperature in the fluidized bed is 650 ℃; the residence time of the pretreated carbon fibers inside the fluidized bed was 30 s.
Through detection, the carbon nitride reinforcement generated in situ on the surface of the carbon fiber in the embodiment 1 has the interface shear strength of 71.2MPa, the interlayer shear strength of 84.9MPa and the interface shear strength improvement rate of 80.25 percent, and meets the use requirement of the product.
Example 2
The invention provides an industrialized method for continuously modifying the surface of carbon fiber, which comprises the following steps:
(1) carbon fiber pretreatment
Dipping the carbon fiber precursor which is not coated with the sizing agent in the aqueous solution containing the component A for ultrasonic treatment, and then drying to obtain the pretreated carbon fiber. Wherein the component A is dicyandiamide, and the mass concentration of the component A in an aqueous solution is 60 g/L; the temperature of the aqueous solution is 40 ℃; the drying temperature is 700 ℃, and the drying time is 30 s; the immersion time of the aqueous solution was 30 s.
(2) Carbon nitride reinforcement generated on surface of carbon fiber in situ
And (2) enabling the pretreated carbon fiber obtained in the step (1) to pass through a fluidized bed containing a component B, and generating a carbon nitride reinforcement in situ on the surface of the carbon fiber. Wherein the component B is urea with the mass concentration of 1.1g/cm3(ii) a The temperature in the fluidized bed is 475 ℃; the residence time of the pretreated carbon fibers in the fluidized bed is 110 s.
Through detection, the carbon nitride reinforcement generated in situ on the surface of the carbon fiber in the embodiment 2 has the interface shear strength of 78.7MPa, the interlayer shear strength of 87.5MPa and the interface shear strength improvement rate of 99.20%, and meets the use requirement of the product.
Example 3
The invention provides an industrialized method for continuously modifying the surface of carbon fiber, which comprises the following steps:
(1) carbon fiber pretreatment
Dipping the carbon fiber precursor which is not coated with the sizing agent in the aqueous solution containing the component A for ultrasonic treatment, and then drying to obtain the pretreated carbon fiber. Wherein the component A is melamine, and the mass concentration of the component A in an aqueous solution is 10 g/L; the temperature of the aqueous solution is 35 ℃; the drying temperature is 500 ℃, and the drying time is 40 s; the immersion time of the aqueous solution was 60 s.
(2) Carbon nitride reinforcement generated on surface of carbon fiber in situ
And (2) enabling the pretreated carbon fiber obtained in the step (1) to pass through a fluidized bed containing a component B, and generating a carbon nitride reinforcement in situ on the surface of the carbon fiber. Wherein the component B is thiourea, and the mass concentration of the component B is 1.2g/cm3(ii) a Temperature in the fluidized bedThe temperature is 550 ℃; the residence time of the pretreated carbon fiber inside the fluidized bed is 100 s.
Through detection, the carbon nitride reinforcement generated in situ on the surface of the carbon fiber in the embodiment 3 has the interface shear strength of 69.3MPa, the interlayer shear strength of 85.1MPa and the interface shear strength improvement rate of 75.44%, and meets the use requirement of the product.
Example 4
The invention provides an industrialized method for continuously modifying the surface of carbon fiber, which comprises the following steps:
(1) carbon fiber pretreatment
Dipping the carbon fiber precursor which is not coated with the sizing agent in the aqueous solution containing the component A for ultrasonic treatment, and then drying to obtain the pretreated carbon fiber. Wherein the component A is urea, and the mass concentration of the component A in an aqueous solution is 1100 g/L; the temperature of the aqueous solution is 25 ℃; the drying temperature is 1000 ℃, and the drying time is 10 s; the immersion time of the aqueous solution was 10 s.
(2) Carbon nitride reinforcement generated on surface of carbon fiber in situ
And (2) enabling the pretreated carbon fiber obtained in the step (1) to pass through a fluidized bed containing a component B, and generating a carbon nitride reinforcement in situ on the surface of the carbon fiber. Wherein the component B is melamine and urea, and the mass concentration of the melamine is 0.6g/cm3The mass concentration of the urea is 0.4g/cm3(ii) a The temperature in the fluidized bed is 450 ℃; the residence time of the pretreated carbon fibers inside the fluidized bed was 120 s.
Through detection, the carbon nitride reinforcement generated in situ on the surface of the carbon fiber in the embodiment 4 has the interface shear strength of 83.1MPa, the interlayer shear strength of 86.4MPa and the interface shear strength improvement rate of 110.27%, and meets the use requirement of the product.
Example 5
The invention provides an industrialized method for continuously modifying the surface of carbon fiber, which comprises the following steps:
(1) carbon fiber pretreatment
Dipping the carbon fiber precursor which is not coated with the sizing agent in the aqueous solution containing the component A for ultrasonic treatment, and then drying to obtain the pretreated carbon fiber. Wherein the component A is thiourea, and the mass concentration of the thiourea in the aqueous solution is 150 g/L; the temperature of the aqueous solution is 50 ℃; the drying temperature is 400 ℃, and the drying time is 50 s; the immersion time of the aqueous solution was 90 s.
(2) Carbon nitride reinforcement generated on surface of carbon fiber in situ
And (2) enabling the pretreated carbon fiber obtained in the step (1) to pass through a fluidized bed containing a component B, and generating a carbon nitride reinforcement in situ on the surface of the carbon fiber. Wherein the component B is melamine and thiourea, and the mass concentration of the melamine is 0.4g/cm3The mass concentration of thiourea is 0.8g/cm3(ii) a The temperature in the fluidized bed is 525 ℃; the residence time of the pretreated carbon fibers inside the fluidized bed was 90 s.
Through detection, the carbon nitride reinforcement generated in situ on the surface of the carbon fiber in the embodiment 5 has the interface shear strength of 77.5MPa, the interlayer shear strength of 87.1MPa and the interface shear strength improvement rate of 96.20 percent, and meets the use requirement of the product.
Example 6
The invention provides an industrialized method for continuously modifying the surface of carbon fiber, which comprises the following steps:
(1) carbon fiber pretreatment
Dipping the carbon fiber precursor which is not coated with the sizing agent in the aqueous solution containing the component A for ultrasonic treatment, and then drying to obtain the pretreated carbon fiber. Wherein the component A is cyanamide and dicyandiamide, the mass concentration of the cyanamide in the aqueous solution is 500g/L, and the mass concentration of the dicyandiamide in the aqueous solution is 60 g/L; the temperature of the aqueous solution is 30 ℃; the drying temperature is 350 ℃, and the drying time is 60 s; the immersion time of the aqueous solution was 80 s.
(2) Carbon nitride reinforcement generated on surface of carbon fiber in situ
And (2) enabling the pretreated carbon fiber obtained in the step (1) to pass through a fluidized bed containing a component B, and generating a carbon nitride reinforcement in situ on the surface of the carbon fiber. Wherein the component B comprises urea and thiourea, and the mass concentration of the urea is 0.9g/cm3The mass concentration of thiourea is 0.2g/cm3(ii) a The temperature in the fluidized bed is 480 ℃; the residence time of the pretreated carbon fibers inside the fluidized bed was 60 seconds.
Through detection, the carbon nitride reinforcement generated in situ on the surface of the carbon fiber in the embodiment 6 has the interface shear strength of 66.2MPa, the interlayer shear strength of 76.3MPa and the interface shear strength improvement rate of 67.59%, and meets the use requirement of the product.
Example 7
The invention provides an industrialized method for continuously modifying the surface of carbon fiber, which comprises the following steps:
(1) carbon fiber pretreatment
Dipping the carbon fiber precursor which is not coated with the sizing agent in the aqueous solution containing the component A for ultrasonic treatment, and then drying to obtain the pretreated carbon fiber. The component A comprises melamine and urea, the mass concentration of the melamine in the aqueous solution is 10g/L, and the mass concentration of the urea in the aqueous solution is 900 g/L; the temperature of the aqueous solution is 45 ℃; the drying temperature is 800 ℃, and the drying time is 35 s; the immersion time of the aqueous solution was 40 s.
(2) Carbon nitride reinforcement generated on surface of carbon fiber in situ
And (2) enabling the pretreated carbon fiber obtained in the step (1) to pass through a fluidized bed containing a component B, and generating a carbon nitride reinforcement in situ on the surface of the carbon fiber. Wherein the component B is melamine, urea and thiourea, and the mass concentration of the melamine is 0.2g/cm3The mass concentration of the urea is 0.6g/cm3The mass concentration of thiourea is 0.3g/cm3(ii) a The temperature in the fluidized bed is 500 ℃; the residence time of the pretreated carbon fibers in the fluidized bed was 80 seconds.
Through detection, the carbon nitride reinforcement generated in situ on the surface of the carbon fiber in the embodiment 7 has the interface shear strength of 64.3MPa, the interlayer shear strength of 77.5MPa and the interface shear strength improvement rate of 62.78%, and meets the use requirement of the product.
Example 8
The invention provides an industrialized method for continuously modifying the surface of carbon fiber, which comprises the following steps:
(1) carbon fiber pretreatment
Dipping the carbon fiber precursor which is not coated with the sizing agent in the aqueous solution containing the component A for ultrasonic treatment, and then drying to obtain the pretreated carbon fiber. The component A comprises cyanamide, dicyandiamide and thiourea, wherein the mass concentration of the cyanamide in an aqueous solution is 400g/L, the mass concentration of the dicyandiamide in the aqueous solution is 30g/L, and the mass concentration of the thiourea in the aqueous solution is 150 g/L; the temperature of the aqueous solution is 25 ℃; the drying temperature is 450 ℃, and the drying time is 50 s; the immersion time of the aqueous solution was 55 s.
(2) Carbon nitride reinforcement generated on surface of carbon fiber in situ
And (2) enabling the pretreated carbon fiber obtained in the step (1) to pass through a fluidized bed containing a component B, and generating a carbon nitride reinforcement in situ on the surface of the carbon fiber. Wherein the component B is urea, and the mass concentration of the urea is 1.0g/cm3(ii) a The temperature in the fluidized bed is 625 ℃; the residence time of the pretreated carbon fibers inside the fluidized bed was 50 s.
Through detection, the carbon nitride reinforcement generated in situ on the surface of the carbon fiber in the embodiment 8 has the interface shear strength of 76.8MPa, the interlayer shear strength of 88.2MPa and the interface shear strength improvement rate of 94.43%, and meets the use requirement of the product.
Example 9
The invention provides an industrialized method for continuously modifying the surface of carbon fiber, which comprises the following steps:
(1) carbon fiber pretreatment
Dipping the carbon fiber precursor which is not coated with the sizing agent in the aqueous solution containing the component A for ultrasonic treatment, and then drying to obtain the pretreated carbon fiber. The component A comprises cyanamide, dicyandiamide, melamine and urea, wherein the mass concentration of the cyanamide in an aqueous solution is 400g/L, the mass concentration of the dicyandiamide in the aqueous solution is 10g/L, the mass concentration of the melamine in the aqueous solution is 8g/L, and the mass concentration of the urea in the aqueous solution is 1000 g/L; the temperature of the aqueous solution is 35 ℃; the drying temperature is 600 ℃, and the drying time is 35 s; the immersion time of the aqueous solution was 50 s.
(2) Carbon nitride reinforcement generated on surface of carbon fiber in situ
And (2) enabling the pretreated carbon fiber obtained in the step (1) to pass through a fluidized bed containing a component B, and generating a carbon nitride reinforcement in situ on the surface of the carbon fiber. Wherein the component B is melamine and urea, and the mass concentration of the melamine is 0.4g/cm3The mass concentration of the urea is 0.7g/cm3(ii) a The temperature in the fluidized bed is 580 ℃; the residence time of the pretreated carbon fibers inside the fluidized bed was 70 s.
Through detection, the carbon nitride reinforcement generated in situ on the surface of the carbon fiber in the embodiment 9 has the interface shear strength of 86.2MPa, the interlayer shear strength of 102.9MPa and the interface shear strength improvement rate of 118.22%, and meets the use requirement of the product.
Example 10
The invention provides an industrialized method for continuously modifying the surface of carbon fiber, which comprises the following steps:
(1) carbon fiber pretreatment
Dipping the carbon fiber precursor which is not coated with the sizing agent in the aqueous solution containing the component A for ultrasonic treatment, and then drying to obtain the pretreated carbon fiber. The component A comprises cyanamide, dicyandiamide, melamine, urea and thiourea, wherein the mass concentration of the cyanamide in an aqueous solution is 200g/L, the mass concentration of the dicyandiamide in the aqueous solution is 20g/L, the mass concentration of the melamine in the aqueous solution is 6g/L, the mass concentration of the urea in the aqueous solution is 700g/L, and the mass concentration of the thiourea in the aqueous solution is 100 g/L; the temperature of the aqueous solution is 40 ℃; the drying temperature is 900 ℃, and the drying time is 15 s; the immersion time of the aqueous solution was 70 s.
(2) Carbon nitride reinforcement generated on surface of carbon fiber in situ
And (2) enabling the pretreated carbon fiber obtained in the step (1) to pass through a fluidized bed containing a component B, and generating a carbon nitride reinforcement in situ on the surface of the carbon fiber. Wherein the component B is melamine and thiourea, and the mass concentration of the melamine is 0.5g/cm3The mass concentration of thiourea is 0.7g/cm3(ii) a The temperature in the fluidized bed is 600 ℃; the residence time of the pretreated carbon fibers inside the fluidized bed was 40 s.
Through detection, the carbon nitride reinforcement generated in situ on the surface of the carbon fiber in the embodiment 10 has the interface shear strength of 79.7MPa, the interlayer shear strength of 94.6MPa and the interface shear strength improvement rate of 101.77%, and meets the use requirement of the product.
As shown in the figures 1 and 2, the invention provides an industrial method for continuously modifying the surface of carbon fiber, wherein a carbon nitride reinforcement is generated on the surface of the carbon fiber through in-situ polymerization, the specific surface area of the carbon fiber is increased, the surface reactivity of the carbon fiber is enhanced by amino functional groups on the surface of the carbon nitride, the wettability of the carbon fiber and resin is greatly improved, the mechanical locking between the carbon fiber and epoxy resin is increased, meanwhile, the amino groups can react with epoxy resin molecules to form a chemical bonding effect on an interface, the interface bonding strength of a composite material is greatly improved, and the interface performance of the composite material is improved. At present, no report related to the use of carbon nitride for modifying carbon fiber is found, and the invention discloses the first time and fills the blank of the technology. In the above embodiments 1 to 10 of the present invention, the interfacial shear strength of the in-situ generated carbon nitride reinforcement on the surface of the carbon fiber is 64.3 to 86.2MPa, the interlaminar shear strength is 76.3 to 102.9MPa, wherein the increase rate of the interfacial shear strength is 62.78 to 118.22%, and according to the related documents, the increase rate of the interfacial shear strength after the carbon fiber is modified by the nano material is generally 30 to 100%, thus the present invention adopts a new carbon fiber surface modification method, which greatly improves the interfacial bonding strength of the composite material, achieves a good effect of improving the interfacial properties of the composite material, and meets the use requirements of the product.
The invention provides an industrial method for continuously modifying the surface of carbon fiber, which is shown in the flow chart of the following steps from the embodiment 1 to the embodiment 10: the carbon fiber pretreatment tank 2 and the tubular drying furnace 3 are used for pretreating the carbon fibers 1, wherein an aqueous solution containing a component A is contained in the carbon fiber pretreatment tank 2, the component A is composed of one or more of cyanamide, dicyandiamide, melamine, urea or thiourea and is used for impregnating the carbon fibers 1 precursor which is not coated with a sizing agent, the aqueous solution is further subjected to ultrasonic treatment, the temperature of the aqueous solution is set to be 20-50 ℃, and the concentration of the aqueous solution of the component A is set to be a supersaturated solution to increase the concentration, so that the rapid impregnation of the carbon fibers 1 precursor is facilitated; the tubular drying furnace 3 is a drying device, the drying temperature is 300-1000 ℃, and the rapid drying after the impregnation of the carbon fiber 1 precursor is facilitated, so that the component A is firmly adsorbed on the surface of the carbon fiber 1. The fluidized bed 4 is used for in-situ generation of the carbon nitride reinforcement on the surface of the carbon fiber 1, and contains a component B, wherein the component B is composed of one or more of melamine, urea or thiourea, and the temperature in the fluidized bed 4 is set to be 450-650 ℃, which is favorable for in-situ generation of the carbon nitride reinforcement on the surface of the carbon fiber 1. And guide rollers 5 are arranged in the carbon fiber pretreatment tank 2, the tubular drying furnace 3 and the fluidized bed 4 and at the joint between the carbon fiber pretreatment tank and the tubular drying furnace for guiding and conveying the carbon fibers 1, so that continuous production is formed, and the working efficiency is improved. The dipping time of the carbon fiber in unit length in the carbon fiber pretreatment tank 2 is 10-90 s, the drying time of the tubular drying furnace 3 is 10-65 s, and the retention time of the pretreated carbon fiber 1 in the vulcanizing bed 4 is 30-120 s, so that the industrial production of the continuous modification of the surface of the carbon fiber 1 in unit length needs 50-275 s. The existing carbon fiber surface nanoparticle grafting modification method mostly adopts an intermittent treatment process, has complicated working procedures and low production efficiency, generally needs several hours or even more than ten hours, and seriously influences the industrial development process of the carbon fiber composite material.
However, the above embodiments are only examples of the present invention, and the scope of the present invention should not be limited by these examples, and all equivalent changes and modifications made in the claims of the present invention should be covered by the present invention.
Claims (5)
1. An industrial method for continuously modifying the surface of carbon fiber is characterized by comprising the following steps:
(1) carbon fiber pretreatment
Dipping the carbon fiber precursor which is not coated with the sizing agent in a saturated aqueous solution containing the component A, wherein the temperature of the saturated aqueous solution is 20-50 ℃; then drying to obtain pretreated carbon fibers; the component A is composed of one or more of cyanamide, dicyandiamide, melamine, urea or thiourea; in the step (1), the mass concentration of the cyanamide is 200-775 g/L, the mass concentration of the dicyandiamide is 10-60 g/L, the mass concentration of the melamine is 6-10 g/L, the mass concentration of the urea is 700-1100 g/L, and the mass concentration of the thiourea is 100-150 g/L;
(2) carbon nitride reinforcement generated on surface of carbon fiber in situ
Passing the pretreated carbon fiber obtained in the step (1) through a fluidized bed containing a component B, wherein the temperature in the fluidized bed is 450-650 ℃, and the carbon fiber surface is subjected to original treatmentGenerating a carbon nitride reinforcement; the component B consists of one or more of melamine, urea or thiourea; the mass concentration of the melamine in the step (2) is 0.2-1 g/cm3The mass concentration of the urea is 0.4-1.1 g/cm3The mass concentration of the thiourea is 0.2-1.2 g/cm3。
2. The industrial method for continuously modifying the surface of the carbon fiber according to claim 1, wherein the drying temperature in the step (1) is 300-1000 ℃.
3. The industrial method for continuously modifying the surface of the carbon fiber according to claim 2, wherein the soaking time of the aqueous solution in the step (1) is 10-90 s.
4. The industrial method for continuously modifying the surface of the carbon fiber according to claim 3, wherein the residence time of the pretreated carbon fiber in the step (2) inside the vulcanization bed is 30-120 s.
5. The industrial method for continuously modifying the surface of carbon fiber according to claim 1, wherein the carbon fiber precursor which is not coated with the sizing agent in the step (1) is dipped in the aqueous solution containing the component A for ultrasonic treatment and then dried to obtain the pretreated carbon fiber.
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| CN109809106A (en) * | 2018-11-28 | 2019-05-28 | 青岛环球输送带有限公司 | A kind of dedicated heat resistance conveyor belt of large junk and its preparation process |
| CN112979334B (en) * | 2021-02-25 | 2022-12-02 | 攀枝花容则钒钛有限公司 | Preparation method of carbon fiber reinforced pantograph carbon slide plate based on 3D printing |
| CN113308879B (en) * | 2021-05-26 | 2023-06-09 | 河南工业大学 | By g-C 3 N 4 Preparation method of modified carbon fiber immobilized carrier |
| CN115430396A (en) * | 2021-06-01 | 2022-12-06 | 中国石油天然气集团有限公司 | Modified activated carbon fiber loaded TiO 2 Composite material and preparation method and application thereof |
| CN113386349B (en) * | 2021-06-16 | 2022-07-12 | 西南交通大学 | 3D printing method of carbon fiber reinforced resin-based plate |
| CN114645376B (en) * | 2022-05-13 | 2022-08-23 | 浙江星辉新材料科技有限公司 | Preparation method of low-density carbon fiber hard heat preservation felt |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015100298A1 (en) * | 2013-12-24 | 2015-07-02 | Baker Hughes Incorporated | Swellable downhole structures including carbon nitride materials, and methods of forming and using such structures |
| CN104911900A (en) * | 2015-06-24 | 2015-09-16 | 哈尔滨工业大学 | Method for preparing CNT (carbon nano tube)/CF (carbon fiber) multi-scale reinforcement in large scale |
| CN105032469A (en) * | 2015-08-11 | 2015-11-11 | 中国人民解放军国防科学技术大学 | Biomass base nitrogen-doped graphene/carbon fiber electrocatalyst and preparation method thereof |
| CN106542509A (en) * | 2016-10-19 | 2017-03-29 | 张家港市东大工业技术研究院 | A kind of efficient method for preparing class Graphene carbonitride |
| CN107758635A (en) * | 2017-10-31 | 2018-03-06 | 张家港市东大工业技术研究院 | The control synthetic method of one species graphene carbonitride ultrathin nanometer piece |
-
2018
- 2018-05-15 CN CN201810460689.4A patent/CN108589267B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015100298A1 (en) * | 2013-12-24 | 2015-07-02 | Baker Hughes Incorporated | Swellable downhole structures including carbon nitride materials, and methods of forming and using such structures |
| CN104911900A (en) * | 2015-06-24 | 2015-09-16 | 哈尔滨工业大学 | Method for preparing CNT (carbon nano tube)/CF (carbon fiber) multi-scale reinforcement in large scale |
| CN105032469A (en) * | 2015-08-11 | 2015-11-11 | 中国人民解放军国防科学技术大学 | Biomass base nitrogen-doped graphene/carbon fiber electrocatalyst and preparation method thereof |
| CN106542509A (en) * | 2016-10-19 | 2017-03-29 | 张家港市东大工业技术研究院 | A kind of efficient method for preparing class Graphene carbonitride |
| CN107758635A (en) * | 2017-10-31 | 2018-03-06 | 张家港市东大工业技术研究院 | The control synthetic method of one species graphene carbonitride ultrathin nanometer piece |
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