CN111073222A - Preparation method of graphene oxide/carbon nanotube reinforced glass fiber laminated plate - Google Patents
Preparation method of graphene oxide/carbon nanotube reinforced glass fiber laminated plate Download PDFInfo
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Abstract
The invention discloses a preparation method of a graphene oxide/carbon nanotube reinforced glass fiber laminated plate, which comprises the following steps: (1) preparing a graphene oxide organic solution; (2) adding epoxy resin into the graphene oxide organic solution to obtain a graphene oxide epoxy resin solution; (3) ball-milling the graphene oxide epoxy resin solution, adding a curing agent, stirring and drying to obtain a graphene oxide/epoxy resin nanocomposite; (4) adding the carbon nano tube into a polyvinylpyrrolidone aqueous solution to obtain a coating solution, dip-coating the coating solution on the surface of the glass fiber cloth and drying to obtain the carbon nano tube modified glass fiber cloth; (5) coating the graphene oxide/epoxy resin nano composite material on the surface of the carbon nano tube modified glass fiber cloth, rolling by using a compression roller, repeatedly paving the carbon nano tube modified glass fiber cloth to the required number of layers by using a laminated plate forming process, pressurizing, and finally drying in an oven to obtain the graphene oxide/carbon nano tube reinforced glass fiber laminated plate.
Description
Technical Field
The invention relates to the technical field of polymer-based composite materials, in particular to a preparation method of a graphene oxide/carbon nanotube reinforced glass fiber laminated plate.
Background
The glass fiber reinforced resin-based composite material laminated plate has the characteristics of high specific strength and specific stiffness, good structural size stability, good fatigue resistance, convenience in molding, low price and the like, and is widely applied to the fields of high-speed rails, automobiles, aerospace and the like. In addition to the strength of the laminate being dependent on the properties of the glass fibers, the matrix resin properties and the interfacial bond strength between the resin and the fibers of the laminate have a direct effect on the mechanical properties of the laminate.
The glass fiber has smooth surface, less active functional groups and poor wettability with an epoxy resin matrix, and the strength of the laminated plate after forming is influenced. Some scholars improve the interface bonding strength between the glass fiber and the epoxy resin by using acid to carry out surface treatment on the glass fiber; some scholars increase the surface roughness of the glass fibers by chemically treating the glass fibers, so as to improve the interface bonding effect of the glass fibers and the resin. It can be seen that improving the surface properties of the glass fibers can increase the interfacial bond strength between the glass fibers and the resin.
Researchers improve the mechanical property of epoxy resin and the wettability of glass fiber by adding nano materials, and graphene oxide and carbon nanotubes are taken as novel carbon nano materials, and various excellent properties of the graphene oxide and the carbon nanotubes have become hot spots for research of composite materials.
Disclosure of Invention
The invention aims to provide a glass fiber laminated plate with firm interface bonding.
The invention is realized by the following technical scheme:
a preparation method of a graphene oxide/carbon nanotube reinforced glass fiber laminated plate comprises the following steps:
1) adding graphene oxide into an organic solvent, and carrying out ultrasonic treatment to obtain a graphene oxide organic solution;
(2) adding epoxy resin into the graphene oxide organic solution to obtain a mixed solution, heating the mixed solution and stirring the mixed solution until all the organic solvent in the mixed solution is evaporated to obtain a graphene oxide epoxy resin solution;
(3) placing the graphene oxide epoxy resin solution into a ball milling barrel for ball milling treatment, drying and exhausting the ball-milled graphene oxide epoxy resin solution in a vacuum oven, slowly adding a curing agent into the exhausted graphene oxide epoxy resin solution while stirring to obtain a mixed solution, and placing the mixed solution in the oven for drying to obtain a graphene oxide/epoxy resin nanocomposite;
(4) adding water into polyvinylpyrrolidone, stirring until the mixture is dissolved, adding carbon nano tubes into polyvinylpyrrolidone aqueous solution, carrying out ultrasonic treatment to obtain coating solution, fully soaking the coating solution on the surface of glass fiber cloth, and then placing the glass fiber soaked with the coating solution in an oven for drying to obtain carbon nano tube modified glass fiber cloth;
(5) coating the obtained graphene oxide/epoxy resin nano composite material on the surface of carbon nano tube modified glass fiber cloth, repeatedly rolling the glass fiber cloth by using a press roller to fully impregnate the graphene oxide/epoxy resin nano composite material, repeatedly paving the glass fiber cloth to the required number of layers by using a laminated plate forming process, vacuumizing and pressurizing the paved laminated plate by using a vacuum bag once, continuously pressurizing the laminated plate on a press machine, and finally drying the laminated plate in an oven to obtain the graphene oxide/carbon nano tube reinforced glass fiber laminated plate.
Further, the organic solvent in the step (1) is any one of ethanol, dimethyl amide, N-methyl-2-pyrrolidone, tetrahydrofuran and acetone.
Further, in the step (1), the graphene oxide adopts multilayer graphene oxide, the purity of the graphene oxide is 95%, the thickness of the graphene oxide is 3.4-8nm, the diameter of each layer is 5-50 μm, and the number of layers is 5-10.
Further, in the step (2), the epoxy resin is any one of novolac epoxy resin, bisphenol a epoxy resin, bisphenol F epoxy resin and 862 epoxy resin, and the mass percentage of the graphene oxide and the epoxy resin is 0.1 wt% to 0.5 wt%.
Further, the curing agent in the step (3) is an amine curing agent cured at normal temperature, and the volume ratio of the epoxy resin to the curing agent is 10: 1.
Further, the carbon nano tube in the step (4) is a multi-wall carbon nano tube, the purity of the carbon nano tube is more than 95%, the inner diameter of the carbon nano tube is 3-5nm, the outer diameter of the carbon nano tube is 8-15nm, and the length of the carbon nano tube is 50 microns.
Further, the glass fiber cloth in the step (4) is any one of a glass fiber unidirectional fabric, a glass fiber plain fabric, a glass fiber twill fabric and a glass fiber satin fabric.
Further, the polyvinylpyrrolidone aqueous solution in the step (4) is a dispersant for the carbon nanotube, the concentration of the dispersant is 0.5mg/ml to 2mg/ml, the dispersant has a de-agglomeration effect on the carbon nanotube and can also enhance the interaction between the carbon nanotube and the epoxy resin interface, and the mass percentage of the carbon nanotube to the polyvinylpyrrolidone aqueous solution is 0.05 wt% to 0.1 wt%.
Further, the forming process of the laminated plate in the step (5) comprises hand lay-up forming, vacuum bag pressure forming and cold press forming.
Further, in the step (5), the vacuum bag is vacuumized and pressurized to 0.1-0.5 MPa (the laminated plate is placed in the vacuum bag, the vacuum bag is vacuumized, and the atmosphere has pressure on the laminated plate), and then the laminated plate is pressurized to 2-5 MPa on a press machine and maintained for 1-2 hours.
The invention has the beneficial effects that:
according to the invention, graphene oxide is added into epoxy resin to improve the interface bonding strength between the epoxy resin and the glass fiber, and the carbon nano tube is used for improving the surface performance of the glass fiber to improve the interface bonding strength between the glass fiber and the resin. The graphene oxide/carbon nano tube reinforced glass fiber laminated plate is prepared by the process method of hand lay-up forming, vacuum bag pressure forming and cold press forming, and has the advantages of high product strength, firm interface bonding, simple preparation method and good practicability.
Drawings
FIG. 1 is a schematic view of an interface of a graphene oxide/carbon nanotube reinforced glass fiber laminate;
wherein: 1. epoxy resin 2, graphene oxide 3, glass fiber cloth 4 and carbon nanotubes.
Detailed Description
The invention will be further illustrated in detail with reference to the following specific examples:
example 1
Adding 500g of novolac epoxy resin into a normal-temperature amine curing agent, mixing the novolac epoxy resin with the curing agent according to a volume ratio of 10:1, coating the novolac epoxy resin on the surface of the glass fiber unidirectional fabric, repeatedly rolling the glass fiber unidirectional fabric by using a compression roller to fully impregnate the novolac epoxy resin, repeatedly paving the novolac epoxy resin to a required number of layers, vacuumizing and pressurizing the laminated board to 0.1MPa by using a vacuum bag for one time, pressurizing to 5MPa on a press machine, maintaining for 2 hours, and finally drying the laminated board in an oven at 70 ℃ for 5 hours to obtain the glass fiber laminated board.
The bending strength of the glass fiber laminated plate is tested according to the GB/T1449-2005 standard, and the bending modulus of the laminated plate is 22GPa, and the bending strength is 274 MPa. The interface bonding strength belongs to the microscopic concept, and is increased by the increase of the bending strength.
Example 2
(1) Adding 0.5g of graphene oxide with the purity of 95%, the number of layers of 5-10 layers, the thickness of 3.4-8nm and the sheet diameter of 5-50 mu m into ethanol, and carrying out ultrasonic treatment for 0.5 hour to obtain a graphene oxide ethanol solution;
(2) adding novolac epoxy resin into the graphene oxide ethanol solution to obtain a mixed solution, wherein the mass percentage of the graphene oxide to the novolac epoxy resin is 0.1 wt%, heating the mixed solution to 80 ℃, and simultaneously stirring the mixed solution for 1.5 hours by using a constant-temperature magnetic stirrer until all ethanol in the mixed solution is evaporated to obtain the graphene oxide novolac epoxy resin solution;
(3) putting the graphene oxide novolac epoxy resin solution into a ball milling barrel, ball milling for 1.5 hours at the rotating speed of 200rpm, drying the ball-milled graphene oxide novolac epoxy resin solution in a vacuum oven for 0.5 hour for exhausting, slowly adding a normal-temperature amine curing agent into the exhausted graphene oxide novolac epoxy resin solution, mixing the novolac epoxy resin and the curing agent according to the volume ratio of 10:1, stirring for 10 minutes to obtain a mixed solution, and drying the mixed solution in an oven at 70 ℃ for 5 hours to obtain a graphene oxide/novolac epoxy resin nanocomposite material with the mass ratio of 0.1 wt%;
(4) coating the graphene oxide/novolac epoxy resin nano composite material on the surface of the glass fiber unidirectional fabric, repeatedly rolling the glass fiber unidirectional fabric by using a compression roller to fully impregnate the graphene oxide/novolac epoxy resin nano composite material, repeatedly paving the composite material to the required number of layers by using a laminated plate forming process, vacuumizing and pressurizing the laminated plate to 0.1MPa by using a vacuum bag for one time, pressurizing to 5MPa on a press machine, maintaining for 2 hours, and finally drying the laminated plate in an oven at 70 ℃ for 5 hours to obtain the graphene oxide reinforced glass fiber laminated plate.
The bending strength of the obtained glass fiber laminated plate is tested according to the GB/T1449-2005 standard, the bending modulus of the graphene oxide reinforced glass fiber laminated plate is 32GPa, and the bending strength is 387MPa, and the bending modulus and the bending strength of the graphene oxide reinforced glass fiber laminated plate in the example 2 are respectively improved by 45% and 41% compared with the example 1.
Example 3
(1) Adding 0.5g of graphene oxide with the purity of 95%, the number of layers of 5-10 layers, the thickness of 3.4-8nm and the sheet diameter of 5-50 mu m into dimethyl amide, and carrying out ultrasonic treatment for 0.5 hour to obtain a graphene oxide dimethyl amide solution;
(2) adding bisphenol A epoxy resin into a graphene oxide dimethyl amide solution to obtain a mixed solution, wherein the mass percentage of the graphene oxide to the bisphenol A epoxy resin is 0.1 wt%, heating the mixed solution to 80 ℃, and simultaneously stirring the mixed solution for 1 hour by using a constant-temperature magnetic stirrer until all dimethyl amide in the mixed solution is evaporated to obtain a graphene oxide bisphenol A epoxy resin solution;
(3) putting the graphene oxide bisphenol A epoxy resin solution into a ball milling barrel, ball milling for 1.5 hours at the rotating speed of 200rpm, then drying the ball-milled graphene oxide bisphenol A epoxy resin solution in a vacuum oven for 0.5 hour for exhausting, slowly adding a normal-temperature amine curing agent into the exhausted graphene oxide bisphenol A epoxy resin solution, mixing the bisphenol A epoxy resin and the curing agent according to the volume ratio of 10:1, stirring for 10 minutes to obtain a mixed solution, and drying the mixed solution in the oven at 70 ℃ for 5 hours to obtain the graphene oxide/bisphenol A epoxy resin nanocomposite with the mass percentage of 0.1 wt%;
(4) adding water into polyvinylpyrrolidone, magnetically stirring until the concentration is 2mg/ml, adding 3g of multi-walled carbon nanotubes with the purity of more than 95%, the inner diameter of 3-5nm, the outer diameter of 8-15nm and the length of 50 mu m into a polyvinylpyrrolidone aqueous solution, wherein the mass percentage of the multi-walled carbon nanotubes to the polyvinylpyrrolidone aqueous solution is 0.05 wt%, carrying out ultrasonic treatment for 0.5 hour to obtain a coating solution, fully dip-coating the coating solution on the surface of the glass fiber plain woven fabric, and then placing the glass fiber plain woven fabric dipped with the coating solution into an oven to dry for 0.5 hour at 40 ℃ to obtain the carbon nanotube modified glass fiber plain woven fabric;
(5) coating the obtained graphene oxide/bisphenol A epoxy resin nanocomposite on the surface of a carbon nanotube modified glass fiber plain woven fabric, repeatedly rolling the glass fiber plain woven fabric by using a press roller to fully impregnate the graphene oxide/bisphenol A epoxy resin nanocomposite, repeatedly paving the laminated board to the required number of layers by using a laminated board forming process, vacuumizing and pressurizing the laminated board to 0.1MPa by using a vacuum bag for one time, pressurizing the laminated board to 2MPa on a press machine, maintaining the pressure for 1 hour, and finally drying the laminated board in an oven at 70 ℃ for 5 hours to obtain the laminated board structure shown in figure 1, wherein 1 represents epoxy resin, 2 represents graphene oxide, 3 represents glass fiber cloth, and 4 represents carbon nanotubes.
The bending strength of the obtained glass fiber laminated plate is tested according to the GB/T1449-2005 standard, and the bending modulus of the graphene oxide/carbon nanotube reinforced glass fiber laminated plate is 34GPa, and the bending strength is 480 MPa. It can be seen that the flexural modulus and flexural strength of the graphene oxide/carbon nanotube reinforced glass fiber laminate in example 3 were improved by 54% and 75% respectively over example 1.
Example 4
(1) Adding 0.5g of graphene oxide with the purity of 95%, the number of layers of 5-10 layers, the thickness of 3.4-8nm and the sheet diameter of 5-50 mu m into ethanol, and carrying out ultrasonic treatment for 0.5 hour to obtain a graphene oxide ethanol solution;
(2) adding bisphenol F epoxy resin into a graphene oxide ethanol solution to obtain a mixed solution, wherein the mass percentage of the graphene oxide to the bisphenol F epoxy resin is 0.5 wt%, heating the mixed solution to 80 ℃, and simultaneously stirring the mixed solution for 2 hours by using a constant-temperature magnetic stirrer until all ethanol in the mixed solution is evaporated to obtain a graphene oxide bisphenol F epoxy resin solution;
(3) putting the graphene oxide bisphenol F epoxy resin solution into a ball milling barrel, carrying out ball milling for 2 hours at the rotating speed of 200rpm, drying the ball-milled graphene oxide bisphenol F epoxy resin solution in a vacuum oven for 0.5 hour for exhausting, slowly adding a normal-temperature amine curing agent into the exhausted graphene oxide bisphenol F epoxy resin solution, mixing the bisphenol F epoxy resin and the curing agent according to the volume ratio of 10:1, stirring for 10 minutes at the same time, and drying the mixed solution in an oven at 70 ℃ for 7 hours to obtain the graphene oxide/bisphenol F epoxy resin nanocomposite with the mass percentage of 0.5 wt%;
(4) adding water into polyvinylpyrrolidone, magnetically stirring until the concentration is 1mg/ml, adding 3g of multi-walled carbon nanotubes with the purity of more than 95%, the inner diameter of 3-5nm, the outer diameter of 8-15nm and the length of 50 mu m into a polyvinylpyrrolidone aqueous solution, wherein the mass percentage of the multi-walled carbon nanotubes to the polyvinylpyrrolidone aqueous solution is 0.08 wt%, carrying out ultrasonic treatment for 1 hour to obtain a coating solution, fully dip-coating the coating solution on the surface of glass fiber twill fabric, and then placing the glass fiber twill fabric dip-coated with the coating solution into an oven to be dried for 0.5 hour at 40 ℃ to obtain the carbon nanotube modified glass fiber twill fabric;
(5) coating the obtained graphene oxide/bisphenol F epoxy resin nanocomposite on the surface of a carbon nano tube modified glass fiber twill fabric, repeatedly rolling the glass fiber twill fabric by using a press roller to fully impregnate the graphene oxide/bisphenol F epoxy resin nanocomposite, repeatedly paving the glass fiber twill fabric to the required number of layers by using a laminated plate forming process, vacuumizing and pressurizing the laminated plate to 0.3MPa by using a vacuum bag for one time, pressurizing to 5MPa on a press machine, maintaining for 1.5 hours, and finally drying the laminated plate in an oven at 70 ℃ for 6 hours to obtain a laminated plate structure shown in figure 1, wherein 1 represents epoxy resin, 2 represents graphene oxide, 3 represents glass fiber cloth, and 4 represents a carbon nano tube.
The bending strength of the obtained glass fiber laminated plate is tested according to the GB/T1449-2005 standard, and the bending modulus of the graphene oxide/carbon nanotube reinforced glass fiber laminated plate is 38GPa, and the bending strength is 590 MPa. It can be seen that the flexural modulus and flexural strength of the graphene oxide/carbon nanotube reinforced glass fiber laminate in example 3 were improved by 72% and 115%, respectively, compared to example 1.
Example 5
(1) Adding 0.5g of graphene oxide with the purity of 95%, the number of layers of 5-10, the thickness of 3.4-8nm and the sheet diameter of 5-50 mu m into N-methyl-2-pyrrolidone, and carrying out ultrasonic treatment for 0.5 hour to obtain a graphene oxide N-methyl-2-pyrrolidone solution;
(2) adding 862 epoxy resin into the graphene oxide N-methyl-2-pyrrolidone solution to obtain a mixed solution, wherein the mass percentage of the graphene oxide to the 862 epoxy resin is 0.3 wt%, heating the mixed solution to 80 ℃, and simultaneously stirring the mixed solution for 2 hours by using a constant-temperature magnetic stirrer until all the N-methyl-2-pyrrolidone in the mixed solution is evaporated to obtain a graphene oxide 862 epoxy resin solution;
(3) putting the oxidized graphene 862 epoxy resin solution into a ball milling barrel, carrying out ball milling for 2 hours at the rotating speed of 200rpm, then drying the ball-milled oxidized graphene 862 epoxy resin solution in a vacuum oven for 0.5 hour for exhausting, slowly adding a normal-temperature amine curing agent into the exhausted oxidized graphene 862 epoxy resin solution, mixing the 862 epoxy resin and the curing agent according to the volume ratio of 10:1, stirring for 10 minutes simultaneously, and placing the mixed solution in the oven for drying for 7 hours at 70 ℃ to obtain the oxidized graphene/862 epoxy resin nanocomposite with the mass percentage of 0.3 wt%;
(4) adding water into polyvinylpyrrolidone, magnetically stirring until the concentration is 0.5mg/ml, adding 3g of multi-walled carbon nanotubes with the purity of more than 95%, the inner diameter of 3-5nm, the outer diameter of 8-15nm and the length of 50 mu m into a polyvinylpyrrolidone aqueous solution, wherein the mass percentage of the multi-walled carbon nanotubes to the polyvinylpyrrolidone aqueous solution is 0.1 wt%, carrying out ultrasonic treatment for 1 hour to obtain a coating solution, fully soaking the coating solution on the surface of a glass fiber satin fabric, and then drying the glass fiber satin fabric soaked with the mixture in an oven at 40 ℃ for 0.5 hour to obtain the carbon nanotube modified glass fiber satin fabric;
(5) coating the obtained graphene oxide/862 epoxy resin nanocomposite on the surface of a glass fiber satin fabric modified by carbon nanotubes, repeatedly rolling the glass fiber satin fabric by using a press roller to fully impregnate the graphene oxide/862 epoxy resin nanocomposite, repeatedly paving the laminate to a required number of layers by using a laminate forming process, vacuumizing and pressurizing the laminate to 0.5MPa by using a vacuum bag for one time, pressurizing the laminate to 3MPa on a press machine, maintaining the pressure for 2 hours, and finally drying the laminate in an oven at 70 ℃ for 7 hours to obtain a laminate structure shown in figure 1, wherein 1 represents epoxy resin, 2 represents graphene oxide, 3 represents glass fiber cloth, and 4 represents carbon nanotubes.
The bending strength of the obtained glass fiber laminated plate is tested according to the GB/T1449-2005 standard, and the bending modulus of the graphene oxide/carbon nanotube reinforced glass fiber laminated plate is 35GPa, and the bending strength is 490 MPa. It can be seen that the flexural modulus and flexural strength of the graphene oxide/carbon nanotube reinforced glass fiber laminate in example 3 were improved by 59% and 78%, respectively, compared to example 1.
Comparative example 1
(1) Adding 0.5g of graphene oxide with the purity of 95%, the number of layers of 5-10 layers, the thickness of 3.4-8nm and the sheet diameter of 5-50 mu m into ethanol, and carrying out ultrasonic treatment for 0.5 hour to obtain a graphene oxide ethanol solution;
(2) adding bisphenol F epoxy resin and 3g of multi-walled carbon nano-tubes with the purity of more than 95%, the inner diameter of 3-5nm, the outer diameter of 8-15nm and the length of 50 mu m into a graphene oxide ethanol solution to obtain a mixed solution, wherein the mass percent of the graphene oxide and the bisphenol F epoxy resin is 0.5 wt%, the mass percent of the multi-walled carbon nano-tubes and the graphene oxide ethanol solution is 0.1 wt%, heating the mixed solution to 80 ℃, and simultaneously stirring the mixed solution by using a constant-temperature magnetic stirrer for 2 hours until all ethanol in the mixed solution is evaporated;
(3) putting the mixed solution obtained in the step (2) into a ball milling barrel, carrying out ball milling for 2 hours at the rotating speed of 200rpm, drying the ball-milled mixed solution in a vacuum oven for 0.5 hour for exhausting, slowly adding a normal-temperature amine curing agent into the exhausted mixed solution, mixing the bisphenol F epoxy resin and the curing agent according to the volume ratio of 10:1, stirring for 10 minutes simultaneously to obtain a mixture, and putting the mixture into the oven for drying for 7 hours at 70 ℃;
(4) and (3) coating the mixture obtained in the step (3) on the surface of glass fiber, repeatedly rolling glass fiber cloth by using a press roller, repeatedly paving the glass fiber cloth to the required number of layers by using a laminated plate forming process, vacuumizing and pressurizing the laminated plate to 0.5MPa for one time by using a vacuum bag, pressurizing to 5MPa on a press machine, maintaining for 2 hours, and finally drying the laminated plate in an oven at 70 ℃ for 7 hours to obtain the graphene oxide/carbon nanotube reinforced glass fiber laminated plate.
The bending strength of the obtained glass fiber laminated plate is tested according to the GB/T1449-2005 standard, and the bending modulus of the graphene oxide/carbon nanotube reinforced glass fiber laminated plate is 34GPa, and the bending strength is 452 MPa. It can be seen that the flexural modulus and flexural strength of the graphene oxide/carbon nanotube reinforced glass fiber laminate in example 3 were improved by 54% and 64%, respectively, compared to example 1.
Comparative example 2
(1) Adding 0.5g of graphene oxide with the purity of 95%, the number of layers of 5-10 layers, the thickness of 3.4-8nm and the sheet diameter of 5-50 mu m into ethanol, and carrying out ultrasonic treatment for 0.5 hour to obtain a graphene oxide ethanol solution;
(2) adding bisphenol F epoxy resin into a graphene oxide ethanol solution to obtain a mixed solution, wherein the mass percent of the graphene oxide and the bisphenol F epoxy resin is 0.5 wt%, adding water into polyvinylpyrrolidone, magnetically stirring to obtain a polyvinylpyrrolidone aqueous solution with the concentration of 1mg/ml, adding 3g of a multiwalled carbon nanotube with the purity of 95%, the inner diameter of 3-5nm, the outer diameter of 8-15nm and the length of 50 mu m, carrying out ultrasonic treatment for 1 hour to obtain a carbon nanotube/polyvinylpyrrolidone aqueous solution, wherein the mass percent of the carbon nanotube/polyvinylpyrrolidone aqueous solution is 0.1 wt%, adding the carbon nanotube/polyvinylpyrrolidone aqueous solution into the mixed solution of the graphene oxide ethanol solution and the bisphenol F epoxy resin, the mass percent of the carbon nanotube/polyvinylpyrrolidone aqueous solution and the graphene oxide ethanol solution is 0.1 wt%, heating the mixed solution to 80 ℃, and simultaneously stirring the mixed solution for 2 hours by using a constant-temperature magnetic stirrer until all ethanol in the mixed solution is evaporated;
(3) putting the mixed solution obtained in the step (2) into a ball milling barrel, carrying out ball milling for 2 hours at the rotating speed of 200rpm, drying the ball-milled mixed solution in a vacuum oven for 0.5 hour for exhausting, slowly adding a normal-temperature amine curing agent into the exhausted mixed solution, mixing the bisphenol F epoxy resin and the curing agent according to the volume ratio of 10:1, stirring for 10 minutes simultaneously to obtain a mixture, and putting the mixture into the oven for drying for 7 hours at 70 ℃;
(4) and (3) coating the mixture obtained in the step (3) on the surface of glass fiber twill fabric, repeatedly rolling the glass fiber twill fabric by using a press roller, repeatedly paving the glass fiber twill fabric to the required number of layers by using a laminated plate forming process, vacuumizing and pressurizing the laminated plate to 0.5MPa for one time by using a vacuum bag, pressurizing to 5MPa on a press machine, maintaining for 2 hours, and finally drying the laminated plate in an oven at 70 ℃ for 7 hours to obtain the graphene oxide/carbon nanotube reinforced glass fiber laminated plate.
The bending strength of the obtained glass fiber laminated plate is tested according to the GB/T1449-2005 standard, and the bending modulus of the graphene oxide/carbon nanotube reinforced glass fiber laminated plate is 33GPa, and the bending strength is 441 MPa. It can be seen that the flexural modulus and flexural strength of the graphene oxide/carbon nanotube reinforced glass fiber laminate in example 3 were improved by 50% and 60%, respectively, compared to example 1.
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the scope of the present invention.
Claims (9)
1. A preparation method of a graphene oxide/carbon nanotube reinforced glass fiber laminated plate is characterized by comprising the following steps:
(1) adding graphene oxide into an organic solvent, and carrying out ultrasonic treatment to obtain a graphene oxide organic solution;
(2) adding epoxy resin into the graphene oxide organic solution to obtain a mixed solution, heating the mixed solution and stirring the mixed solution until all the organic solvent in the mixed solution is evaporated to obtain a graphene oxide epoxy resin solution;
(3) placing the graphene oxide epoxy resin solution into a ball milling barrel for ball milling treatment, drying and exhausting the ball-milled graphene oxide epoxy resin solution in a vacuum oven, slowly adding a curing agent into the exhausted graphene oxide epoxy resin solution while stirring to obtain a mixed solution, and placing the mixed solution in the oven for drying to obtain a graphene oxide/epoxy resin nanocomposite;
(4) adding water into polyvinylpyrrolidone, stirring until the mixture is dissolved, adding carbon nano tubes into polyvinylpyrrolidone aqueous solution, carrying out ultrasonic treatment to obtain coating solution, fully soaking the coating solution on the surface of glass fiber cloth, and then placing the glass fiber soaked with the coating solution in an oven for drying to obtain carbon nano tube modified glass fiber cloth;
(5) coating the obtained graphene oxide/epoxy resin nano composite material on the surface of carbon nano tube modified glass fiber cloth, repeatedly rolling the glass fiber cloth by using a press roller to fully impregnate the graphene oxide/epoxy resin nano composite material, repeatedly paving the glass fiber cloth to the required number of layers by using a laminated plate forming process, vacuumizing and pressurizing the paved laminated plate by using a vacuum bag once, continuously pressurizing the laminated plate on a press machine, and finally drying the laminated plate in an oven to obtain the graphene oxide/carbon nano tube reinforced glass fiber laminated plate.
2. The method for preparing a graphene oxide/carbon nanotube reinforced glass fiber laminate according to claim 1, wherein: the organic solvent in the step (1) is any one of ethanol, dimethyl amide, N-methyl-2-pyrrolidone, tetrahydrofuran and acetone.
3. The method for preparing a graphene oxide/carbon nanotube reinforced glass fiber laminate according to claim 1, wherein: in the step (1), the graphene oxide adopts multilayer graphene oxide, the purity of the graphene oxide is 95%, the thickness of the graphene oxide is 3.4-8nm, the diameter of a sheet layer is 5-50 mu m, and the number of the layers is 5-10.
4. The method for preparing a graphene oxide/carbon nanotube reinforced glass fiber laminate according to claim 1, wherein: in the step (2), the epoxy resin is any one of novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin and 862 epoxy resin, and the mass percentage of the graphene oxide to the epoxy resin is 0.1 wt% -0.5 wt%.
5. The method for preparing a graphene oxide/carbon nanotube reinforced glass fiber laminate according to claim 1, wherein: the curing agent in the step (3) is an amine curing agent cured at normal temperature, and the volume ratio of the epoxy resin to the curing agent is 10: 1.
6. The method for preparing a graphene oxide/carbon nanotube reinforced glass fiber laminate according to claim 1, wherein: in the step (4), the carbon nano tube is a multi-wall carbon nano tube, the purity of the carbon nano tube is more than 95%, the inner diameter of the carbon nano tube is 3-5nm, the outer diameter of the carbon nano tube is 8-15nm, the length of the carbon nano tube is 50 mu m, the concentration of the polyvinylpyrrolidone aqueous solution is 0.5-2 mg/ml, and the mass percentage of the carbon nano tube to the polyvinylpyrrolidone aqueous solution is 0.05-0.1 wt%.
7. The method for preparing a graphene oxide/carbon nanotube reinforced glass fiber laminate according to claim 1, wherein: the glass fiber cloth in the step (4) is any one of glass fiber unidirectional cloth, glass fiber plain weave fabric, glass fiber twill weave fabric and glass fiber satin weave fabric.
8. The method for preparing a graphene oxide/carbon nanotube reinforced glass fiber laminate according to claim 1, wherein: and (5) the laminated plate forming process comprises hand lay-up forming, vacuum bag pressure forming and cold press forming.
9. The method for preparing a graphene oxide/carbon nanotube reinforced glass fiber laminate according to claim 1, wherein: and (5) vacuumizing and pressurizing the vacuum bag to 0.1-0.5 MPa, and pressurizing to 2-5 MPa on a press machine for 1-2 hours.
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