CN111777838A - Method for modifying three-dimensional graphene/epoxy resin composite material through vertical graphene interface - Google Patents
Method for modifying three-dimensional graphene/epoxy resin composite material through vertical graphene interface Download PDFInfo
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Abstract
The invention relates to the technical field of chemical engineering chemistry, and particularly relates to a method for modifying a three-dimensional graphene/epoxy resin composite material by using vertical graphene. Growing vertical graphene on the surface of the three-dimensional graphene/foamed nickel by adopting a plasma chemical vapor deposition method, etching the foamed nickel by utilizing a mixed solution of ferric trichloride and hydrochloric acid to obtain vertical graphene modified three-dimensional graphene, mixing the vertical graphene modified three-dimensional graphene with epoxy resin, and curing at room temperature to obtain the vertical graphene modified three-dimensional graphene/epoxy resin composite material. The vertical graphene modified three-dimensional graphene/epoxy resin composite material disclosed by the invention has a high-quality interface phase, and the surface defects and the nano structure of the vertical graphene obviously improve the interface compatibility and the bonding force, so that the composite material has excellent mechanical properties, electric conductivity, heat conductivity and electromagnetic shielding performance, and can be widely applied to the technical fields of aerospace and high-tech industry.
Description
Technical Field
The invention relates to the technical field of chemistry and chemical engineering, in particular to a method for modifying a three-dimensional graphene/epoxy resin composite material by a vertical graphene interface.
Background
The three-dimensional graphene/epoxy resin composite material is a material compounded by three-dimensional graphene and epoxy resin, and has good mechanical property, corrosion resistance, radiation resistance and high mechanical property; meanwhile, the conductive film has special conductivity, heat conductivity, infrared thermal property and electromagnetic shielding property. Therefore, the three-dimensional graphene/epoxy resin composite material has wide application prospects in the fields of aerospace, oceans, automobile industry, sensing, electronic industry, chemical engineering and medical treatment and the like.
Composite materials generally consist of a reinforcing phase (filler), a matrix phase (polymer) and their interphase (interphase), each of which has unique structures, properties and effects. The base surface is a very important microstructure unit of the composite material, is a bridge for connecting the reinforcing phase and the matrix phase, is also a stress transmission unit, and plays a very important role in the performance of the composite material. Graphene is a single layer of carbon atom material sp2The hybridized hexagonal lattice honeycomb structure has the electron mobility exceeding 20000cm2V-1S-1The specific surface area is up to 2630m2The thermal conductivity is about 3080-5150W/m.K. The three-dimensional graphene can be prepared by using foamed nickel as a template and adopting a chemical vapor deposition technology, and can be used as a reinforcing phase and epoxy resin to prepare a composite material. In the three-dimensional graphene/epoxy resin composite material, because the three-dimensional graphene is generally prepared by a chemical vapor deposition technology, the surface is smooth, the oxygen content is low, and the wettability of the three-dimensional graphene serving as a reinforcing phase with an epoxy resin matrix is poor, the bonding force of an interface between the three-dimensional graphene and the epoxy resin matrix is weak, a large number of structural defects exist at the interface, the stress cannot be effectively transferred, the interface thermal resistance is high, the overall mechanical property, the electrical property, the heat conducting property and the like of the composite material are caused, and the application of the three-dimensional graphene/epoxy resin composite material in the material field and the industrial field is limited. Therefore, by modifying the surface structure and the group of three-dimensional grapheneTherefore, improving the interface quality of the three-dimensional graphene and the epoxy resin, and further improving the interface bonding strength and the heat conduction efficiency of the three-dimensional graphene and the epoxy resin is a key scientific and technical problem for realizing the application of the three-dimensional graphene and the epoxy resin in the high-tech field.
The vertical graphene is prepared by adopting a plasma chemical vapor deposition technology, can grow on the surface of the three-dimensional graphene to form a vertically oriented nano structure, can effectively regulate and control the defect structure and the oxygen content of the surface of the vertical graphene, and has excellent compatibility with epoxy resin. Therefore, the interface environment between the vertical graphene modified graphene and the epoxy resin is introduced into the surface of the three-dimensional graphene, more interface phases are introduced, the interface bonding force is improved, and the mechanical property, the electrical property, the heat-conducting property and the like of the composite material are further improved. Therefore, the vertical graphene is an ideal three-dimensional graphene and epoxy resin interface modification material. However, no relevant literature and patent application of the vertical graphene modified three-dimensional graphene and epoxy resin composite material is found at present.
The patent (application number 201910816268.5) discloses a method for preparing a graphene interface modified carbon fiber/epoxy resin composite material, which is characterized in that graphene slurry is coated on the surface of carbon fiber and is dried and cured by a mold to prepare the composite material, and the defects that the graphene slurry is physically coated and has poor uniformity and bonding force are overcome. The patent (application No. 201610043545.X) discloses a preparation method of a vertically-oriented graphene sheet/high polymer thermal interface material, which comprises the steps of utilizing liquid-phase stripped graphene oxide to reduce the graphene into graphene at high temperature, preparing a continuous graphene film by adopting a hot-press molding process, finally infiltrating the graphene film into a polymer by adopting a manual or mechanical method, preparing a cylinder by utilizing a coreless paper rolling process, curing at high temperature, and cutting into a required shape. The defects that the high-temperature reduction cannot effectively remove oxygen-containing functional groups, the thermal conductivity of the graphene is completely recovered, the technological requirement of the hot-press molding of the ultra-long continuous graphene film is high, and the operation difficulty of technical personnel is very high. The patent (application number 201810407789.0) discloses a preparation method of a novel high-thermal-conductivity graphene or graphite film/carbon fiber composite material, which comprises the steps of punching a graphene film in advance by a stamping technology to obtain a net-shaped graphene film, and then soaking the graphene film in epoxy resin; the graphene film and the carbon fiber cloth prepreg are sequentially laminated, and the carbon fiber needling preform is driven into the composite board by using an ultrasonic impact gun. The defects are that the inherent interface incompatibility problem between the carbon fiber and the graphene and the epoxy resin matrix is not modified, and the two reinforcing phases and the matrix phase are simply physically superposed and mechanically treated. Penqing space Boshi paper (title: cross-scale design of composite material reinforcement and interface reinforcement mechanism research thereof) discloses a preparation method of graphene oxide modified carbon fiber, which takes dendritic PAMAM molecules as a medium, and grafts graphene oxide onto the surface of carbon fiber through chemical bonds to prepare the graphene oxide/carbon fiber cross-scale reinforcement. The defects that the whole process needs two-step amidation grafting reaction, and the grafting density depends on the concentrated nitrification treatment of carbon fiber in the initial step, so that the mechanical strength of the carbon fiber is damaged, and the environmental pollution is caused. The patent (CN201911257312.X) discloses a PDMS-based graphene heat-conducting composite material and a preparation method and application thereof, wherein the method is to perform non-covalent modification on graphene by adopting a hyperbranched polyethylene copolymer of terminal branched-chain grafted polysilsesquioxane, so that the compatibility of the graphene and polydimethylsiloxane is improved, and the heat-conducting property of the flexible heat-conducting composite material is further improved. The method has the disadvantages that the modification method in the patent needs to adopt ultrasonic dispersion and is not suitable for the interface modification of the three-dimensional graphene. The patent (CN201210574175.4) discloses a light flexible graphene/polymer foam electromagnetic shielding material and its preparation and application, the method is to mix the graphene/metal foam composite with the high molecular polymer precursor, so that the surface of the graphene/metal foam composite is coated with a layer of high molecular polymer precursor; and curing the high-molecular polymer precursor in the mixture, and then dissolving and removing the porous metal substrate to obtain the light and flexible graphene/polymer. The defects are that the surface of the graphene is not subjected to any modification treatment, and the problem of interface incompatibility between the graphene and a polymer matrix phase is not effectively solved.
Disclosure of Invention
The technical problem solved by the invention is as follows: the invention overcomes the defects in the prior art, and provides a method for modifying a three-dimensional graphene and epoxy resin interface, which utilizes the direct production of vertical graphene on the surface of the three-dimensional graphene to improve the compatibility and the bonding force of a reinforcing phase and a polymer matrix phase, effectively improve the mechanical property, the electric conductivity, the infrared heating property, the heat conduction property, the electromagnetic shielding property and the like of a composite material, and has the advantages of simplicity, easy amplification and low cost.
The technical scheme of the invention is as follows: a method for modifying a three-dimensional graphene/epoxy resin composite material through a vertical graphene interface comprises the following steps:
the method comprises the following steps: growing graphene by adopting ethanol as a carbon source and adopting Ar/H (argon/hydrogen) in a chemical vapor deposition method2As carrier gas, using foam nickel as graphene growth carrier, the foam nickel is Ar/H at furnace temperature of 850-2Growing for 20-40min at the flow rate of 180/20sccm to obtain three-dimensional graphene;
step two: adopting a plasma chemical vapor deposition technology, taking acetylene as a carbon source, taking the foamed nickel loaded three-dimensional graphene in the step 1 as a growth carrier of the vertical graphene, and performing reaction at the plasma power of 80-120W, the furnace temperature of 650-750 ℃ and CH4/H2The reaction time is 80-150min under the environment with the flow rate of 1/4sccm, and then the three-dimensional graphene modified by the foam nickel loaded vertical graphene is obtained after the three-dimensional graphene is naturally cooled to room temperature and taken out;
step three: the etching process is carried out by mixing ferric trichloride with hydrochloric acid.
Dissolving 0.5-5 g of ferric trichloride in more than 50mL of 3mol/L hydrochloric acid aqueous solution, etching at room temperature for 24 hours, taking out, washing with clear water until the pH value is neutral, and naturally airing, or heating and drying at the temperature of below 100 ℃ to obtain self-supporting vertical graphene modified three-dimensional graphene;
dissolving 0.5-5 g of ferric trichloride in more than 50mL of 3mol/L hydrochloric acid aqueous solution, etching for 5-12 hours at 40-80 ℃, taking out, washing with clear water until the pH value is neutral, and naturally airing, or heating and drying at the temperature of below 100 ℃ to obtain self-supporting vertical graphene modified three-dimensional graphene;
step four: placing a self-supporting vertical graphene modified three-dimensional graphene material in a mold, and mixing epoxy resin, a curing agent and a defoaming agent according to a ratio of 2-5: 1: mixing the components according to the mass ratio of 0.01, and naturally curing to obtain the composite material.
The further technical scheme of the invention is as follows: the curing agent is polyether amine, polythiol, aliphatic polyamine, aromatic polyamine, polyamide and tertiary amine.
The further technical scheme of the invention is as follows: the defoaming agent is dimethyl silicone oil.
The further technical scheme of the invention is as follows: the thickness of the mould is consistent with that of the three-dimensional graphene.
Effects of the invention
The invention has the technical effects that: compared with the prior art, the invention has the following beneficial effects:
according to the invention, the three-dimensional graphene/epoxy resin composite material interface is modified by the vertical graphene, the vertical graphene is directly grown on the surface of the three-dimensional graphene by using the energy of plasma, and the bonding force is stronger compared with the existing physical coating technology; compared with the three-dimensional graphene, the surface of the vertical graphene is in a latticed nano structure, and the surface of the sheet layer has more defect structures, so that the compatibility between the three-dimensional graphene and epoxy resin and the interface bonding force can be improved, the load transfer capacity of the interface is obviously improved, and the interface thermal resistance is reduced; the vertical graphene is directly grown on the surface of the three-dimensional graphene by using a plasma chemical vapor deposition technology, and compared with the existing multistep organic reaction modification route, the technology provided by the invention is simple to operate and can be prepared in a large scale. Therefore, the modification method can obviously improve the mechanical property, the electric conductivity and the heat conductivity of the composite material. Compared with an unmodified three-dimensional graphene/epoxy resin composite material, the tensile strength of the composite material modified by the vertical graphene is improved from 65MPa to 97MPa, the electric conductivity is improved from 209S/m to 302S/m, and the thermal conductivity is improved from 1.83W/m.K to 2.61W/m.K.
Drawings
Fig. 1 is a schematic diagram of a plasma chemical vapor deposition technique for growing vertical graphene on a three-dimensional graphene surface;
fig. 2 is a scanning electron microscope picture of low and high magnification of vertical graphene, wherein (a) is low magnification, (b) is high magnification,
FIG. 3 is a Raman spectrum of three-dimensional graphene
FIG. 4 is a scanning electron microscope picture of vertical graphene modified three-dimensional graphene loaded with nickel foam
Fig. 5 is a scanning electron microscope picture of vertical graphene grown on a three-dimensional graphene surface;
FIG. 6 is a Raman spectrum of vertical graphene
FIG. 7 is an electrical property test chart of a three-dimensional graphene/epoxy resin composite material (before modification) and a vertical graphene modified three-dimensional graphene/epoxy resin composite material (after modification)
FIG. 8 is a bar graph of conductivity for a three-dimensional graphene/epoxy composite (before modification) and a vertical graphene modified three-dimensional graphene/epoxy composite (after modification)
FIG. 9 is a bar graph of tensile strength of pure epoxy, three-dimensional graphene/epoxy composite (before modification) and vertical graphene modified three-dimensional graphene/epoxy composite (after modification)
FIG. 10 is a graph comparing thermal conductivity values of an unmodified three-dimensional graphene/epoxy composite (which is a modified control group) and a vertical graphene modified three-dimensional graphene/epoxy composite (which is a modified experimental group)
Detailed Description
Referring to fig. 1 to 10, a method for modifying a three-dimensional graphene/epoxy resin composite material by a vertical graphene interface includes the following steps:
1. preparing three-dimensional graphene: growing graphene by adopting ethanol as a carbon source and adopting Ar/H (argon/hydrogen) in a chemical vapor deposition method2As carrier gas, foamed nickel carrier, Ar/H at 850-900 deg.C2The flow rate is 180/20sccm, and the growth time is 20-40 min.
2. Growth of vertical graphene on the surface of three-dimensional graphene: by using plasma chemical vapor deposition techniqueUsing acetylene as a carbon source, using the foamed nickel loaded graphene in the step 1 as a carrier, using the plasma power of 80-120W, reacting at the temperature of 650-750 ℃, and performing reaction on CH4/H2The flow rate is 1/4sccm, the reaction time is 80-150min, and the furnace body is naturally cooled to room temperature and then taken out.
3. Preparing a self-supporting vertical graphene modified three-dimensional graphene material: by adopting a mixed solution etching process of ferric trichloride and hydrochloric acid, 0.5-5 g of ferric trichloride is dissolved in more than 50mL of 3mol/L hydrochloric acid aqueous solution, is etched at room temperature for 24 hours or at 40-80 ℃ for 5-12 hours, is taken out and is washed by clear water until the pH value is neutral, and is naturally dried or is heated and dried at the temperature of below 100 ℃.
4. Preparing a vertical graphene interface modified three-dimensional graphene/epoxy resin composite material: placing a self-supporting vertical graphene modified three-dimensional graphene material in a mold, and mixing epoxy resin, a curing agent and a defoaming agent according to a ratio of 5-2: 1: mixing the components according to the mass ratio of 0.01, and naturally curing to obtain the composite material.
Referring to the attached figure 2, it can be seen that a high-power scanning electron microscope picture shows that the three-dimensional graphene has a smooth surface, poor interface compatibility with epoxy resin and weak binding force, the epoxy resin is not easily attached to the smooth graphene surface, and the composite material has defects such as cavities easily formed at the interface, so that the roughness of the graphene surface is improved, and the interface compatibility and the binding force between the graphene surface and the epoxy resin can be remarkably improved by introducing a defect structure, thereby improving the performance of the composite material. Referring to fig. 3, the raman spectrum shows that the three-dimensional graphene has no D band peak of the defect on the surface, which indicates that the three-dimensional graphene is high-quality crystalline graphene, and the surface has no structural defect, so that the interface compatibility with the epoxy resin is poor. See FIG. 6, at 1354cm compared to three-dimensional graphene-1A D band peak with defects appears, which shows that the vertical graphene has more surface defects, and is beneficial to improving the compatibility of the vertical graphene and epoxy resin, so that the interface phase quality is improved, and the binding force is improved. Referring to fig. 7, a direct current I-V curve shows that the conductivity of the composite material is significantly improved after the vertical graphene modification. Referring to fig. 8, the conductivity of the unmodified three-dimensional graphene/epoxy resin composite material is 209S/m, and the material is modified by the vertical grapheneAfter that, the conductivity increased to 302S/m, which is significantly higher than that of the unmodified control group. Referring to fig. 9, the tensile strength of the unmodified three-dimensional graphene/epoxy resin composite material is 65MPa, and after the vertical graphene is modified, the tensile strength is increased to 97MPa, which is significantly higher than that of an unmodified control group. Referring to fig. 10, the thermal conductivity of the unmodified three-dimensional graphene/epoxy resin composite material is 1.83W/m · K, and after the vertical graphene is modified, the thermal conductivity is improved to 2.61W/m · K, which is significantly higher than that of the unmodified control group.
The process is described in further detail below:
1. the method comprises the following steps of providing a material for growing vertical graphene on the surface of self-supporting three-dimensional graphene:
the method for obtaining the three-dimensional graphene adopts a chemical vapor deposition method, ethanol is used as a carbon source to grow the graphene, and Ar/H is adopted for supplying the ethanol2And in a bubbling mode, graphene is obtained on the surface of the foamed nickel by adjusting the growth temperature, the growth time and the flow rate of the carrier gas. The foamed nickel is firstly prepared by using Ar/H2As carrier gas, reducing for 20min at 100/100sccm and 1000 ℃; then adjusting the temperature to 875 ℃ and adjusting Ar/H2The flow rate is 180/20sccm, ethanol is supplied by a bubbling method, and the graphene growth time is 20 min.
Obtaining vertical graphene by adopting a plasma chemical vapor deposition method, taking the foamed nickel loaded graphene prepared in the steps as a carrier, taking acetylene as a carbon source, increasing the reaction temperature to 700 ℃ within 50min with the plasma power of 100W, and performing reaction at CH4/H2The flow rate is 1/4sccm, the reaction time of the vertical graphene is 100min, and the furnace body is naturally cooled to room temperature and then taken out.
The obtained self-supporting vertical graphene modified three-dimensional graphene material is etched by adopting a mixed solution of ferric trichloride and hydrochloric acid. Cutting the three-dimensional graphene material modified by the vertical graphene loaded on the surface of the foamed nickel prepared by the plasma chemical vapor deposition technology into the dimensions of 1 centimeter multiplied by 5 centimeters multiplied by 0.16 centimeters; preparing a mixed solution of ferric trichloride and hydrochloric acid, dissolving 1 g of ferric trichloride in 50mL of 3mol/L hydrochloric acid aqueous solution, etching at room temperature for 24 hours, and heating and drying below 50 ℃ for 12 hours.
2. Preparing a vertical graphene interface modified three-dimensional graphene/epoxy resin composite material:
preparing an epoxy resin mixture, weighing 5g of epoxy resin E51, 2.5g of curing agent D-230 and 0.025g of defoaming agent simethicone, mechanically stirring for 30min, and ultrasonically defoaming for 30min to obtain a mixture; placing the self-supporting vertical graphene modified three-dimensional graphene material in a mold, wherein the depth of the mold is 1.6 mm, the thickness of the mold is consistent with that of the three-dimensional graphene, slowly adding the mixture into the mold, uniformly soaking the three-dimensional graphene in the epoxy resin mixture, and naturally curing at room temperature of 20 ℃ for 36 hours to obtain the vertical graphene interface modified three-dimensional graphene/epoxy resin composite material.
Claims (4)
1. A method for modifying a three-dimensional graphene/epoxy resin composite material through a vertical graphene interface is characterized by comprising the following steps:
the method comprises the following steps: growing graphene by adopting ethanol as a carbon source and adopting Ar/H (argon/hydrogen) in a chemical vapor deposition method2As carrier gas, using foam nickel as graphene growth carrier, the foam nickel is Ar/H at furnace temperature of 850-2Growing for 20-40min at the flow rate of 180/20sccm to obtain three-dimensional graphene;
step two: adopting a plasma chemical vapor deposition technology, taking acetylene as a carbon source, taking the foamed nickel loaded three-dimensional graphene in the step 1 as a growth carrier of the vertical graphene, and performing reaction at the plasma power of 80-120W, the furnace temperature of 650-750 ℃ and CH4/H2The reaction time is 80-150min under the environment with the flow rate of 1/4sccm, and then the three-dimensional graphene modified by the foam nickel loaded vertical graphene is obtained after the three-dimensional graphene is naturally cooled to room temperature and taken out;
step three: the etching process is carried out by mixing ferric trichloride with hydrochloric acid.
Dissolving 0.5-5 g of ferric trichloride in more than 50mL of 3mol/L hydrochloric acid aqueous solution, etching at room temperature for 24 hours, taking out, washing with clear water until the pH value is neutral, and naturally airing, or heating and drying at the temperature of below 100 ℃ to obtain self-supporting vertical graphene modified three-dimensional graphene;
dissolving 0.5-5 g of ferric trichloride in more than 50mL of 3mol/L hydrochloric acid aqueous solution, etching for 5-12 hours at 40-80 ℃, taking out, washing with clear water until the pH value is neutral, and naturally airing, or heating and drying at the temperature of below 100 ℃ to obtain self-supporting vertical graphene modified three-dimensional graphene;
step four: placing a self-supporting vertical graphene modified three-dimensional graphene material in a mold, and mixing epoxy resin, a curing agent and a defoaming agent according to a ratio of 2-5: 1: mixing the components according to the mass ratio of 0.01, and naturally curing to obtain the composite material.
2. The method for vertical graphene interface modification of the three-dimensional graphene/epoxy resin composite material according to claim 1, wherein the curing agent is polyether amine, polythiol, aliphatic polyamine, aromatic polyamine, polyamide and tertiary amine.
3. The method for vertical graphene interface modification of the three-dimensional graphene/epoxy resin composite material according to claim 1, wherein the defoaming agent is dimethicone.
4. The method of claim 1, wherein the mold conforms to the thickness of the three-dimensional graphene.
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| CN114410069A (en) * | 2021-12-24 | 2022-04-29 | 南京航空航天大学 | Three-dimensional graphene-shape memory polymer composite material and preparation method thereof |
| CN114410069B (en) * | 2021-12-24 | 2023-07-11 | 南京航空航天大学 | Three-dimensional graphene-shape memory polymer composite material and preparation method thereof |
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