CN110452414B - Preparation method of highly-oriented graphene reinforced bismaleimide resin matrix composite material - Google Patents

Preparation method of highly-oriented graphene reinforced bismaleimide resin matrix composite material Download PDF

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CN110452414B
CN110452414B CN201910785916.5A CN201910785916A CN110452414B CN 110452414 B CN110452414 B CN 110452414B CN 201910785916 A CN201910785916 A CN 201910785916A CN 110452414 B CN110452414 B CN 110452414B
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graphene
resin matrix
matrix composite
composite material
curing
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CN110452414A (en
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彭庆宇
赵旭
赫晓东
周敏
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Harbin Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/10—Conditioning or physical treatment of the material to be shaped by grinding, e.g. by triturating; by sieving; by filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • 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
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/004—Shaping under special conditions
    • B29C2791/006—Using vacuum

Abstract

The invention discloses a preparation method of a highly-oriented graphene reinforced bismaleimide resin matrix composite material. The method solves the problem that the graphene cannot be highly oriented in the resin matrix by the existing method, improves the mechanical property of the resin matrix, changes an isotropic material into an anisotropic material, expands the application range of the composite material, strengthens the competitive advantage, and provides a novel oriented preparation method for nano filling.

Description

Preparation method of highly-oriented graphene reinforced bismaleimide resin matrix composite material
Technical Field
The invention belongs to the technical field of material science, and relates to a preparation method of a highly oriented graphene reinforced resin matrix composite material.
Background
In the 21 st century, aerospace has shown a wider development prospect, and high-level or ultra-high-level aerospace activities are more frequent, have far more functions than the scientific and technical field, and have wider and more profound influences on political, economic, military and even human social life. It should be noted that the great achievements achieved by the aerospace industry are not separable from the development and breakthrough of aerospace materials technology. The material is the foundation and the precursor of modern high and new technology and industry, and is a precondition for breakthrough of the high and new technology to a great extent. The general development trend of materials is light weight, high strength, high modulus, high temperature resistance and low cost, and the structure-function integration and intellectualization are more important material development directions due to the development requirements of modern high-performance aircrafts.
The low-dimensional, nano and composite technology is an important technical approach for promoting the structural-functional integration and intelligent development of new aerospace materials and realizing the revolutionary transition of performance. The application of graphene composite materials in the aerospace field is facing important development opportunities. At present, the nano composite material is still in the laboratory and small-batch production stage, and with the increase of the demand in the aerospace field and the development of the nano carbon composite material technology, the engineering and industrialization of the nano carbon composite material also lay a foundation for improving the competitiveness of the nano carbon composite material in the market. However, the nano-scale of the nano-carbon material brings excellent performance to the nano-carbon material, but the nano-scale of the nano-carbon material also becomes the greatest difficulty of engineering application of the nano-carbon material, generally, graphene is randomly distributed in a resin matrix, and the composite material shows the characteristic of isotropy, so that unnecessary waste and complexity are caused to the design of certain special required components and devices. Therefore, in response to the special requirement, an oriented graphene composite material needs to be prepared, and the performance of the oriented graphene composite material shows anisotropy, so that the design requirement of a component with the special requirement is met, the use efficiency is improved, the cost is reduced, and unnecessary waste of raw materials is reduced.
Disclosure of Invention
Aiming at the urgency of the research on the anisotropic graphene reinforced nano composite material, the invention provides a preparation method of a highly oriented graphene reinforced bismaleimide resin matrix composite material. The method solves the problem that the graphene cannot be highly oriented in the resin matrix by the existing method, improves the mechanical property of the resin matrix, changes an isotropic material into an anisotropic material, expands the application range of the composite material, strengthens the competitive advantage, and provides a novel oriented preparation method for nano filling.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a highly oriented graphene reinforced bismaleimide resin-based composite material comprises the following steps:
step one, preparing graphene sponge:
the first method comprises the following steps of preparing the graphene sponge by adopting an improved freeze drying method: freezing the dispersed graphene aqueous solution with the concentration of 5-20 mg/ml at low temperature (below 0 ℃), and simultaneously obtaining porous graphene sponge (with the density of 5-20 mg/ml) by using a freeze-drying method;
the second method comprises the following steps of preparing the graphene sponge by adopting a reduction method: freezing 5-30 mg/ml graphene oxide aqueous solution at low temperature (below 0 ℃), and simultaneously obtaining porous graphene oxide sponge (with the density of 5-30 mg/ml) by using a freeze-drying method; preparing graphene sponge by adopting an excessive hydrazine hydrate chemical reduction method at the temperature of 70-90 ℃ for 24h or a thermal reduction method at the temperature of 200-1000 ℃;
step two, preparing graphene reinforced resin matrix composite material precursor slurry:
absorbing pure bismaleimide resin into the graphene sponge porous structure prepared in the step one by using a negative pressure method and a vacuum infusion method, and specifically comprising the following steps: placing the graphene sponge to a viscosity of 10 by using a negative pressure method-3~10-1In the pure bismaleimide resin of Pa.S, the oven is vacuumized by a vacuum pump (10)4~105Pa), namely a vacuum infusion method, absorbing pure bismaleimide resin into a porous structure of the graphene sponge, and filling a three-dimensional graphene framework;
taking graphene sponge pre-impregnated with resin as a precursor, uniformly mixing the graphene three-dimensional skeleton impregnated with the resin with a pure bismaleimide resin matrix while crushing the graphene three-dimensional skeleton by a stirring (800-2000 r/min) ultrasonic-assisted method, and preparing the mixture of the graphene three-dimensional skeleton and the pure bismaleimide resin matrix according to actual requirements to obtain high-dispersion graphene reinforced resin matrix composite precursor slurry;
step three, preparing a precursor of the directional graphene reinforced resin matrix composite material:
controlling the temperature field of the graphene reinforced resin matrix composite precursor slurry to be lower than 0 ℃, regulating the viscosity of the graphene reinforced resin matrix composite precursor slurry to be 1-10 Pa.S, and preparing the oriented graphene reinforced resin matrix composite precursor by controlling the force field (generally 50-500 MPa) under proper viscosity and utilizing a cold pressing mode;
step four, preparing the oriented graphene reinforced resin matrix composite material:
injecting the precursor of the oriented graphene reinforced resin matrix composite material prepared in the third step into a mold, removing bubbles in vacuum, controlling a temperature field and a base force field to meet the curing requirement, and finally preparing the oriented graphene reinforced resin matrix composite material after curing is completed, wherein: the curing is gradient curing, and the gradient curing conditions are as follows: curing for 2 hours at 160-180 ℃ and the pressure is 50 MPa; curing at 190-210 ℃ for 1 hour under the pressure of 50 MPa; curing at 220-240 ℃ for 4 hours and 50MPa, and curing at 250-260 ℃ for 4 hours and 50 MPa.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts a freeze-drying method to prepare a graphene macroscopic body in advance, and prepares the graphene reinforced resin matrix composite slurry by a vacuum-assisted infusion molding method. The key preparation technology of the oriented graphene reinforced resin matrix composite material is overcome, the problem of orientation of graphene in a resin matrix is solved, high orientation of the graphene in the resin is realized, and the highly oriented graphene reinforced resin matrix composite material is obtained.
2. The preparation method realizes the preparation and microstructure regulation of the graphene three-dimensional framework reinforcement, and the graphene sponge with controllable density of 5-20 mg/ml is obtained. And obtaining the oriented graphene reinforced resin matrix composite, wherein scanning proves that the graphene is highly oriented in the resin matrix, and the mechanical property of the oriented graphene reinforced resin matrix composite is improved by 10-40% along the oriented direction.
3. According to the preparation method, a brand new preparation concept is adopted, the graphene three-dimensional framework is used as a dispersion body, the graphene reinforced resin matrix composite slurry is prepared by adopting a vacuum infusion method and a high-speed stirring ultrasonic auxiliary method, a precursor of the oriented graphene reinforced resin matrix composite is prepared by controlling a temperature field and a force field, and the oriented graphene reinforced resin matrix composite is obtained after pressurization gradient curing, so that not only is the graphene oriented in the resin matrix obtained, but also the mechanical property of the composite is improved.
Drawings
Fig. 1 is a diagram of a three-dimensional graphene framework obtained in the first step of example 2;
FIG. 2 is a real object diagram of a precursor of the oriented graphene reinforced resin matrix composite obtained in step three of example 2;
FIG. 3 is a micro-scanning photograph of the oriented graphene reinforced resin matrix composite obtained in the fourth step of example 2;
FIG. 4 is a photograph showing the mechanical properties of the oriented graphene reinforced resin matrix composite obtained in the fourth step of example 2.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings, but not limited thereto, and any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be covered by the protection scope of the present invention.
The first embodiment is as follows: the embodiment provides a preparation method for preparing a highly-oriented graphene reinforced bismaleimide resin matrix composite material, which comprises the steps of preparing a composite material slurry precursor from a three-dimensional graphene framework by a vacuum infusion method, preparing graphene resin matrix composite material slurry by a high-speed stirring ultrasonic-assisted method, preparing the oriented graphene reinforced resin matrix composite material precursor by controlling a temperature field and a force field, and finally preparing the highly-dispersed graphene reinforced resin matrix composite material by a pressurization gradient curing method. The method specifically comprises the following steps:
step one, preparing graphene sponge:
the first method comprises the following steps of preparing the graphene sponge by adopting an improved freeze drying method: freezing the dispersed graphene aqueous solution with the concentration of 5-20 mg/ml at low temperature (below 0 ℃), and simultaneously obtaining porous graphene sponge (with the density of 5-20 mg/ml) by using a freeze-drying method;
the second method comprises the following steps of preparing the graphene sponge by adopting a reduction method: freezing 5-30 mg/ml graphene oxide aqueous solution at low temperature (below 0 ℃), and simultaneously obtaining porous graphene oxide sponge (with the density of 5-30 mg/ml) by using a freeze-drying method; preparing graphene sponge by adopting an excessive hydrazine hydrate chemical reduction method at the temperature of 70-90 ℃ for 24h or a thermal reduction method at the temperature of 200-1000 ℃;
step two, preparing graphene reinforced resin matrix composite material precursor slurry:
absorbing resin into the graphene sponge porous structure prepared in the step one by using a negative pressure method and a vacuum infusion method, and specifically comprising the following steps: placing the graphene sponge to a viscosity of 10 by using a negative pressure method-3~10-1In the resin of Pa.S, the oven was evacuated by a vacuum pump (10)4~105Pa), namely a vacuum infusion method, which sucks resin into the porous structure of the graphene sponge;
taking graphene sponge pre-impregnated with resin as a precursor, and uniformly mixing the graphene three-dimensional skeleton impregnated with resin with a pure bismaleimide resin matrix while crushing the graphene three-dimensional skeleton by a stirring (800-2000 r/min) ultrasonic-assisted method to obtain high-dispersion graphene reinforced resin matrix composite precursor slurry;
step three, preparing a precursor of the directional graphene reinforced resin matrix composite material:
controlling the temperature field of the graphene reinforced resin matrix composite precursor slurry to be lower than 0 ℃, regulating the viscosity of the graphene reinforced resin matrix composite precursor slurry to be 1-10 Pa.S, and preparing the oriented graphene reinforced resin matrix composite precursor by controlling the force field (generally 50-500 MPa) under proper viscosity and utilizing a cold pressing mode;
step four, preparing the oriented graphene reinforced resin matrix composite material:
injecting the precursor of the oriented graphene reinforced resin matrix composite material prepared in the third step into a mold, removing bubbles in vacuum, controlling a temperature field and a base force field to meet the curing requirement, and finally preparing the oriented graphene reinforced resin matrix composite material after curing is completed, wherein: the curing is gradient curing, and the gradient curing conditions are as follows: curing for 2 hours at 160-180 ℃ and the pressure is 50 MPa; curing at 190-210 ℃ for 1 hour under the pressure of 50 MPa; curing at 220-240 ℃ for 4 hours and 50MPa, and curing at 250-260 ℃ for 4 hours and 50 MPa.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: in the first step, the concentration of the graphene aqueous solution is 5-10 mg/ml; the concentration of the graphene oxide aqueous solution is 5-20 mg/ml.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the first step, the chemical reduction hydrazine hydrate is used at the temperature of 90 ℃ for 24 hours; the thermal reduction temperature is 600-800 ℃.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: in the second step, the viscosity of the resin is 10-3~10-2Pa·S。
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: in the third step, the stirring speed is 1000-1500 r/min.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: in the third step, the viscosity of the graphene reinforced resin matrix composite material slurry is 1-5 Pa.S; the force field is 50-300 MPa.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: in the fourth step, the gradient curing conditions are as follows: curing for 2 hours at 170-180 ℃ and the pressure is 50 MPa; curing for 1 hour at 200-210 ℃ and the pressure is 50 MPa; curing for 4 hours at 230-240 ℃ and the pressure is 50 MPa; curing at 250 ℃ for 4 hours under the pressure of 50 MPa.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1
In this embodiment, the method for preparing the highly-oriented graphene reinforced bismaleimide resin-based composite material is implemented according to the following steps:
step one, preparing graphene sponge:
the first method comprises the following steps of preparing the graphene sponge by adopting an improved freeze drying method: freezing the dispersed graphene aqueous solution with the concentration of 10mg/ml at low temperature (below 0 ℃), and simultaneously obtaining porous graphene sponge (with the density of 10 mg/ml) by using a freeze-drying method;
the second method comprises the following steps of preparing the graphene sponge by adopting a reduction method: freezing 10mg/ml graphene oxide aqueous solution at low temperature (below 0 ℃), and simultaneously obtaining porous graphene oxide sponge (with the density of 10 mg/ml) by using a freeze-drying method; preparing graphene sponge by adopting a method of carrying out chemical reduction on excess hydrazine hydrate at the temperature of 90 ℃ for 24h or thermal reduction at the temperature of 700 ℃;
step two, preparing graphene reinforced resin matrix composite material precursor slurry:
absorbing resin into the graphene sponge porous structure prepared in the step one by using a negative pressure method and a vacuum infusion method, and specifically comprising the following steps: placing the graphene sponge to a viscosity of 10 by using a negative pressure method-1In the resin of Pa.S, the oven was evacuated by a vacuum pump (10)4~105Pa), namely a vacuum infusion method, which sucks resin into the porous structure of the graphene sponge;
taking graphene sponge pre-impregnated with resin as a precursor, and uniformly mixing the graphene three-dimensional skeleton impregnated with resin with a pure bismaleimide resin matrix while crushing the graphene three-dimensional skeleton by a stirring (800-2000 r/min) ultrasonic-assisted method to obtain high-dispersion graphene reinforced resin matrix composite precursor slurry;
step three, preparing a precursor of the directional graphene reinforced resin matrix composite material:
controlling the temperature field of the graphene reinforced resin matrix composite precursor slurry to be lower than 0 ℃, regulating the viscosity of the graphene reinforced resin matrix composite precursor slurry to be 10 Pa & S, and preparing the oriented graphene reinforced resin matrix composite precursor by controlling the force field (generally 500 MPa) under proper viscosity and utilizing a cold pressing mode;
step four, preparing the oriented graphene reinforced resin matrix composite material:
injecting the precursor of the oriented graphene reinforced resin matrix composite material prepared in the third step into a mold, removing bubbles in vacuum, controlling a temperature field and a base force field to meet the curing requirement, and finally preparing the oriented graphene reinforced resin matrix composite material after curing is completed, wherein: the curing is gradient curing, and the gradient curing conditions are as follows: curing at 180 ℃ for 2h, wherein the pressure is 50 MPa; curing at 210 ℃ for 1 hour under the pressure of 50 MPa; curing at 240 ℃ for 4 hours under the pressure of 50MPa, and curing at 260 ℃ for 4 hours under the pressure of 50 MPa.
In the embodiment, a freeze-drying method is adopted to prepare a graphene macroscopic body in advance, and the graphene reinforced resin matrix composite slurry is prepared by a vacuum-assisted infusion molding method. The key preparation technology of the oriented graphene reinforced resin matrix composite material is overcome, the problem of orientation of graphene in a resin matrix is solved, high orientation of the graphene in the resin is realized, and the highly oriented graphene reinforced resin matrix composite material is obtained. According to the embodiment, the preparation and microstructure regulation of the graphene three-dimensional framework reinforcement are realized, and the graphene sponge with the controllable density of 10mg/ml is obtained. In the embodiment, the oriented graphene reinforced resin matrix composite material is obtained, and scanning proves that the graphene is highly oriented in the resin matrix, and meanwhile, the mechanical property of the oriented graphene reinforced resin matrix composite material is improved by 10% along the oriented direction.
Example 2:
in this embodiment, the method for preparing the highly-oriented graphene reinforced bismaleimide resin-based composite material is implemented according to the following steps:
step one, preparing graphene sponge:
the first method comprises the following steps of preparing the graphene sponge by adopting an improved freeze drying method: freezing the dispersed graphene aqueous solution with the concentration of 20mg/ml at low temperature (below 0 ℃), and simultaneously obtaining porous graphene sponge (with the density of 20 mg/ml) by using a freeze-drying method;
the second method comprises the following steps of preparing the graphene sponge by adopting a reduction method: freezing a 20mg/ml graphene oxide aqueous solution at a low temperature (below 0 ℃), and simultaneously obtaining porous graphene oxide sponge (with the density of 20 mg/ml) by using a freeze-drying method; preparing graphene sponge by adopting a method of carrying out chemical reduction on excess hydrazine hydrate at the temperature of 90 ℃ for 24h or thermal reduction at the temperature of 1000 ℃;
step two, preparing graphene reinforced resin matrix composite material precursor slurry:
absorbing resin into the graphene sponge porous structure prepared in the step one by using a negative pressure method and a vacuum infusion method, and specifically comprising the following steps: placing the graphene sponge to a viscosity of 10 by using a negative pressure method-2In the resin of Pa.S, the oven was evacuated by a vacuum pump (10)5Pa), namely a vacuum infusion method, which sucks resin into the porous structure of the graphene sponge;
taking graphene sponge pre-impregnated with resin as a precursor, and uniformly mixing the graphene three-dimensional skeleton impregnated with resin with a pure bismaleimide resin matrix while crushing the graphene three-dimensional skeleton by a stirring (1500 r/min) ultrasonic-assisted method to obtain high-dispersion graphene reinforced resin matrix composite precursor slurry;
step three, preparing a precursor of the directional graphene reinforced resin matrix composite material:
controlling the temperature field of the graphene reinforced resin matrix composite precursor slurry to be lower than 0 ℃, regulating the viscosity of the graphene reinforced resin matrix composite precursor slurry to be 10 Pa & S, and preparing the oriented graphene reinforced resin matrix composite precursor by controlling the force field (generally 500 MPa) under proper viscosity and utilizing a cold pressing mode;
step four, preparing the oriented graphene reinforced resin matrix composite material:
injecting the precursor of the oriented graphene reinforced resin matrix composite material prepared in the third step into a mold, removing bubbles in vacuum, controlling a temperature field and a base force field to meet the curing requirement, and finally preparing the oriented graphene reinforced resin matrix composite material after curing is completed, wherein: the curing is gradient curing, and the gradient curing conditions are as follows: curing at 160 ℃ for 2h under the pressure of 50 MPa; curing at 190 ℃ for 1 hour under the pressure of 50 MPa; curing at 220 ℃ for 4 hours and 50MPa of pressure, and curing at 250 ℃ for 4 hours and 50MPa of pressure.
Fig. 1 is a diagram of a sample of the graphene sponge obtained in the first step of this embodiment, and as can be seen from fig. 1, the surface of the three-dimensional skeleton of the obtained graphene sponge is flat; fig. 2 is a diagram of a graphene reinforced resin matrix composite precursor obtained in the third step of the present embodiment, and as can be seen from fig. 2, the obtained graphene reinforced resin matrix composite precursor is folded for multiple times to have a flat surface; FIG. 3 is a micro-scanning photograph of the oriented graphene reinforced resin matrix composite obtained in the fourth step of the present embodiment, and it can be seen from FIG. 3 that graphene is oriented in the resin matrix; fig. 4 is a mechanical property photograph of the oriented graphene reinforced resin matrix composite obtained in the fourth step of the present embodiment, and as can be seen from fig. 4, the mechanical property is improved by 30%.
In the embodiment, a freeze-drying method is adopted to prepare a graphene macroscopic body in advance, and the graphene reinforced resin matrix composite slurry is prepared by a vacuum-assisted infusion molding method. The key preparation technology of the oriented graphene reinforced resin matrix composite material is overcome, the problem of orientation of graphene in a resin matrix is solved, high orientation of the graphene in the resin is realized, and the highly oriented graphene reinforced resin matrix composite material is obtained. According to the embodiment, the preparation and microstructure regulation of the graphene three-dimensional framework reinforcement are realized, and the graphene sponge with the controllable density of 20mg/ml is obtained. In the embodiment, the oriented graphene reinforced resin matrix composite material is obtained, and scanning proves that the graphene is highly oriented in the resin matrix, and meanwhile, the mechanical property of the oriented graphene reinforced resin matrix composite material is improved by 30% along the oriented direction.
Example 3:
in this embodiment, the method for preparing the highly-oriented graphene reinforced bismaleimide resin-based composite material is implemented according to the following steps:
step one, preparing graphene sponge:
the first method comprises the following steps of preparing the graphene sponge by adopting an improved freeze drying method: freezing the dispersed graphene aqueous solution with the concentration of 10mg/ml at low temperature (below 0 ℃), and simultaneously obtaining porous graphene sponge (with the density of 10 mg/ml) by using a freeze-drying method;
the second method comprises the following steps of preparing the graphene sponge by adopting a reduction method: freezing 10mg/ml graphene oxide aqueous solution at low temperature (below 0 ℃), and simultaneously obtaining porous graphene oxide sponge (with the density of 10 mg/ml) by using a freeze-drying method; preparing graphene sponge by adopting a method of carrying out chemical reduction on excess hydrazine hydrate at the temperature of 90 ℃ for 24h or thermal reduction at the temperature of 800 ℃;
step two, preparing graphene reinforced resin matrix composite material precursor slurry:
absorbing resin into the graphene sponge porous structure prepared in the step one by using a negative pressure method and a vacuum infusion method, and specifically comprising the following steps: placing the graphene sponge to a viscosity of 10 by using a negative pressure method-1In the resin of Pa.S, the oven was evacuated by a vacuum pump (10)5Pa), namely a vacuum infusion method, which sucks resin into the porous structure of the graphene sponge;
taking graphene sponge pre-impregnated with resin as a precursor, and uniformly mixing the graphene three-dimensional skeleton impregnated with resin with a pure bismaleimide resin matrix while crushing the graphene three-dimensional skeleton by a stirring (2000 r/min) ultrasonic-assisted method to obtain high-dispersion graphene reinforced resin matrix composite precursor slurry;
step three, preparing a precursor of the directional graphene reinforced resin matrix composite material:
controlling the temperature field of the graphene reinforced resin matrix composite precursor slurry to be lower than 0 ℃, regulating the viscosity of the graphene reinforced resin matrix composite precursor slurry to be 10 Pa & S, and preparing the oriented graphene reinforced resin matrix composite precursor by controlling the force field (generally 400 MPa) under proper viscosity and utilizing a cold pressing mode;
step four, preparing the oriented graphene reinforced resin matrix composite material:
injecting the precursor of the oriented graphene reinforced resin matrix composite material prepared in the third step into a mold, removing bubbles in vacuum, controlling a temperature field and a base force field to meet the curing requirement, and finally preparing the oriented graphene reinforced resin matrix composite material after curing is completed, wherein: the curing is gradient curing, and the gradient curing conditions are as follows: curing at 180 ℃ for 2h, wherein the pressure is 50 MPa; curing at 210 ℃ for 1 hour under the pressure of 50 MPa; curing at 240 ℃ for 4 hours under the pressure of 50MPa, and curing at 260 ℃ for 4 hours under the pressure of 50 MPa.
In the embodiment, a freeze-drying method is adopted to prepare a graphene macroscopic body in advance, and the graphene reinforced resin matrix composite slurry is prepared by a vacuum-assisted infusion molding method. The key preparation technology of the oriented graphene reinforced resin matrix composite material is overcome, the problem of orientation of graphene in a resin matrix is solved, high orientation of the graphene in the resin is realized, and the highly oriented graphene reinforced resin matrix composite material is obtained. According to the embodiment, the preparation and microstructure regulation of the graphene three-dimensional framework reinforcement are realized, and the graphene sponge with the controllable density of 10mg/ml is obtained. In the embodiment, the oriented graphene reinforced resin matrix composite material is obtained, and scanning proves that the graphene is highly oriented in the resin matrix, and meanwhile, the mechanical property of the oriented graphene reinforced resin matrix composite material is improved by 10% along the oriented direction.
Example 4:
in this embodiment, the method for preparing the highly-oriented graphene reinforced bismaleimide resin-based composite material is implemented according to the following steps:
step one, preparing graphene sponge:
the first method comprises the following steps of preparing the graphene sponge by adopting an improved freeze drying method: freezing the dispersed graphene aqueous solution with the concentration of 8mg/ml at low temperature (below 0 ℃), and simultaneously obtaining porous graphene sponge (with the density of 8 mg/ml) by using a freeze-drying method;
the second method comprises the following steps of preparing the graphene sponge by adopting a reduction method: freezing 8mg/ml graphene oxide aqueous solution at low temperature (below 0 ℃), and simultaneously obtaining porous graphene oxide sponge (with the density of 8 mg/ml) by using a freeze-drying method; preparing graphene sponge by adopting a method of carrying out chemical reduction on excess hydrazine hydrate at the temperature of 90 ℃ for 24h or thermal reduction at the temperature of 700 ℃;
step two, preparing graphene reinforced resin matrix composite material precursor slurry:
by vacuum infusion using negative pressureThe method comprises the following steps of absorbing resin into the graphene sponge porous structure prepared in the step one: placing the graphene sponge to a viscosity of 10 by using a negative pressure method-1In the resin of Pa.S, the oven was evacuated by a vacuum pump (10)5Pa), namely a vacuum infusion method, which sucks resin into the porous structure of the graphene sponge;
taking graphene sponge pre-impregnated with resin as a precursor, and uniformly mixing the graphene three-dimensional skeleton impregnated with resin with a pure bismaleimide resin matrix while crushing the graphene three-dimensional skeleton by a stirring (1800 r/min) ultrasonic-assisted method to obtain high-dispersion graphene reinforced resin matrix composite precursor slurry;
step three, preparing a precursor of the directional graphene reinforced resin matrix composite material:
controlling the temperature field of the graphene reinforced resin matrix composite precursor slurry to be lower than 0 ℃, regulating the viscosity of the graphene reinforced resin matrix composite precursor slurry to be 10 Pa & S, and preparing the oriented graphene reinforced resin matrix composite precursor by controlling the force field (generally 500 MPa) under proper viscosity and utilizing a cold pressing mode;
step four, preparing the oriented graphene reinforced resin matrix composite material:
injecting the precursor of the oriented graphene reinforced resin matrix composite material prepared in the third step into a mold, removing bubbles in vacuum, controlling a temperature field and a base force field to meet the curing requirement, and finally preparing the oriented graphene reinforced resin matrix composite material after curing is completed, wherein: the curing is gradient curing, and the gradient curing conditions are as follows: curing at 180 ℃ for 2h, wherein the pressure is 50 MPa; curing at 200 ℃ for 1 hour under the pressure of 50 MPa; curing at 240 ℃ for 4 hours under the pressure of 50MPa, and curing at 250 ℃ for 4 hours under the pressure of 50 MPa.
In the embodiment, a freeze-drying method is adopted to prepare a graphene macroscopic body in advance, and the graphene reinforced resin matrix composite slurry is prepared by a vacuum-assisted infusion molding method. The key preparation technology of the oriented graphene reinforced resin matrix composite material is overcome, the problem of orientation of graphene in a resin matrix is solved, high orientation of the graphene in the resin is realized, and the highly oriented graphene reinforced resin matrix composite material is obtained. According to the embodiment, the preparation and microstructure regulation of the graphene three-dimensional framework reinforcement are realized, and the graphene sponge with the controllable density of 8mg/ml is obtained. In the embodiment, the oriented graphene reinforced resin matrix composite material is obtained, and scanning proves that the graphene is highly oriented in the resin matrix, and meanwhile, the mechanical property of the oriented graphene reinforced resin matrix composite material is improved by 15% along the orientation direction.

Claims (5)

1. A preparation method of a highly oriented graphene reinforced bismaleimide resin-based composite material is characterized by comprising the following steps:
step one, preparing graphene reinforced resin matrix composite material precursor slurry:
absorbing pure bismaleimide resin into a graphene sponge porous structure by a vacuum infusion method by using a negative pressure method;
taking graphene sponge pre-impregnated with resin as a precursor, and uniformly mixing the resin-impregnated graphene three-dimensional skeleton with a pure bismaleimide resin matrix while crushing the resin-impregnated graphene three-dimensional skeleton by a stirring ultrasonic-assisted method to obtain high-dispersion graphene reinforced resin matrix composite precursor slurry;
step two, preparing a precursor of the directional graphene reinforced resin matrix composite material:
controlling a temperature field of graphene reinforced resin matrix composite precursor slurry to enable the temperature to be lower than 0 ℃, regulating and controlling the viscosity of the graphene reinforced resin matrix composite precursor slurry to be 1-10 Pa.S, and preparing the oriented graphene reinforced resin matrix composite precursor by controlling a force field in a cold pressing mode under the appropriate viscosity, wherein the force field is 50-500 MPa;
step three, preparing the oriented graphene reinforced resin matrix composite material:
injecting a precursor of the oriented graphene reinforced resin matrix composite material into a mold, removing bubbles in the mold in vacuum, controlling a temperature field and a force field to meet the curing requirement, and finally preparing the oriented graphene reinforced resin matrix composite material after curing, wherein the curing is gradient curing, and the gradient curing condition is as follows: curing for 2 hours at 160-180 ℃ and the pressure is 50 MPa; curing at 190-210 ℃ for 1 hour under the pressure of 50 MPa; curing at 220-240 ℃ for 4 hours and 50MPa, and curing at 250-260 ℃ for 4 hours and 50 MPa.
2. The method for preparing the highly-oriented graphene reinforced bismaleimide resin based composite material as claimed in claim 1, wherein in the step one, the specific steps of absorbing the resin into the porous structure of the graphene sponge are as follows: placing the graphene sponge to a viscosity of 10 by using a negative pressure method-3~10-1In the resin of Pa.S, the oven is vacuumized by a vacuum pump 104~105Pa, a vacuum infusion method, draws the resin into the porous structure of the graphene sponge.
3. The preparation method of the highly oriented graphene reinforced bismaleimide resin based composite material as claimed in claim 1 or 2, wherein the preparation method of the graphene sponge is as follows: the preparation method of the graphene sponge by adopting an improved freeze drying method comprises the following specific steps: and freezing the dispersed graphene aqueous solution with the concentration of 5-20 mg/ml at a low temperature, and simultaneously obtaining the porous graphene sponge by using a freeze-drying method.
4. The preparation method of the highly oriented graphene reinforced bismaleimide resin based composite material as claimed in claim 1 or 2, wherein the preparation method of the graphene sponge is as follows: freezing 5-30 mg/ml of graphene oxide aqueous solution at low temperature, and simultaneously obtaining porous graphene oxide sponge by using a freeze-drying method; and carrying out chemical reduction on excessive hydrazine hydrate at the temperature of 70-90 ℃ for 24h or carrying out thermal reduction at the temperature of 200-1000 ℃ to prepare the graphene sponge.
5. The preparation method of the highly-oriented graphene reinforced bismaleimide resin matrix composite material as claimed in claim 1, wherein the rotation speed of the stirring is 800-2000 r/min.
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