CN110452415B - Preparation method of high-dispersion graphene reinforced bismaleimide resin-based composite material - Google Patents

Preparation method of high-dispersion graphene reinforced bismaleimide resin-based composite material Download PDF

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CN110452415B
CN110452415B CN201910785918.4A CN201910785918A CN110452415B CN 110452415 B CN110452415 B CN 110452415B CN 201910785918 A CN201910785918 A CN 201910785918A CN 110452415 B CN110452415 B CN 110452415B
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graphene
bismaleimide resin
sponge
dispersion
composite
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CN110452415A (en
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彭庆宇
赫晓东
赵旭
周敏
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00Conditioning or physical treatment of the material to be shaped
    • B29B13/10Conditioning or physical treatment of the material to be shaped by grinding, e.g. by triturating; by sieving; by filtering
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/184Preparation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00Shaping characteristics in general
    • B29C2791/004Shaping under special conditions
    • B29C2791/006Using vacuum

Abstract

The invention discloses a preparation method of a high-dispersion graphene reinforced bismaleimide resin matrix composite material. The invention solves the problem that the graphene cannot be highly dispersed in the bismaleimide resin matrix in the prior art, expands the application range of the bismaleimide resin matrix, improves the temperature resistance of the bismaleimide resin and the mechanical property of the bismaleimide resin matrix at the same time by preparing the graphene reinforced bismaleimide high-temperature resin composite material in any proportion based on the bismaleimide resin slurry filled with the graphene, increases the competitive advantage of the bismaleimide resin matrix in the application field, and provides a novel high-dispersion preparation method for nano filling.

Description

Preparation method of high-dispersion graphene reinforced bismaleimide resin-based composite material
Technical Field
The invention belongs to the technical field of material science, and relates to a preparation method of a dispersed graphene reinforced resin matrix composite material.
Background
The composite material is different from other traditional materials, has the characteristics of multiple scales, multiple layers, multiple combinations and multiple functions, and can optimize the performance of the material through the design of the top layer to achieve the expected functional application. Advanced composite materials originated in the 50 th of the 20 th century and were valued and developed in response to the needs of advanced technical fields such as aviation, aerospace and national defense.
Bismaleimide resins (BMI) have similar flowability and moldability as typical thermoset resins and can be formed by processes similar to those used for epoxy resins; meanwhile, the BMI resin has good high temperature resistance, radiation resistance, humidity and heat resistance, low moisture absorption rate, linear expansion coefficient and other excellent characteristics, and overcomes the defects of relatively low heat resistance of epoxy resin and high pressure and high molding temperature of high-temperature resistant polyimide resin. Therefore, the bismaleimide resin is combined with the advantages of bismaleimide resin and is generally applied to the fields of aerospace and the like which need light weight and high temperature resistance.
The nanometer reinforced material has powerful promotion effect on the future development of aerospace industry due to light weight, high strength and multiple functions. And the new material graphene which obtains the Nobel prize in 2010 is more warping in the nano reinforcement family. In recent years, graphene reinforced nanocomposites have been stronger and lighter than other nanoreinforced composites, which is why graphene is one of the best candidates for composite design as reinforcement. The graphene has excellent mechanical properties and outstanding electrical and thermal properties, and provides a better choice for design, preparation and application of a structure-function integrated material in the future development of aerospace industry. To do good, the worker should first benefit his device. Although the application of graphene is wide in the future, graphene is a two-dimensional nano material and cannot be independently applied, so that the graphene is an important way for realizing application. In recent years, researches show that good and bad dispersibility of graphene in a matrix is a decisive factor influencing high and low performance of the composite material, which is also important in recent years for researching the nano composite material.
Disclosure of Invention
Aiming at the desideratum of the research on the graphene reinforced bismaleimide resin composite material and the problem of the dispersibility of the graphene in the bismaleimide resin, the invention provides a preparation method of a high-dispersion graphene reinforced bismaleimide resin composite material. The invention solves the problem that the graphene cannot be highly dispersed in the bismaleimide resin matrix in the prior art, expands the application range of the bismaleimide resin matrix, improves the temperature resistance of the bismaleimide resin and the mechanical property of the bismaleimide resin matrix at the same time by preparing the graphene reinforced bismaleimide high-temperature resin composite material in any proportion based on the bismaleimide resin slurry filled with the graphene, increases the competitive advantage of the bismaleimide resin matrix in the application field, and provides a novel high-dispersion preparation method for nano filling.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a high-dispersion 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 0.1-20 mg/ml at low temperature (below 0 ℃), and simultaneously obtaining porous graphene sponge (with the density of 0.1-20 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 0.1-30 mg/ml graphene oxide aqueous solution at low temperature (below 0 ℃), and simultaneously obtaining porous graphene oxide sponge (with the density of 0.1-30 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 a graphene reinforced bismaleimide resin matrix composite material precursor:
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-4~10-2In 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 until the graphene three-dimensional skeleton is filled;
step three, preparing high-dispersion graphene reinforced bismaleimide resin-based composite material slurry:
taking graphene sponge pre-impregnated with bismaleimide resin as a precursor, smashing the bismaleimide resin impregnated graphene sponge by using a shearing force through a stirring (800-2000 r/min) ultrasonic method to obtain bismaleimide resin slurry filled with graphene with high-proportion dispersion, uniformly mixing the bismaleimide resin slurry filled with graphene and a pure bismaleimide resin matrix, and preparing the mixture ratio of the bismaleimide resin slurry and the pure bismaleimide resin matrix according to actual requirements to obtain high-dispersion graphene reinforced bismaleimide resin matrix composite slurry;
step four, preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite material:
injecting the high-dispersion graphene reinforced bismaleimide resin matrix composite slurry prepared in the third step into a mold, removing bubbles in vacuum, controlling a temperature field to meet the curing requirement, and finally preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite after curing is completed, wherein: the curing is gradient curing, and the gradient curing conditions are as follows: curing at 160-180 ℃ for 2h, curing at 190-210 ℃ for 1 h, curing at 220-240 ℃ for 4h, and curing at 250-260 ℃ for 4 h.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, a freeze-drying method is adopted to prepare a graphene macroscopic body in advance, and a vacuum-assisted infusion molding method is adopted to prepare the graphene reinforced bismaleimide resin matrix composite material, so that the key preparation technology of the graphene reinforced bismaleimide resin matrix composite material is overcome, the key problems of uneven dispersion and agglomeration of graphene in the bismaleimide resin matrix are solved, the high-density and high-uniformity dispersion of graphene in bismaleimide resin is realized, and the high-dispersion graphene reinforced bismaleimide resin matrix composite material is obtained.
2. The preparation method realizes the preparation and microstructure regulation of the graphene nanobelt sponge reinforcement and the graphene sponge macroscopic reinforcement, and the graphene sponge with controllable density of 0.1-20 mg/ml is obtained. The graphene reinforced bismaleimide resin matrix composite material is obtained, and scanning proves that the graphene can be highly dispersed in a bismaleimide resin matrix, and the mechanical property of the bismaleimide resin matrix composite material is improved by 10-30% at the same time.
3. According to the invention, through a brand new preparation concept, the graphene three-dimensional framework is used as a dispersion body, a graphene reinforced resin matrix composite slurry precursor is prepared by adopting a vacuum infusion method, the graphene reinforced resin matrix composite slurry is prepared by adopting a high-speed stirring ultrasonic auxiliary method, and the high-dispersion graphene reinforced bismaleimide resin matrix composite is obtained after gradient curing, so that the graphene is effectively dispersed into the bismaleimide resin matrix, and meanwhile, the mechanical property of the composite is improved.
Drawings
FIG. 1 is a diagram of a graphene sponge obtained in step one of example 2;
FIG. 2 is a drawing of a graphene reinforced bismaleimide resin based composite material slurry obtained in the third step of example 2;
FIG. 3 is a micro-scanning photograph of the graphene reinforced bismaleimide resin based composite material obtained in the fourth step of example 2;
FIG. 4 is a photograph showing the mechanical properties of the graphene reinforced bismaleimide resin-based composite material 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 high-dispersion 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 the high-dispersion graphene bismaleimide resin matrix composite material slurry by a high-speed stirring ultrasonic-assisted method, and finally preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite material by a 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 0.1-20 mg/ml at low temperature (below 0 ℃), and simultaneously obtaining porous graphene sponge (with the density of 0.1-20 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 0.1-30 mg/ml graphene oxide aqueous solution at low temperature (below 0 ℃), and simultaneously obtaining porous graphene oxide sponge (with the density of 0.1-30 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 a graphene reinforced bismaleimide resin matrix composite material precursor:
placing the graphene sponge to a viscosity of 10 by using a negative pressure method-4~10-2In 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;
step three, preparing high-dispersion graphene reinforced bismaleimide resin-based composite material slurry:
taking graphene sponge pre-impregnated with bismaleimide resin as a precursor, and uniformly mixing the bismaleimide resin impregnated graphene three-dimensional skeleton with a pure bismaleimide resin matrix while smashing the bismaleimide resin impregnated graphene three-dimensional skeleton by a stirring (800-2000 r/min) ultrasonic assisted method to obtain high-dispersion graphene reinforced bismaleimide resin matrix composite precursor slurry;
step four, preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite material:
injecting the high-dispersion graphene reinforced bismaleimide resin matrix composite slurry prepared in the third step into a mold, removing bubbles in vacuum, controlling a temperature field to meet the curing requirement, and finally preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite after curing is completed, wherein: the curing is gradient curing, and the gradient curing conditions are as follows: curing at 160-180 ℃ for 2h, curing at 190-210 ℃ for 1 h, curing at 220-240 ℃ for 4h, and curing at 250-260 ℃ for 4 h.
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 fourth step, the gradient curing conditions are as follows: curing for 2 hours at 170-180 ℃; curing for 1 hour at 200-210 ℃; curing for 4 hours at 230-240 ℃; curing at 250 ℃ for 4 hours.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1
In this embodiment, the method for preparing the high-dispersion graphene reinforced bismaleimide resin matrix 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 5mg/ml at low temperature (below 0 ℃), and simultaneously obtaining porous graphene sponge (with the density of 5 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 5mg/ml graphene oxide aqueous solution at low temperature (below 0 ℃), and simultaneously obtaining porous graphene oxide sponge (with the density of 5 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 a graphene reinforced bismaleimide resin matrix composite material precursor:
placing the graphene sponge to a viscosity of10-2In the pure bismaleimide resin of Pa.S, the oven is vacuumized by a vacuum pump (10)4Pa), namely a vacuum infusion method, absorbing pure bismaleimide resin into a porous structure of the graphene sponge;
thirdly, preparing the high-dispersion graphene reinforced bismaleimide resin-based composite material slurry:
taking graphene sponge pre-impregnated with bismaleimide resin as a precursor, and uniformly mixing the graphene three-dimensional skeleton impregnated with bismaleimide resin with a pure bismaleimide resin matrix while crushing the graphene three-dimensional skeleton by a stirring (1000 r/min) ultrasonic-assisted method to obtain high-dispersion graphene reinforced bismaleimide resin matrix composite precursor slurry;
step four, preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite material:
injecting the high-dispersion graphene reinforced bismaleimide resin matrix composite slurry prepared in the third step into a mold, removing bubbles in vacuum, controlling a temperature field to meet the curing requirement, and finally preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite after curing is completed, wherein: the curing is gradient curing, and the gradient curing conditions are as follows: curing at 180 ℃ for 2h, at 210 ℃ for 1 h, at 240 ℃ for 4h and at 260 ℃ for 4 h.
In the embodiment, a freeze-drying method is adopted to prepare a graphene macroscopic body in advance, and a vacuum-assisted infusion molding method is adopted to prepare the graphene reinforced bismaleimide resin matrix composite material. The key preparation technology of the graphene reinforced bismaleimide resin matrix composite material is overcome, the key problems of uneven dispersion and agglomeration of graphene in the bismaleimide resin matrix are solved, high-density and high-uniformity dispersion of graphene in bismaleimide resin is realized, and the high-dispersion graphene reinforced bismaleimide resin matrix composite material is obtained. The preparation and microstructure regulation of the graphene nanoribbon sponge reinforcement and the graphene sponge macroscopic reinforcement are realized, and the graphene sponge with controllable density of 5mg/ml is obtained. The graphene reinforced bismaleimide resin matrix composite material is obtained, and scanning proves that the graphene can be highly dispersed in the bismaleimide resin matrix, and the mechanical property of the bismaleimide resin matrix composite material is improved by 10% compared with that of the bismaleimide resin matrix composite material.
Example 2
In this embodiment, the method for preparing the high-dispersion graphene reinforced bismaleimide resin matrix 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 1000 ℃;
step two, preparing a graphene reinforced bismaleimide resin matrix composite material precursor:
placing the graphene sponge to a viscosity of 10 by using a negative pressure method-2In the pure bismaleimide resin of Pa.S, the oven is vacuumized by a vacuum pump (10)5Pa), namely a vacuum infusion method, absorbing pure bismaleimide resin into a porous structure of the graphene sponge;
thirdly, preparing the high-dispersion graphene reinforced bismaleimide resin-based composite material slurry:
taking graphene sponge pre-impregnated with bismaleimide resin as a precursor, and uniformly mixing the graphene three-dimensional skeleton impregnated with bismaleimide 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 bismaleimide resin matrix composite precursor slurry;
step four, preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite material:
injecting the high-dispersion graphene reinforced bismaleimide resin matrix composite slurry prepared in the third step into a mold, removing bubbles in vacuum, controlling a temperature field to meet the curing requirement, and finally preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite after curing is completed, wherein: the curing is gradient curing, and the gradient curing conditions are as follows: curing at 180 ℃ for 2h, at 210 ℃ for 1 h, at 240 ℃ for 4h and at 260 ℃ for 4 h.
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 bismaleimide resin-based composite material obtained in the third step of this embodiment, and as can be seen from fig. 2, the surface of the obtained graphene-reinforced bismaleimide resin-based composite material has good flatness and formability; fig. 3 is a microscopic scanning photograph of the graphene reinforced bismaleimide resin based composite material obtained in the fourth step of the present embodiment, and as can be seen from fig. 3, graphene is uniformly dispersed in the bismaleimide resin matrix; fig. 4 is a mechanical property photograph of the graphene-reinforced bismaleimide resin-based composite material obtained in the fourth step of the present embodiment, and as can be seen from fig. 4, the mechanical property of the obtained graphene-reinforced bismaleimide resin-based composite material is improved by 20%.
In the embodiment, a freeze-drying method is adopted to prepare a graphene macroscopic body in advance, and a vacuum-assisted infusion molding method is adopted to prepare the graphene reinforced bismaleimide resin matrix composite material. The key preparation technology of the graphene reinforced bismaleimide resin matrix composite material is overcome, the key problems of uneven dispersion and agglomeration of graphene in the bismaleimide resin matrix are solved, high-density and high-uniformity dispersion of graphene in bismaleimide resin is realized, and the high-dispersion graphene reinforced bismaleimide resin matrix composite material is obtained. The preparation and microstructure regulation of the graphene nanoribbon sponge reinforcement and the graphene sponge macroscopic reinforcement are realized, and the graphene sponge with controllable density of 10mg/ml is obtained. The graphene reinforced bismaleimide resin matrix composite material is obtained, and scanning proves that the graphene can be highly dispersed in the bismaleimide resin matrix, and the mechanical property of the bismaleimide resin matrix composite material is improved by 20% at the same time.
Example 3
In this embodiment, the method for preparing the high-dispersion graphene reinforced bismaleimide resin matrix 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 800 ℃;
step two, preparing a graphene reinforced bismaleimide resin matrix composite material precursor:
placing the graphene sponge to a viscosity of 10 by using a negative pressure method-3In the pure bismaleimide resin of Pa.S, the oven is vacuumized by a vacuum pump (10)5Pa), namely a vacuum infusion method, absorbing pure bismaleimide resin into a porous structure of the graphene sponge;
thirdly, preparing the high-dispersion graphene reinforced bismaleimide resin-based composite material slurry:
taking graphene sponge pre-impregnated with bismaleimide resin as a precursor, and uniformly mixing the graphene three-dimensional skeleton impregnated with bismaleimide 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 bismaleimide resin matrix composite precursor slurry;
step four, preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite material:
injecting the high-dispersion graphene reinforced bismaleimide resin matrix composite slurry prepared in the third step into a mold, removing bubbles in vacuum, controlling a temperature field to meet the curing requirement, and finally preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite after curing is completed, wherein: the curing is gradient curing, and the gradient curing conditions are as follows: curing at 180 ℃ for 2h, at 210 ℃ for 1 h, at 240 ℃ for 4h and at 260 ℃ for 4 h.
In the embodiment, a freeze-drying method is adopted to prepare a graphene macroscopic body in advance, and a vacuum-assisted infusion molding method is adopted to prepare the graphene reinforced bismaleimide resin matrix composite material. The key preparation technology of the graphene reinforced bismaleimide resin matrix composite material is overcome, the key problems of uneven dispersion and agglomeration of graphene in the bismaleimide resin matrix are solved, high-density and high-uniformity dispersion of graphene in bismaleimide resin is realized, and the high-dispersion graphene reinforced bismaleimide resin matrix composite material is obtained. The preparation and microstructure regulation of the graphene nanoribbon sponge reinforcement and the graphene sponge macroscopic reinforcement are realized, and the graphene sponge with controllable density of 8mg/ml is obtained. The graphene reinforced bismaleimide resin matrix composite material is obtained, and scanning proves that the graphene can be highly dispersed in the bismaleimide resin matrix, and the mechanical property of the bismaleimide resin matrix composite material is improved by 15% at the same time.
Example 4
In this embodiment, the method for preparing the high-dispersion graphene reinforced bismaleimide resin matrix 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 15mg/ml at low temperature (below 0 ℃), and simultaneously obtaining porous graphene sponge (with the density of 15 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 15mg/ml graphene oxide aqueous solution at a low temperature (below 0 ℃), and simultaneously obtaining porous graphene oxide sponge (with the density of 15 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 a graphene reinforced bismaleimide resin matrix composite material precursor:
using a negative pressure method to convert graphene into graphenePlacing the sponge until the viscosity is 10-4In the pure bismaleimide resin of Pa.S, the oven is vacuumized by a vacuum pump (10)4Pa), namely a vacuum infusion method, absorbing pure bismaleimide resin into a porous structure of the graphene sponge;
thirdly, preparing the high-dispersion graphene reinforced bismaleimide resin-based composite material slurry:
taking graphene sponge pre-impregnated with bismaleimide resin as a precursor, and uniformly mixing the graphene three-dimensional skeleton impregnated with bismaleimide 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 bismaleimide resin matrix composite precursor slurry;
step four, preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite material:
injecting the high-dispersion graphene reinforced bismaleimide resin matrix composite slurry prepared in the third step into a mold, removing bubbles in vacuum, controlling a temperature field to meet the curing requirement, and finally preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite after curing is completed, wherein: the curing is gradient curing, and the gradient curing conditions are as follows: curing at 180 ℃ for 2h, at 210 ℃ for 1 h, at 240 ℃ for 4h and at 260 ℃ for 4 h.
In the embodiment, a freeze-drying method is adopted to prepare a graphene macroscopic body in advance, and a vacuum-assisted infusion molding method is adopted to prepare the graphene reinforced bismaleimide resin matrix composite material. The key preparation technology of the graphene reinforced bismaleimide resin matrix composite material is overcome, the key problems of uneven dispersion and agglomeration of graphene in the bismaleimide resin matrix are solved, high-density and high-uniformity dispersion of graphene in bismaleimide resin is realized, and the high-dispersion graphene reinforced bismaleimide resin matrix composite material is obtained. The preparation and microstructure regulation of the graphene nanoribbon sponge reinforcement and the graphene sponge macroscopic reinforcement are realized, and the graphene sponge with controllable density of 15mg/ml is obtained. The graphene reinforced bismaleimide resin matrix composite material is obtained, and scanning proves that the graphene can be highly dispersed in the bismaleimide resin matrix, and the mechanical property of the bismaleimide resin matrix composite material is improved by 30% compared with that of the bismaleimide resin matrix composite material.

Claims (4)

1. A preparation method of a high-dispersion graphene reinforced bismaleimide resin-based composite material is characterized by comprising the following steps:
step one, preparing a graphene reinforced bismaleimide resin matrix composite material precursor:
using a negative pressure method, and vacuum infusion to obtain a viscosity of 10-4~10-2Absorbing the pure bismaleimide resin of Pa & S into a graphene sponge porous structure;
step two, preparing high-dispersion graphene reinforced bismaleimide resin-based composite material slurry:
taking graphene sponge pre-impregnated with bismaleimide resin as a precursor, smashing the bismaleimide resin impregnated graphene sponge by utilizing shearing force through a stirring ultrasonic method to obtain graphene-filled bismaleimide resin slurry, and uniformly mixing the graphene-filled bismaleimide resin slurry with a pure bismaleimide resin matrix to obtain high-dispersion graphene reinforced resin matrix composite slurry, wherein the stirring rotating speed is 800-2000 r/min;
step three, preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite material:
injecting the high-dispersion graphene reinforced bismaleimide resin matrix composite slurry into a mold, removing bubbles in vacuum, controlling a temperature field to meet the curing requirement, and finally preparing the high-dispersion graphene reinforced bismaleimide resin matrix composite after curing, wherein the curing is gradient curing, and the gradient curing condition is as follows: curing at 160-180 ℃ for 2h, curing at 190-210 ℃ for 1 h, curing at 220-240 ℃ for 4h, and curing at 250-260 ℃ for 4 h.
2. The preparation method of the highly dispersed graphene reinforced bismaleimide resin based composite material as claimed in claim 1, wherein in the step one, the specific steps of absorbing pure bismaleimide 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-4~10-2Method for vacuumizing baking oven in Pa.S pure bismaleimide resin by vacuum pump, namely vacuum infusion methodPure bismaleimide resin is absorbed into the porous structure of graphene sponge.
3. The preparation method of the high dispersion 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 0.1-20 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 high dispersion 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 0.1-30 mg/ml 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.
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