CN110819107A - Method for preparing bismaleimide resin matrix composite material by chemical vapor deposition method and application - Google Patents

Method for preparing bismaleimide resin matrix composite material by chemical vapor deposition method and application Download PDF

Info

Publication number
CN110819107A
CN110819107A CN201910949212.7A CN201910949212A CN110819107A CN 110819107 A CN110819107 A CN 110819107A CN 201910949212 A CN201910949212 A CN 201910949212A CN 110819107 A CN110819107 A CN 110819107A
Authority
CN
China
Prior art keywords
composite material
cnt
carbon fiber
pei
preparing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910949212.7A
Other languages
Chinese (zh)
Other versions
CN110819107B (en
Inventor
邱军
施煜楠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tongji University
Original Assignee
Tongji University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tongji University filed Critical Tongji University
Priority to CN201910949212.7A priority Critical patent/CN110819107B/en
Publication of CN110819107A publication Critical patent/CN110819107A/en
Application granted granted Critical
Publication of CN110819107B publication Critical patent/CN110819107B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention relates to a method for preparing a bismaleimide resin matrix composite material of a carbon fiber-carbon nano tube reinforcing phase by adopting a chemical vapor deposition method, which is characterized in that NiNO with Ni ions is loaded on the surface of carbon fibers in advance by utilizing the chemical vapor deposition method3The particles are reduced at high temperature to obtain nano Ni particles with pure surfacesEthanol is used as a carbon source, catalytic cracking is carried out on the surface of catalyst particles, and carbon nano tubes grow through the deposition of carbon atoms. And then compounding the prepared carbon fiber-carbon nanotube micro-nano reinforcing phase with BMI-PEI-CNT matrix resin to prepare the bismaleimide resin matrix composite material with high strength and high modulus. Compared with the prior art, the method can conveniently control the length, the diameter, the distribution and the density of the carbon nano tube on the surface of the carbon fiber, thereby realizing the synergistic effect of the carbon fiber and the carbon nano tube, changing the extension paths of horizontal stress and vertical stress at an interface, dispersing stress concentration and improving the mechanical property of the composite material.

Description

Method for preparing bismaleimide resin matrix composite material by chemical vapor deposition method and application
Technical Field
The invention relates to a preparation method of a bismaleimide resin matrix composite material, in particular to a method for preparing the bismaleimide resin matrix composite material by a chemical vapor deposition method and application thereof.
Background
Carbon fiber/Bismaleimide (BMI) resin composites have also been widely used in primary and secondary aircraft payload applications. However, because the BMI molecular chain structure has a rigid group aromatic ring and an imide ring, the matrix material has the disadvantages of high brittleness and easy fracture, and the matrix BMI material needs to be modified by toughening, reinforcing and the like. The interfacial properties of carbon fiber/BMI composites also tend to limit their application in specific structural components.
How to increase the strength and toughness of carbon fiber/BMI composite materials by a modification technology under the condition of not changing the basic molding process of the composite materials is a key technology which needs to be solved urgently and has important scientific and engineering values.
CN102634208B discloses a nano composite modification method for bismaleimide resin matrix composite, which comprises the steps of firstly adding N- (4-aminophenyl) maleimide modified layered silicate clay mineral into liquid O, O' -Diallyl Bisphenol A (DBA), carrying out intercalation pretreatment under the combined action of mechanical stirring and ultrasonic dispersion, then adding Bismaleimide Diphenylmethane (BDM) resin for prepolymerization, cooling and adding acetone to prepare a resin solution with a certain concentration. And then fully soaking the continuous fiber or the fabric thereof in the resin solution, heating to obtain a prepreg, and finally preparing the hybrid multi-scale composite material according to a certain molding process. According to the technical scheme, the prepreg is obtained only by adding DBA and then carrying out prepolymerization, the obtained bismaleimide resin matrix composite material still belongs to a conventional performance material, and the mechanical property of the bismaleimide resin matrix composite material still cannot meet the requirements of the current engineering material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for preparing a bismaleimide resin matrix composite material by adopting a carbon fiber-carbon nanotube micro-nano synergistic enhanced phase chemical vapor deposition method.
The purpose of the invention can be realized by the following technical scheme:
the method for preparing the bismaleimide resin matrix composite material by the chemical vapor deposition method comprises the following steps:
carbon fiber surface treatment: placing the carbon fibers in excessive acetone, heating and refluxing for a period of time at constant temperature, repeatedly washing with acetone, and drying; and (3) placing the carbon fiber in excessive concentrated nitric acid, reacting at constant temperature for a period of time, repeatedly washing with deionized water, and drying.
Loading metal ions: placing the carbon fiber subjected to surface treatment in NiNO3Soaking in water solution, taking out the carbon fiber, placing in an oven, drying the surface moisture of the carbon fiber, and separating out and crystallizing nickel nitrate particles on the surface of the carbon fiber.
Growing the carbon nano tube: placing the carbon fiber treated in the two steps at the center of a tubular quartz tube, introducing nitrogen into the tubular furnace in advance before heating, and introducing N into the tubular furnace when the temperature is raised to a certain temperature2And H2When the temperature in the tube furnace is raised to the reaction temperature, ethanol vapor is introduced into the tube furnace to prepare the CF-v-CNT.
Preparation of CNT-PEI enhanced bismaleimide matrix phase: dispersing CNT-PEI in ethanol, performing ultrasonic treatment and stirring to obtain a stable suspension. And (3) dropwise adding BA (o, o' -diallyl bisphenol A) into the suspension according to the mass ratio, wherein the process is carried out under the conditions of ultrasound and stirring. And stirring the mixed system at a constant temperature until the ethanol in the system is completely dried to obtain CNT-PEI/BA glue solution with good dispersion of the CNT-PEI. And then adding BMI (N, N '-4, 4' -diphenylmethane bismaleimide) with corresponding mass into the CNT-PEI/BA glue solution, and stirring and reacting under a constant temperature condition to obtain a prepolymer of the BMI and BA.
Preparation of prepreg: placing the prepared CF-v-CNT in an oven for drying, uniformly coating the prepared prepolymer glue solution on the surface of the carbon fiber, drying a solvent in the glue solution in the oven, cooling and airing, and controlling the glue content in the prepreg in the process.
Compression molding of the composite material: cutting the prepreg into the shape of a mold cavity, flatly laying the prepreg in a mold, putting the mold into a vacuum forming machine, repeatedly boosting the pressure and releasing the pressure to remove bubbles in the middle of a laying layer, and curing the material according to a mold pressing process. And after solidification, randomly cooling to room temperature, demolding to obtain a composite material plate, and cutting the composite material plate into a sample with a required size according to experimental requirements.
Further, in the step of carbon fiber surface treatment, the carbon fibers are placed in excess acetone, the temperature of heating reflux is controlled to be 40-80 ℃, the time is controlled to be 12-48 hours, and then acetone is repeatedly used for washing so as to remove the epoxy glue layer on the surfaces of the carbon fibers.
Further, in the step of treating the surface of the carbon fiber, the reaction temperature of the carbon fiber in the excessive concentrated nitric acid is controlled to be 40-80 ℃, the reaction time is controlled to be 0.5-4 h, and the wettability of the surface of the carbon fiber can be improved through the treatment of the concentrated nitric acid, so that the wetting of a catalyst particle solution and the uniform distribution of catalyst particles are facilitated.
Further, in the step of loading metal ions, the carbon fibers are placed in NiNO3When soaked in aqueous solution, NiNO3The concentration of the aqueous solution is controlled to be 0.05-0.5 mol/L, and the soaking time is controlled to be 0.5-2 h.
Further, in the step of growing the carbon nano tube, N is introduced into the tube furnace before the temperature is raised2For exhausting air in the tube furnace to prevent oxygen in the air from influencing the activity of the catalyst in the subsequent reaction, introducing N2The time of (2) is controlled within 10-40 min. When the temperature is raised to 350-450 ℃, introducing N into the tube furnace2And H2Mixed gas of (2), H in the course of the reaction2To reduce the gas, N2Gas as carrier gas and shielding gas, N2And H2The volume ratio of the nickel nitrate is controlled to be 2: 1-4: 1, and the nickel nitrate is firstly decomposed into Ni at high temperature2O and NO2Then Ni2O is reduced by hydrogen to a Ni simple substance having a nano size with high activity.
Further, in the step of growing the carbon nano tube, when N is introduced2And H2After the temperature of the mixed gas is continuously increased to 650-750 ℃, ethanol steam is introduced into the tubular furnace, wherein ethanol is used as a carbon source, and the ethanol gas in a boiling state passes through N2The carbon nano-tube is taken into a tube furnace, the ethanol steam can be cracked and deposited, and the carbon nano-tube can grow in the process, so that the CF-v-CNT is prepared.
Further, in the step of preparing the CNT-PEI enhanced bismaleimide matrix phase, the mass fraction of the CNT-PEI dispersed in ethanol is controlled to be 0.5-5.0 wt%, the ultrasonic power is 50-100 KHz, the time is controlled to be 10-60 min, the ultrasonic dispersion is to mix liquid materials from a microscopic (molecular level) angle, component liquid drops can be more effectively dispersed and refined in the ultrasonic functional stage, and the CNT-PEI can be more finely and sufficiently dispersed in deionized water, so that the CNT-PEI can be more sufficiently dispersed in a resin matrix in a subsequent prepolymerization stage. When the prepolymer of BMI and BA is prepared, the mass ratio of BMI to BA is controlled to be 1: 0.5-1: 1.
Further, in the step of preparing the prepreg, the temperature of the functional carbon fiber cloth CF-v-CNT which is placed in an oven for drying is controlled to be 40-90 ℃. After the prepolymer glue solution is uniformly coated on the surface of the carbon fiber, the temperature of a solvent in the glue solution is controlled to be 80-180 ℃ in an oven, and the glue content in the prepreg is controlled to be 25-60 wt%.
Further, cutting the prepreg into the shape of a mold cavity in composite material compression molding, flatly laying the prepreg in a mold, putting the mold into a vacuum forming machine at 100-160 ℃, repeatedly boosting the pressure and releasing the pressure in a small range to remove bubbles in the middle of laying, curing the material according to a molding process of 150 ℃/2h + l60 ℃/2h + l80 ℃/2h +210 ℃/2h, randomly cooling to room temperature after curing, demolding to obtain a composite material plate, and cutting the composite material plate into a sample with a required size according to experimental requirements.
Further, the three-phase bismaleimide resin matrix composite material prepared by the invention is in a block shape.
The bismaleimide resin matrix composite material prepared by the invention obviously improves the relevant mechanical properties (impact property, bending resistance and interface shearing property) of the composite material due to the functionalized compounding of the carbon nanotube-carbon fiber. As the carbon nano tube improves the mechanical locking of the composite material interface, a large number of amino groups in the PEI functionalized layer can react with the BMI matrix to form a chemically crosslinked composite material interface, thereby optimizing the combination between the reinforced phase and the matrix resin. According to the invention, the carbon nano tube is grown on the surface of the carbon fiber by depositing carbon atoms by adopting a chemical vapor deposition method, and then the prepared carbon fiber-carbon nano tube micro-nano reinforcing phase is compounded with BMI-PEI-CNT matrix resin to prepare the bismaleimide resin matrix composite material with high strength and high modulus, so that the bismaleimide resin matrix composite material has important significance for the application in the field of large aircraft engineering manufacturing.
Compared with the bismaleimide composite material synthesized by the existing method, the three-phase bismaleimide resin-based composite material prepared by the invention not only solves the problem of weak interface bonding strength of the carbon nanotube and the matrix resin, but also further improves the impact property, the bending resistance, the interface shearing property and the like of the composite material, so that the composite material has excellent mechanical properties.
Compared with the prior art, the invention has the following advantages:
1) the method takes the carbon fiber as a substrate, the carbon fiber is subjected to surface treatment to ensure that the carbon fiber has good wettability, then catalyst particles are loaded on the surface of the carbon fiber by an impregnation method, and finally carbon nanotubes are directly grown on the surface of the carbon fiber in a catalytic manner to construct the CF-v-CNT composite fiber. The reinforcing phase prepared by the method can make the carbon nano tube grow on the surface of the carbon fiber in a three-dimensional form, thereby fully playing the role of the carbon nano tube in reinforcing the interface performance of the composite material.
2) The method successfully grows the carbon nano tube on the surface of the carbon fiber by adopting a vapor deposition method to form a CF-v-CNT micro-nano composite reinforcing phase, and then compounds the prepared carbon fiber-carbon nano tube micro-nano reinforcing phase with BMI-PEI-CNT matrix resin to modify bismaleimide matrix resin. Considering the influence of enhancing the mechanical property of the relative composite material, the interface shear strength, the impact strength, the bending modulus and the bending strength of the CF-v-CNT/BMI-PEI-CNT composite material are respectively improved by 62.2 percent, 14.5 percent, 7.0 percent and 12.7 percent compared with the CF/BMI-PEI-CNT, the CNT in the CF-v-CNT can effectively improve the mechanical locking function of the interface of the composite material, and the crack needs to overcome the obstruction of the CNT when expanding at the interface of the composite material, so the mechanical property of the composite material can be effectively improved.
3) The high-strength high-modulus bismaleimide resin-based composite material prepared by the material compounding method can be widely applied to engineering materials, such as engineering manufacturing fields of large airplanes and the like.
Drawings
FIG. 1 is a graph of the mechanical properties and rate of change of CF, CF-COOH and CF-v-CNT reinforced BMI and BMI-PEI-CNT composites.
In the figure: (a) interface shear performance test results; (b) the impact strength test results; (c) the flexural modulus test results; (d) and (5) testing the bending strength.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1:
the embodiment is a method for preparing a bismaleimide resin matrix composite material by adopting a carbon fiber-carbon nanotube micro-nano synergistic enhanced phase chemical vapor deposition method, and the method comprises the following steps:
(1) carbon fiber surface treatment: placing the carbon fiber in excessive acetone, heating and refluxing for 24h at 60 ℃, repeatedly washing with acetone, and drying. And (3) placing the carbon fiber in excessive concentrated nitric acid, reacting for 2h at a constant temperature of 60 ℃, repeatedly washing with deionized water and drying.
(2) Loading metal ions: placing the carbon fiber subjected to surface treatment in 0.1mol/L NiNO3Soaking in the water solution for 1h, taking out the carbon fiber, placing in an oven, drying the surface moisture of the carbon fiber, and separating out and crystallizing nickel nitrate particles on the surface of the carbon fiber.
(3) Growing the carbon nano tube: placing the carbon fiber treated in the above two steps at the center of a tubular quartz tube, and introducing N into the tubular furnace for 30min before heating2When the temperature is raised to 400 ℃, N is introduced into the tube furnace2And H2Mixed gas (N) of (2)2And H2Is controlled to be 3:1), when the temperature in the tube furnace rises to 700 ℃, ethanol steam is introduced into the tube furnace, and CF-v-CNT is prepared.
(4) Preparation of CNT-PEI enhanced bismaleimide matrix phase: 2.5 wt% CNT-PEI was dispersed in ethanol, sonicated at 80KHz and stirred for 40min to obtain a stable suspension. And (3) dropwise adding BA into the suspension according to the mass ratio, wherein the process is carried out under the conditions of ultrasound and stirring. And stirring the mixed system at a constant temperature until the ethanol in the system is completely dried to obtain CNT-PEI/BA glue solution with good dispersion of the CNT-PEI. And then adding BMI with corresponding mass into the CNT-PEI/BA glue solution, stirring and reacting for 30min at 140 ℃ to obtain a prepolymer of BMI and BA, wherein the mass ratio of BMI to BA when preparing the prepolymer of BMI and BA is controlled at 1: 0.87.
(5) Preparation of prepreg: placing the prepared CF-v-CNT in an oven at 80 ℃ for drying, uniformly coating the prepared prepolymer glue solution on the surface of the carbon fiber, drying a solvent in the glue solution in the oven at 140 ℃, cooling and airing, and controlling the glue content in the prepreg to be 45 wt%.
(6) Compression molding of the composite material: cutting the prepreg into a shape of a mold cavity, flatly laying the prepreg in a mold, putting the mold into a 140 ℃ vacuum forming machine, repeatedly boosting the pressure and releasing the pressure in a small range to remove bubbles in the middle of the laying layer, and curing the material by a mold pressing process of 150 ℃/2h + l60 ℃/2h + l80 ℃/2h +210 ℃/2 h. And after solidification, randomly cooling to room temperature, demolding to obtain a composite material plate, and cutting the composite material plate into a sample with a required size according to experimental requirements.
According to the invention, according to the modification technology of the carbon nano tube, the carbon nano tube is successfully grown on the surface of the carbon fiber by adopting a vapor deposition method to form a CF-v-CNT micro-nano composite reinforcing phase, and then the prepared carbon fiber-carbon nano tube micro-nano reinforcing phase is compounded with BMI-PEI-CNT matrix resin to modify and enhance the mechanical property of the bismaleimide matrix resin.
According to the invention, the carbon nano tube is successfully grown on the surface of the carbon fiber by using a vapor deposition method, a CF-v-CNT micro-nano enhanced phase is constructed, and the interface shear strength of the CF-v-CNT/BMI-PEI-CNT composite material is improved by 62.2% compared with that of the CF/BMI-PEI-CNT.
The high-strength high-modulus bismaleimide-based resin composite material prepared by the invention can be applied to the field of large-scale airplane manufacturing.
Example 2:
the embodiment is a method for preparing a bismaleimide resin matrix composite material by adopting a carbon fiber-carbon nanotube micro-nano synergistic enhanced phase chemical vapor deposition method, and the method comprises the following steps:
(1) carbon fiber surface treatment: placing the carbon fiber in excessive acetone, heating and refluxing for 24h at 60 ℃, repeatedly washing with acetone, and drying. And (3) placing the carbon fiber in excessive concentrated nitric acid, reacting for 2h at a constant temperature of 60 ℃, repeatedly washing with deionized water and drying.
(2) Loading metal ions: placing the carbon fiber subjected to surface treatment in 0.15mol/L NiNO3Soaking in the water solution for 1h, taking out the carbon fiber, placing in an oven, drying the surface moisture of the carbon fiber, and separating out and crystallizing nickel nitrate particles on the surface of the carbon fiber.
(3) Growing the carbon nano tube: placing the carbon fiber treated in the above two steps at the center of a tubular quartz tube, and introducing N into the tubular furnace for 30min before heating2When the temperature is raised to 380 ℃, N is introduced into the tube furnace2And H2Mixed gas (N) of (2)2And H2Is controlled to be 3:1), when the temperature in the tube furnace rises to 710 ℃, ethanol steam is introduced into the tube furnace, and CF-v-CNT is prepared.
(4) Preparation of CNT-PEI enhanced bismaleimide matrix phase: 2.5 wt% CNT-PEI was dispersed in ethanol, sonicated at 80KHz and stirred for 40min to obtain a stable suspension. And (3) dropwise adding BA into the suspension according to the mass ratio, wherein the process is carried out under the conditions of ultrasound and stirring. And stirring the mixed system at a constant temperature until the ethanol in the system is completely dried to obtain CNT-PEI/BA glue solution with good dispersion of the CNT-PEI. And then adding BMI with corresponding mass into the CNT-PEI/BA glue solution, stirring and reacting for 30min at 140 ℃ to obtain a prepolymer of BMI and BA, wherein the mass ratio of BMI to BA when preparing the prepolymer of BMI and BA is controlled at 1: 0.87.
(5) Preparation of prepreg: placing the prepared CF-v-CNT in an oven at 80 ℃ for drying, uniformly coating the prepared prepolymer glue solution on the surface of the carbon fiber, drying the solvent in the glue solution in the oven at 140 ℃, cooling and airing, and controlling the glue content in the prepreg to be 40 wt%.
(6) Compression molding of the composite material: cutting the prepreg into a shape of a mold cavity, flatly laying the prepreg in a mold, putting the mold into a 140 ℃ vacuum forming machine, repeatedly boosting the pressure and releasing the pressure in a small range to remove bubbles in the middle of the laying layer, and curing the material by a mold pressing process of 150 ℃/2h + l60 ℃/2h + l80 ℃/2h +210 ℃/2 h. And after solidification, randomly cooling to room temperature, demolding to obtain a composite material plate, and cutting the composite material plate into a sample with a required size according to experimental requirements.
According to the invention, according to the modification technology of the carbon nano tube, the carbon nano tube is successfully grown on the surface of the carbon fiber by adopting a vapor deposition method to form a CF-v-CNT micro-nano composite reinforcing phase, and then the prepared carbon fiber-carbon nano tube micro-nano reinforcing phase is compounded with BMI-PEI-CNT matrix resin to modify and enhance the mechanical property of the bismaleimide matrix resin.
The impact strength of the CF-v-CNT/BMI-PEI-CNT composite material is improved by 14.5 percent compared with that of the CF/BMI-PEI-CNT, and the high-strength high-modulus bismaleimide resin composite material prepared by the invention can be applied to the field of large-scale airplane manufacturing.
Example 3:
the embodiment is a method for preparing a bismaleimide resin matrix composite material by adopting a carbon fiber-carbon nanotube micro-nano synergistic enhanced phase chemical vapor deposition method, and the method comprises the following steps:
(1) carbon fiber surface treatment: placing the carbon fiber in excessive acetone, heating and refluxing for 24h at 65 ℃, repeatedly washing with acetone and drying. And (3) placing the carbon fiber in excessive concentrated nitric acid, reacting for 2h at a constant temperature of 65 ℃, repeatedly washing with deionized water and drying.
(2) Loading metal ions: placing the carbon fiber subjected to surface treatment in 0.1mol/L NiNO3Soaking in the water solution for 1.5h, taking out the carbon fiber, placing in an oven, drying the surface moisture of the carbon fiber, and separating out and crystallizing nickel nitrate particles on the surface of the carbon fiber.
(3) Growing the carbon nano tube: placing the carbon fiber treated in the above two steps at the center of a tubular quartz tube, and introducing 40min N into the tubular furnace before heating2When the temperature is raised to 400 ℃, N is introduced into the tube furnace2And H2Mixed gas (N) of (2)2And H2Is controlled to be 3:1), when the temperature in the tube furnace rises to 700 ℃, ethanol steam is introduced into the tube furnace, and CF-v-CNT is prepared.
(4) Preparation of CNT-PEI enhanced bismaleimide matrix phase: 2.5 wt% CNT-PEI was dispersed in ethanol, sonicated at 80KHz and stirred for 50min to obtain a stable suspension. And (3) dropwise adding BA into the suspension according to the mass ratio, wherein the process is carried out under the conditions of ultrasound and stirring. And stirring the mixed system at a constant temperature until the ethanol in the system is completely dried to obtain CNT-PEI/BA glue solution with good dispersion of the CNT-PEI. And then adding BMI with corresponding mass into the CNT-PEI/BA glue solution, stirring and reacting for 30min at 140 ℃ to obtain a prepolymer of BMI and BA, wherein the mass ratio of BMI to BA when preparing the prepolymer of BMI and BA is controlled at 1: 0.87.
(5) Preparation of prepreg: placing the prepared CF-v-CNT in an oven at 80 ℃ for drying, uniformly coating the prepared prepolymer glue solution on the surface of the carbon fiber, drying a solvent in the glue solution in the oven at 140 ℃, cooling and airing, wherein the glue content in the prepreg is controlled at 50 wt%.
(6) Compression molding of the composite material: cutting the prepreg into a shape of a mold cavity, flatly laying the prepreg in a mold, putting the mold into a 140 ℃ vacuum forming machine, repeatedly boosting the pressure and releasing the pressure in a small range to remove bubbles in the middle of the laying layer, and curing the material by a mold pressing process of 150 ℃/2h + l60 ℃/2h + l80 ℃/2h +210 ℃/2 h. And after solidification, randomly cooling to room temperature, demolding to obtain a composite material plate, and cutting the composite material plate into a sample with a required size according to experimental requirements.
According to the invention, according to the modification technology of the carbon nano tube, the carbon nano tube is successfully grown on the surface of the carbon fiber by adopting a vapor deposition method to form a CF-v-CNT micro-nano composite reinforcing phase, and then the prepared carbon fiber-carbon nano tube micro-nano reinforcing phase is compounded with BMI-PEI-CNT matrix resin to modify and enhance the mechanical property of the bismaleimide matrix resin.
The flexural modulus and flexural strength of the CF-v-CNT/BMI-PEI-CNT composite material are respectively improved by 7.0 percent and 12.7 percent compared with the CF/BMI-PEI-CNT, and the high-strength high-modulus bismaleimide resin composite material prepared by the invention can be applied to the field of large-scale airplane manufacturing.
Example 4:
the embodiment is a method for preparing a polyaniline nano-ring wire with wave absorption performance, and is different from embodiment 3 in that: in the step (2), the carbon fiber subjected to surface treatment is placed in 0.25mol/L NiNO3Soaking in the aqueous solution for 0.5h, and the other steps are the same as example 1. The final result showed 0.25mol/L NiNO3The aqueous solution had a poorer flexural strength than in example 1.
Example 5:
the embodiment is a method for preparing a polyaniline nano-ring wire with wave absorption performance, and is different from embodiment 2 in that: in the step (4), the mass fraction of the CNT-PEI dispersed in the ethanol is 2.6 wt%, the ultrasonic power is 80KHz, the time is controlled to be 45min, and other steps are the same. The final results show that an interfacial shear strength performance corresponding to a concentration of 2.6 wt% is inferior to that of example 1.
Example 6
The following experiments were used to verify the effect of the present invention:
experiment one:
firstly, carbon fiber surface treatment: placing the carbon fiber in excessive acetone, heating and refluxing for 24h at 60 ℃, repeatedly washing with acetone, and drying. And (3) placing the carbon fiber in excessive concentrated nitric acid, reacting for 2h at a constant temperature of 60 ℃, repeatedly washing with deionized water and drying.
Secondly, loading metal ions: placing the carbon fiber subjected to surface treatment in 0.1mol/L NiNO3Soaking in the water solution for 1h, taking out the carbon fiber, placing in an oven, drying the surface moisture of the carbon fiber, and separating out and crystallizing nickel nitrate particles on the surface of the carbon fiber.
Thirdly, growing the carbon nano tube: placing the carbon fiber treated in the above two steps at the center of a tubular quartz tube, and introducing N into the tubular furnace for 30min before heating2When the temperature is raised to 400 ℃, N is introduced into the tube furnace2And H2Mixed gas (N) of (2)2And H2Is controlled to be 3:1), when the temperature in the tube furnace rises to 700 ℃, ethanol steam is introduced into the tube furnace, and CF-v-CNT is prepared.
Fourthly, preparing a CNT-PEI enhanced bismaleimide matrix phase: 2.5 wt% CNT-PEI was dispersed in ethanol, sonicated at 80KHz and stirred for 40min to obtain a stable suspension. And (3) dropwise adding BA into the suspension according to the mass ratio, wherein the process is carried out under the conditions of ultrasound and stirring. And stirring the mixed system at a constant temperature until the ethanol in the system is completely dried to obtain CNT-PEI/BA glue solution with good dispersion of the CNT-PEI. And then adding BMI with corresponding mass into the CNT-PEI/BA glue solution, stirring and reacting for 30min at 140 ℃ to obtain a prepolymer of BMI and BA, wherein the mass ratio of BMI to BA when preparing the prepolymer of BMI and BA is controlled at 1: 0.87.
Fifthly, preparing the prepreg: placing the prepared CF-v-CNT in an oven at 80 ℃ for drying, uniformly coating the prepared prepolymer glue solution on the surface of the carbon fiber, drying a solvent in the glue solution in the oven at 140 ℃, cooling and airing, and controlling the glue content in the prepreg to be 45 wt%.
Sixthly, compression molding of the composite material: cutting the prepreg into a shape of a mold cavity, flatly laying the prepreg in a mold, putting the mold into a 140 ℃ vacuum forming machine, repeatedly boosting the pressure and releasing the pressure in a small range to remove bubbles in the middle of the laying layer, and curing the material by a mold pressing process of 150 ℃/2h + l60 ℃/2h + l80 ℃/2h +210 ℃/2 h. And after solidification, randomly cooling to room temperature, demolding to obtain a composite material plate, and cutting the composite material plate into a sample with a required size according to experimental requirements.
The bismaleimide resin matrix composite material prepared by the chemical vapor deposition method adopting the carbon fiber-carbon nanotube micro-nano synergistic enhanced phase is prepared by the experiment, and the influence of the mechanical properties of the CF, CF-COOH and CF-v-CNT enhanced BMI and BMI-PEI-CNT composite material is respectively measured.
The tensile property and the bending property of the composite material are measured by adopting a DXLL-5000 type microcomputer control universal tester. The Charpy XCJ-50 type simply supported beam impact tester is used for testing the impact property of the composite material, and the three-phase bismaleimide resin matrix composite material prepared by the test has higher strength and modulus. As shown in FIG. 1, the interfacial shear strength of the CF-v-CNT/BMI composite material is improved by 56.4% compared with that of the CF/BMI composite material, and the interfacial shear strength of the CF-v-CNT/BMI-PEI-CNT composite material is improved by 62.2% compared with that of the CF/BMI-PEI-CNT composite material. The CF-v-CNT prepared by the chemical vapor deposition method can effectively improve the interfacial shear property of the composite material. The interface shearing performance of the CF-v-CNT/BMI-PEI-CNT composite material is improved by 65.1 percent compared with the CF/BMI composite material by combining the influence of a matrix phase and a reinforcing phase. When the matrix materials of the composite material are the same, the change rule of the impact strength of the fiber reinforced BMI composite material is consistent with that of the fiber reinforced BMI-PEI-CNT composite material, and the impact strength of the composite material is reduced due to acidification treatment of the carbon fibers and is increased along with growth of the CNT. The impact strength of the CF-v-CNT/BMI composite material is improved by 10.8 percent relative to the CF/BMI. The impact strength of the CF-v-CNT/BMI-PEI-CNT composite material is improved by 14.5 percent relative to the CF/BMI-PEI-CNT composite material. The impact strength of the CF-v-CNT/BMI-PEI-CNT composite is improved by 20.0 percent relative to the CF/BMI composite by combining the effects of the matrix phase and the reinforcing phase. The flexural modulus of the CF-v-CNT/BMI-PEI-CNT composite material is improved by 7.0 percent compared with that of the CF/BMI-PEI-CNT composite material. The carbon nanotube grown by the carbon fiber surface CVD method can also effectively improve the interface mechanical locking effect of the material, thereby improving the bending rigidity of the material. The flexural modulus of the CF-v-CNT/BMI-PEI-CNT composite material is improved by 14.2 percent compared with the CF/BMI composite material by combining the influence of the matrix phase and the reinforcing phase.
Experiment two:
firstly, carbon fiber surface treatment: placing the carbon fiber in excessive acetone, heating and refluxing for 24h at 60 ℃, repeatedly washing with acetone, and drying. And (3) placing the carbon fiber in excessive concentrated nitric acid, reacting for 2h at a constant temperature of 60 ℃, repeatedly washing with deionized water and drying.
Secondly, loading metal ions: placing the carbon fiber subjected to surface treatment in 0.15mol/L NiNO3Soaking in the water solution for 1h, taking out the carbon fiber, placing in an oven, drying the surface moisture of the carbon fiber, and separating out and crystallizing nickel nitrate particles on the surface of the carbon fiber.
Thirdly, growing the carbon nano tube: placing the carbon fiber treated in the above two steps at the center of a tubular quartz tube, and introducing N into the tubular furnace for 30min before heating2When the temperature is raised to 380 ℃, N is introduced into the tube furnace2And H2Mixed gas (N) of (2)2And H2Is controlled to be 3:1), when the temperature in the tube furnace rises to 710 ℃, ethanol steam is introduced into the tube furnace, and CF-v-CNT is prepared.
Fourthly, preparing a CNT-PEI enhanced bismaleimide matrix phase: 2.5 wt% CNT-PEI was dispersed in ethanol, sonicated at 80KHz and stirred for 40min to obtain a stable suspension. And (3) dropwise adding BA into the suspension according to the mass ratio, wherein the process is carried out under the conditions of ultrasound and stirring. And stirring the mixed system at a constant temperature until the ethanol in the system is completely dried to obtain CNT-PEI/BA glue solution with good dispersion of the CNT-PEI. And then adding BMI with corresponding mass into the CNT-PEI/BA glue solution, stirring and reacting for 30min at 140 ℃ to obtain a prepolymer of BMI and BA, wherein the mass ratio of BMI to BA when preparing the prepolymer of BMI and BA is controlled at 1: 0.87.
Fifthly, preparing the prepreg: placing the prepared CF-v-CNT in an oven at 80 ℃ for drying, uniformly coating the prepared prepolymer glue solution on the surface of the carbon fiber, drying the solvent in the glue solution in the oven at 140 ℃, cooling and airing, and controlling the glue content in the prepreg to be 40 wt%.
Sixthly, compression molding of the composite material: cutting the prepreg into a shape of a mold cavity, flatly laying the prepreg in a mold, putting the mold into a 140 ℃ vacuum forming machine, repeatedly boosting the pressure and releasing the pressure in a small range to remove bubbles in the middle of the laying layer, and curing the material by a mold pressing process of 150 ℃/2h + l60 ℃/2h + l80 ℃/2h +210 ℃/2 h. And after solidification, randomly cooling to room temperature, demolding to obtain a composite material plate, and cutting the composite material plate into a sample with a required size according to experimental requirements.
The bismaleimide resin matrix composite material prepared by the chemical vapor deposition method adopting the carbon fiber-carbon nanotube micro-nano synergistic enhanced phase is prepared by the experiment, and the influence of the mechanical properties of the CF, CF-COOH and CF-v-CNT enhanced BMI and BMI-PEI-CNT composite material is respectively measured.
The impact performance of the composite material is measured by adopting a DXLL-5000 model microcomputer control universal tester, and the impact strength of the CF-v-CNT/BMI composite material is improved by 9.4 percent relative to the impact strength of the CF/BMI composite material. The impact strength of the CF-v-CNT/BMI-PEI-CNT composite material is improved by 12.7 percent relative to the CF/BMI-PEI-CNT composite material.
Experiment three:
firstly, carbon fiber surface treatment: placing the carbon fiber in excessive acetone, heating and refluxing for 24h at 65 ℃, repeatedly washing with acetone and drying. And (3) placing the carbon fiber in excessive concentrated nitric acid, reacting for 2h at a constant temperature of 65 ℃, repeatedly washing with deionized water and drying.
Secondly, loading metal ions: placing the carbon fiber subjected to surface treatment in 0.1mol/L NiNO3Soaking in the water solution for 1.5h, taking out the carbon fiber, placing in an oven, drying the surface moisture of the carbon fiber, and separating out and crystallizing nickel nitrate particles on the surface of the carbon fiber.
Thirdly, growing the carbon nano tube: placing the carbon fiber treated in the above two steps at the center of a tubular quartz tube, and introducing 40min N into the tubular furnace before heating2When the temperature is raised to 400 ℃, N is introduced into the tube furnace2And H2Mixed gas (N) of (2)2And H2Is controlled to be 3:1), when the temperature in the tube furnace rises to 700 ℃, ethanol steam is introduced into the tube furnace, and CF-v-CNT is prepared.
Fourthly, preparing a CNT-PEI enhanced bismaleimide matrix phase: 2.5 wt% CNT-PEI was dispersed in ethanol, sonicated at 80KHz and stirred for 50min to obtain a stable suspension. And (3) dropwise adding BA into the suspension according to the mass ratio, wherein the process is carried out under the conditions of ultrasound and stirring. And stirring the mixed system at a constant temperature until the ethanol in the system is completely dried to obtain CNT-PEI/BA glue solution with good dispersion of the CNT-PEI. And then adding BMI with corresponding mass into the CNT-PEI/BA glue solution, stirring and reacting for 30min at 140 ℃ to obtain a prepolymer of BMI and BA, wherein the mass ratio of BMI to BA when preparing the prepolymer of BMI and BA is controlled at 1: 0.87.
Fifthly, preparing the prepreg: placing the prepared CF-v-CNT in an oven at 80 ℃ for drying, uniformly coating the prepared prepolymer glue solution on the surface of the carbon fiber, drying a solvent in the glue solution in the oven at 140 ℃, cooling and airing, wherein the glue content in the prepreg is controlled at 50 wt%.
Sixthly, compression molding of the composite material: cutting the prepreg into a shape of a mold cavity, flatly laying the prepreg in a mold, putting the mold into a 140 ℃ vacuum forming machine, repeatedly boosting the pressure and releasing the pressure in a small range to remove bubbles in the middle of the laying layer, and curing the material by a mold pressing process of 150 ℃/2h + l60 ℃/2h + l80 ℃/2h +210 ℃/2 h. And after solidification, randomly cooling to room temperature, demolding to obtain a composite material plate, and cutting the composite material plate into a sample with a required size according to experimental requirements.
The bismaleimide resin matrix composite material prepared by the chemical vapor deposition method adopting the carbon fiber-carbon nanotube micro-nano synergistic enhanced phase is prepared by the experiment, and the influence of the mechanical properties of the CF, CF-COOH and CF-v-CNT enhanced BMI and BMI-PEI-CNT composite material is respectively measured.
The impact performance of the composite material is measured by using a Charpy XCJ-50 type simply supported beam impact tester, and the flexural modulus of the CF-v-CNT/BMI composite material is improved by 3.2 percent compared with that of the CF/BMI composite material. The flexural modulus of the CF-v-CNT/BMI-PEI-CNT composite material is improved by 6.3 percent compared with that of the CF/BMI-PEI-CNT composite material.
In the description herein, references to the description of "one embodiment," "an example," "a specific example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A method for preparing a bismaleimide resin matrix composite material by a chemical vapor deposition method is characterized by comprising the following steps:
s1: surface treatment, namely placing the carbon fiber in acetone, heating and refluxing at constant temperature, washing with acetone, drying, then placing the carbon fiber in concentrated nitric acid, washing with deionized water after constant temperature reaction, and drying;
s2: loading metal ions, soaking the carbon fiber subjected to surface treatment in a nickel nitrate aqueous solution, taking out and drying to crystallize and separate out nickel nitrate on the surface of the carbon fiber;
s3: growing a carbon nano tube, and heating and reacting the carbon fiber loaded with metal ions in a mixed atmosphere of nitrogen, hydrogen and ethanol steam to obtain CF-v-CNT;
s4: preparing a prepolymer glue solution, namely dispersing CNT-PEI (carbon nanotube-polyetherimide) in ethanol, stirring to obtain a CNT-PEI/ethanol suspension, dripping o, o ' -diallyl bisphenol A into the CNT-PEI/ethanol suspension, stirring at a constant temperature until the ethanol is evaporated to dryness to obtain a CNT-PEI/BA glue solution, and then adding N, N ' -4,4 ' -diphenylmethane bismaleimide into the CNT-PEI/BA glue solution to obtain a prepolymer;
s5: preparing a prepreg, namely uniformly coating the prepolymer glue solution prepared in the S4 process on the surface of the CF-v-CNT prepared in the S3 process, and drying to obtain the prepreg;
s6: and (3) compression molding, namely flatly laying the prepreg obtained in the S5 process in a mold, removing air bubbles, and then putting the prepreg into a vacuum forming machine for compression molding to obtain the bismaleimide resin matrix composite material.
2. The method for preparing the bismaleimide resin matrix composite material through the chemical vapor deposition method according to claim 1, wherein the temperature of constant-temperature heating reflux in S1 is 40-80 ℃, and the heating reflux time is 12-48 h;
s1, placing the carbon fiber in concentrated nitric acid, and reacting at a constant temperature of 40-80 ℃ for 0.5-4 h.
3. The method for preparing the bismaleimide resin matrix composite material through the chemical vapor deposition method as claimed in claim 1, wherein the concentration of the nickel nitrate aqueous solution in S2 is 0.05-0.5 mol/L, and the soaking time is controlled to be 0.5-2 h.
4. The method for preparing the bismaleimide resin matrix composite material through the chemical vapor deposition method as claimed in claim 1, wherein 10-40 min N is firstly introduced into S3 during the heating and temperature raising process2When the temperature is raised to 350-450 ℃, introducing N2And H2Mixed gas of (2), N2And H2The volume ratio of (A) to (B) is 2: 1-4: 1.
5. The method for preparing bismaleimide resin matrix composite material through chemical vapor deposition according to claim 4, wherein N is introduced into S32And H2And continuously raising the temperature of the mixed gas to 650-750 ℃, and introducing ethanol steam into the tubular furnace.
6. The method for preparing bismaleimide resin-based composite material through chemical vapor deposition according to claim 1, wherein the mass fraction of CNT-PEI dispersed in ethanol during S4 is 0.5-5.0 wt%, and the mass ratio of N, N ' -4,4 ' -diphenylmethane bismaleimide to o, o ' -diallyl bisphenol A is 1: 0.5-1: 1.
7. The method for preparing the bismaleimide resin matrix composite material by the chemical vapor deposition method according to claim 1, wherein the content of the prepolymer glue solution in the prepreg obtained in S5 is 25-60 wt%;
the drying temperature is 80-180 ℃.
8. The method for preparing a bismaleimide resin matrix composite material through a chemical vapor deposition method according to claim 1, wherein the step of removing bubbles in S6 is repeated small-amplitude pressure rise and pressure relief to remove bubbles in the middle of the layering, and the temperature range of a vacuum forming machine when bubbles are removed is 100-160 ℃.
9. The method for preparing bismaleimide resin matrix composite material through chemical vapor deposition as claimed in claim 1, wherein the temperature gradient during compression molding in a vacuum molding machine in S6 is 150 ℃/2h + l60 ℃/2h + l80 ℃/2h +210 ℃/2 h.
10. Use of a bismaleimide resin based composite prepared as in claim 1 in engineering materials.
CN201910949212.7A 2019-10-08 2019-10-08 Method for preparing bismaleimide resin matrix composite material by chemical vapor deposition method and application Active CN110819107B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910949212.7A CN110819107B (en) 2019-10-08 2019-10-08 Method for preparing bismaleimide resin matrix composite material by chemical vapor deposition method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910949212.7A CN110819107B (en) 2019-10-08 2019-10-08 Method for preparing bismaleimide resin matrix composite material by chemical vapor deposition method and application

Publications (2)

Publication Number Publication Date
CN110819107A true CN110819107A (en) 2020-02-21
CN110819107B CN110819107B (en) 2021-12-31

Family

ID=69548708

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910949212.7A Active CN110819107B (en) 2019-10-08 2019-10-08 Method for preparing bismaleimide resin matrix composite material by chemical vapor deposition method and application

Country Status (1)

Country Link
CN (1) CN110819107B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787128A (en) * 2010-02-04 2010-07-28 同济大学 Method for preparing hybrid composite material of carbon fibers/carbon nanotubes/bismaleimide resin
CN102120882A (en) * 2011-01-12 2011-07-13 同济大学 Preparation method of carbon nano tube and functionalized carbon fiber reinforced bismaleimide resin matrix composite
CN103665769A (en) * 2013-11-26 2014-03-26 上海复合材料科技有限公司 Method for preparing nanometer-micrometer multi-scale fiber prepreg
CN106971859A (en) * 2017-04-14 2017-07-21 同济大学 A kind of carbon fiber/carbon nanotube flexible super capacitor electrode material and its preparation
CN109610159A (en) * 2018-12-20 2019-04-12 山东大学 A kind of preparation method growing carbon nanotube in carbon fibre fabric surface catalysis using bimetallic catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787128A (en) * 2010-02-04 2010-07-28 同济大学 Method for preparing hybrid composite material of carbon fibers/carbon nanotubes/bismaleimide resin
CN102120882A (en) * 2011-01-12 2011-07-13 同济大学 Preparation method of carbon nano tube and functionalized carbon fiber reinforced bismaleimide resin matrix composite
CN103665769A (en) * 2013-11-26 2014-03-26 上海复合材料科技有限公司 Method for preparing nanometer-micrometer multi-scale fiber prepreg
CN106971859A (en) * 2017-04-14 2017-07-21 同济大学 A kind of carbon fiber/carbon nanotube flexible super capacitor electrode material and its preparation
CN109610159A (en) * 2018-12-20 2019-04-12 山东大学 A kind of preparation method growing carbon nanotube in carbon fibre fabric surface catalysis using bimetallic catalyst

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
QIU JUN等: "Carbon fibers surface-grown with helical carbon nanotubes and polyaniline for high-performance electrode materials and flexible supercapacitors", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 *
QIU JUN等: "Effect of hyperbranched polyethyleneimine grafting functionalization of carbon nanotubes on mechanical, thermal stability and electrical properties of carbon nanotubes/bismaleimide composites", 《RSC ADV.》 *
郑林宝等: "CF-CNTs 多尺度增强体的制备及CF-CNTs/环氧树脂复合材料力学性能", 《复合材料学报》 *

Also Published As

Publication number Publication date
CN110819107B (en) 2021-12-31

Similar Documents

Publication Publication Date Title
US11167991B2 (en) Method for preparing carbon nanotube/polymer composite
JP4868478B2 (en) Three-dimensional interpenetrating network of macromolecules of randomly oriented carbon fibrils and organic polymers
CN109608822B (en) MOF-5 nondestructive modified carbon fiber reinforced resin-based wet friction material and preparation method thereof
CN104277421A (en) Preparation method of multicomponent-modified carbon-fiber-reinforced epoxy resin composite material
CN114197205B (en) Modified carbon fiber and preparation method and application thereof
CN112694715B (en) Glass fiber composite material and preparation method thereof
CN107722595B (en) Preparation method of fiber-graphene-thermoplastic polyarylether multi-scale composite material
CN112323482A (en) Carbon fiber obtained by electrophoretic deposition-electropolymerization combined modification and resin matrix composite material thereof
CN110776740B (en) Method for preparing three-phase bismaleimide resin matrix composite material by chemical grafting method and application thereof
CN110713612B (en) Low-temperature-resistant circulating composite material and preparation method thereof
CN102796373A (en) Graphene/cyanate ester/bimaleimide composite material and preparation method thereof
CN110819107B (en) Method for preparing bismaleimide resin matrix composite material by chemical vapor deposition method and application
CN114507417A (en) Modified epoxy resin and use method thereof
JPH0536521B2 (en)
Banerjee et al. Tuneable chemistry at the interface and self-healing towards improving structural properties of carbon fiber laminates: a critical review
CN113004655A (en) Preparation method of glass fiber reinforced thermosetting resin prepreg
CN106633666B (en) A kind of preparation method of carbon nanotube and resin composite materials
CN114425890A (en) Glass fiber cloth/polypropylene composite material and preparation method and application thereof
JPH0816032B2 (en) High-strength carbon-carbon composite manufacturing method
JPS61268441A (en) Composite material of generated fine carbon fiber
JPH03197360A (en) Production of carbon fiber-reinforced carbon material
CN117247573A (en) Preparation method for regulating and controlling interface transition layer of carbon fiber reinforced resin composite material
CN112223861B (en) Energy-saving silicon phenol fireproof insulation board
CN116876093B (en) Polyacrylamide/graphene composite fiber and preparation method thereof
CN114989569A (en) Epoxy resin composite material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant