CN113248867A - Epoxy resin-based composite material and preparation method and application thereof - Google Patents
Epoxy resin-based composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an epoxy resin-based composite material and a preparation method and application thereof, wherein the method comprises the following steps: (1) preparing cellulose nanocrystals; (2) mixing cellulose nanocrystals, a first solvent, a surfactant and carbon nanotubes, and reacting to obtain cellulose-carbon nanotubes; (3) mixing the cellulose-carbon nanotubes, the second solvent and the carbon fibers so as to attach the cellulose-carbon nanotubes to the carbon fibers, and drying; (4) and (4) carrying out compression molding on the product obtained in the step (3) and epoxy resin so as to obtain the epoxy resin-based composite material. In the invention, the cellulose nanocrystals are used as the carriers of the carbon nanotubes, so that the dispersibility of the carbon nanotubes in the solution is greatly improved, and the agglomeration phenomenon of the carbon nanotubes is avoided, so that the carbon nanotubes are uniformly and controllably attached to the carbon fibers to form a microscopic I-shaped structure, and the mechanical properties of the epoxy resin-based composite material, such as bending strength, modulus and the like, are greatly improved.
Description
Technical Field
The invention belongs to the technical field of carbon fiber materials, and particularly relates to an epoxy resin-based composite material, and a preparation method and application thereof.
Background
Carbon fiber has been widely used in various industries as a lightweight high-strength material. In the automotive industry, carbon fibers have been successfully applied to various aspects of surface covering parts, structural parts and the like of automobiles, and compared with metals, carbon fibers have high mechanical strength but have slightly insufficient modulus. Particularly, when the carbon fiber composite material is used as a carbon fiber composite material with a bending structure, the bending modulus is further improved, and the lightweight application effect is obviously improved.
The carbon nano tube has good mechanical property, and the composite material added with the carbon nano tube usually shows good strength, elasticity, fatigue resistance and isotropy, so that the performance of the composite material is greatly improved.
Disclosure of Invention
The inventor finds that if the carbon nanotubes and the carbon fibers are directly mixed, the phenomenon of carbon nanotube agglomeration and aggregation can occur, the carbon nanotubes cannot be uniformly dispersed on the carbon fibers, so that the nanometer effect of the carbon nanotubes cannot be embodied, the modification effect of the carbon fibers can be seriously influenced, and the mechanical property of the composite material is influenced.
In view of the above, the present invention provides an epoxy resin-based composite material, and a preparation method and an application thereof, in which carboxyl groups, hydroxyl groups, and the like in carbon nanotubes react with hydroxyl groups in cellulose nanocrystals in a solution to form molecular bonds, so that the carbon nanotubes are attached to the cellulose nanocrystals; the cellulose nanocrystals are used as carriers of the carbon nanotubes, so that the dispersibility of the carbon nanotubes in a solution is greatly improved, and the agglomeration phenomenon of the carbon nanotubes is avoided, so that the carbon nanotubes are uniformly and controllably attached to carbon fibers to form a microscopic I-shaped structure, and the bonding of a fiber resin microscopic interface is improved, thereby greatly improving the mechanical properties, such as bending strength, modulus and the like, of the epoxy resin-based composite material.
In one aspect of the invention, a method of preparing an epoxy resin-based composite is provided. According to an embodiment of the invention, the method comprises:
(1) preparing cellulose nanocrystals;
(2) mixing the cellulose nanocrystals, a first solvent, a surfactant and carbon nanotubes, and reacting to obtain cellulose-carbon nanotubes;
(3) mixing the cellulose-carbon nanotubes, a second solvent and carbon fibers so as to attach the cellulose-carbon nanotubes to the carbon fibers, and drying;
(4) and (4) carrying out compression molding on the product obtained in the step (3) and epoxy resin so as to obtain the epoxy resin-based composite material.
According to the method for preparing the epoxy resin-based composite material, carboxyl, hydroxyl and other groups in the carbon nano tube react with hydroxyl in the cellulose nano crystal in the solution to form molecular bonds, so that the carbon nano tube is attached to the cellulose nano crystal; the cellulose nanocrystals are used as carriers of the carbon nanotubes, so that the dispersibility of the carbon nanotubes in a solution is greatly improved, and the agglomeration phenomenon of the carbon nanotubes is avoided, so that the carbon nanotubes are uniformly and controllably attached to carbon fibers to form a microscopic I-shaped structure, and the bonding of a fiber resin microscopic interface is improved, thereby greatly improving the mechanical properties, such as bending strength, modulus and the like, of the epoxy resin-based composite material.
In addition, the method for preparing the epoxy resin-based composite material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, in the step (2), the first solvent is a first mixed solution of a first organic solvent and water, and the volume fraction of the first organic solvent in the first mixed solution is 5% to 15%.
In some embodiments of the invention, the first organic solvent is selected from at least one of tetrahydrofuran, pyridine, and diethyl ether.
In some embodiments of the invention, the surfactant is a sulfonic acid surfactant or a quaternary ammonium salt surfactant.
In some embodiments of the invention, the sulfonic acid surfactant is selected from at least one of sodium benzenesulfonate, sodium dodecylsulfate and sodium sulfosuccinate.
In some embodiments of the invention, in step (2), the mass ratio of the carbon nanotubes to the cellulose nanocrystals is 1 (1-5).
In some embodiments of the invention, in step (2), the mass ratio of the surfactant to the cellulose nanocrystals is 5 (1-5).
In some embodiments of the invention, in step (2), the mass to volume ratio of the cellulose nanocrystals to the first solvent is (0.1-0.5) g/100 mL.
In some embodiments of the invention, in step (2), the reaction temperature is 40 ℃ to 60 ℃ and the reaction time is 30min to 2 h.
In some embodiments of the invention, in step (3), the mass ratio of the cellulose-carbon nanotubes to the carbon fibers is (0.1-1): 10.
In some embodiments of the invention, in step (3), the mass to volume ratio of the cellulose-carbon nanotubes to the second solvent is (0.1-1) g/100 mL.
In some embodiments of the present invention, in the step (3), the second solvent is a second mixed solution of a second organic solvent and water, and the volume fraction of the second organic solvent in the second mixed solution is 5% to 15%.
In some embodiments of the invention, the second organic solvent is selected from at least one of ethanol, ethylene glycol, propanol, tetrahydrofuran, and pyridine.
In some embodiments of the invention, in step (3), the carbon fibers are carbon fiber filaments.
In some embodiments of the present invention, in step (3), the mixing the cellulose-carbon nanotubes, the second solvent and the carbon fibers comprises:
(3-1) mixing the cellulose-carbon nanotubes with the second solvent, and ultrasonically dispersing for 20-40min to obtain a mixed solution;
(3-2) immersing the carbon fiber filaments from one end of the mixed solution, and pulling the carbon fiber filaments to advance in the mixed solution until being taken out from the other end of the mixed solution.
In some embodiments of the present invention, in the step (3-2), the immersion time of the carbon fiber filaments in the mixed solution is 30 to 150 s.
In some embodiments of the present invention, the specific process of step (1) is:
mixing the dissociated fiber slurry, NaBr and TEMPO, adding NaClO solution under stirring, reacting, and maintaining the pH of the reaction solution at 9.0-11.0.
In some embodiments of the invention, the reaction temperature is 0 ℃ to 20 ℃ and the reaction time is 6 to 48 hours.
In some embodiments of the invention, the mass ratio of NaBr, TEMPO and NaClO is 1 (0.05-1) to (0.01-0.2).
In some embodiments of the invention, the mass ratio of the fiber slurry to the TEMPO is 2000 (0.05-1).
In some embodiments of the invention, the fiber slurry has a degree of dissociation of 1% to 3%.
In some embodiments of the invention, in step (4), the volume content of the carbon fibers in the epoxy resin-based composite material is 50% to 70%.
In a second aspect of the invention, an epoxy-based composite is provided. According to the embodiment of the invention, the epoxy resin-based composite material is prepared by adopting the method in the embodiment. Therefore, the mechanical properties of the epoxy resin-based composite material, such as bending strength, modulus and the like, are greatly improved, and the composite material is applied to automobile parts and can better improve the light weight effect.
In a third aspect of the invention, an automotive component is provided. According to the embodiment of the invention, the automobile part is prepared by adopting the epoxy resin-based composite material prepared in the embodiment or the epoxy resin-based composite material prepared by adopting the method in the embodiment as a production raw material. Therefore, the composite material is applied to automobile parts, the mechanical properties of the automobile parts, such as bending strength, modulus and the like, are greatly improved, and the light weight effect can be better improved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a flow chart of a method of preparing an epoxy resin based composite material according to one embodiment of the present invention.
FIG. 2 is a flow chart of a method of preparing an epoxy resin-based composite material according to yet another embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, a method of preparing an epoxy resin-based composite is provided. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: preparation of cellulose nanocrystals
In this step, the specific method for preparing the cellulose nanocrystals is not particularly limited, and those skilled in the art can prepare the cellulose nanocrystals using an oxidation system of (TEMPO) -NaClO-NaBr, or can prepare the cellulose nanocrystals using other methods.
According to one embodiment of the invention, the oxidation system of (TEMPO) -NaClO-NaBr is adopted to prepare the cellulose nanocrystals, and the specific process is as follows: and mixing the dissociated fiber slurry, NaBr and TEMPO, adding NaClO solution under stirring, reacting, keeping the pH of the reaction solution at 9.0-11.0, performing membrane filtration on the reaction product after the reaction is finished, and washing the reaction product to be neutral to obtain the cellulose nanocrystal. In the reaction, sodium hypochlorite is used as an oxidant to oxidize partial hydroxyl in cellulose into carboxyl without changing the form and cleanliness, and the cellulose is homogenized and oxidized into nano-cellulose crystals which can be better compounded with carbon nano-tubes.
As a specific example, the pH of the reaction solution is adjusted with an alkali solution, such as NaOH solution, KOH, or the like.
According to still another embodiment of the present invention, the reaction temperature is 0 ℃ to 20 ℃ and the reaction time is 6 to 48 hours, thereby better preparing the cellulose nanocrystals.
According to another embodiment of the invention, the mass ratio of NaBr, TEMPO and NaClO is 1 (0.05-1) to (0.01-0.2), thereby better preparing the cellulose nanocrystals.
According to yet another embodiment of the invention, the mass ratio of the fiber slurry to the TEMPO is 2000 (0.05-1), thereby better producing cellulose nanocrystals.
According to yet another embodiment of the present invention, the fiber slurry has a dissociation degree of 1% to 3%, thereby better preparing cellulose nanocrystals. The fiber slurry refers to a plant cellulose slurry obtained by removing sugar and lipid components from a plant by a pretreatment.
S200: mixing the cellulose nanocrystals, a first solvent, a surfactant and the carbon nanotubes, and reacting to obtain cellulose-carbon nanotubes
In the step, the cellulose nanocrystals, the first solvent, the surfactant and the carbon nanotubes are mixed, and the carbon nanotubes react with hydroxyl groups of the cellulose nanocrystals in the mixed solution to form molecular bonds, so that the carbon nanotubes are attached to the cellulose nanocrystals; the cellulose nanocrystals are used as carriers of the carbon nanotubes, so that the dispersibility of the carbon nanotubes in a solution is greatly improved, and the agglomeration phenomenon of the carbon nanotubes is avoided, thereby being beneficial to the uniform and controllable attachment of the carbon nanotubes on carbon fibers in subsequent steps. After the carbon nano tubes are subjected to cellulose nano crystal composite dispersion, the surface tension of the carbon nano tubes is reduced to a great extent, and the phenomena of adsorption and agglomeration among the carbon nano tubes are prevented.
According to another embodiment of the present invention, the first solvent is a first mixed solution of a first organic solvent and water, and the volume fraction of the first organic solvent in the first mixed solution is 5% to 15% (e.g., 5%, 8%, 10%, 15%, etc.), thereby increasing the dispersibility of the carbon nanotubes in the mixed solution. In the embodiment of the present invention, the specific kind of the first organic solvent is not particularly limited, and may be arbitrarily selected by those skilled in the art according to practical circumstances, and as a preferable embodiment, the first organic solvent is at least one selected from tetrahydrofuran, pyridine and diethyl ether, and tetrahydrofuran is more preferable.
In the embodiment of the invention, the surfactant plays the roles of a dispersing agent and an accelerating agent, and promotes the reaction of the carbon nano tube and the cellulose nano crystal. In the embodiment of the present invention, the specific kind of the surfactant is not particularly limited, and may be arbitrarily selected by those skilled in the art according to practical situations, and as a preferable embodiment, the surfactant is a sulfonic acid surfactant or a quaternary ammonium salt surfactant, and as a specific example, the sulfonic acid surfactant is at least one selected from sodium benzenesulfonate, sodium dodecylsulfate, and sodium sulfosuccinate.
According to still another embodiment of the present invention, the mass ratio of the carbon nanotubes to the cellulose nanocrystals is 1 (1-5), for example, 1:1/2/3/4/5, and thus the mass ratio of the carbon nanotubes to the cellulose nanocrystals is limited to the above range, and further the carbon nanotubes are sufficiently effectively attached to the cellulose nanocrystals, and the inventors have found that if the content of the cellulose nanocrystals is too low, the carbon nanotubes cannot be sufficiently attached to the cellulose nanocrystals, and thus the intended dispersion effect cannot be obtained; if the content of the cellulose nanocrystals is too high, carbon nanotubes can be effectively attached to carbon fibers in the subsequent steps, and the performance of the carbon nanotube-carbon fiber composite material is further affected.
According to another embodiment of the present invention, the mass ratio of the surfactant to the cellulose nanocrystals is 5 (1-5), such as 5:1/2/3/4/5, so that the surfactant is kept at a suitable concentration in the mixed solution, thereby effectively preventing the carbon nanotubes from agglomerating and ensuring good solubility of the carbon nanotubes and the cellulose nanocrystals.
According to another embodiment of the present invention, the ratio of the mass volume of the cellulose nanocrystals to the first solvent is (0.1-0.5) g/100mL, such as 0.1g/100mL, 0.2g/100mL, 0.3g/100mL, 0.4g/100mL, 0.5g/100mL, etc., so that the cellulose nanocrystals can be maintained at a suitable concentration in the above mixed solution, thereby ensuring the adsorption efficiency of the carbon nanotubes on the cellulose nanocrystals, and avoiding the effect of steric hindrance on the adsorption of the carbon nanotubes.
According to another embodiment of the present invention, the reaction temperature is 40 ℃ to 60 ℃ (e.g., 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, etc.), and the reaction time is 30min to 2h (e.g., 30min, 1h, 1.5h, 2h, etc.), so that the reaction can be carried out mildly in this temperature range, which is favorable for the reaction of hydroxyl groups in the cellulose nanocrystals and carboxyl groups, hydroxyl groups, etc. in the carbon nanotubes; the inventors found that if the reaction temperature is too high, agglomeration of the carbon nanotubes may be caused; if the reaction temperature is too low, the reaction efficiency and yield will be low. The inventors found that if the reaction time is too long, agglomeration of the carbon nanotubes may occur; if the reaction time is too short, the carbon nanotubes cannot be sufficiently attached to the cellulose nanocrystals.
S300: mixing the cellulose-carbon nanotubes, a second solvent and carbon fibers to attach the cellulose-carbon nanotubes to the carbon fibers, and drying
In the step, the cellulose-carbon nanotubes, the second solvent and the carbon fibers are mixed so as to be attached to the carbon fibers, so that the carbon nanotubes are uniformly and controllably attached to the carbon fibers to form a microscopic I-shaped structure, and the mechanical properties, such as bending strength, modulus and the like, of the epoxy resin-based composite material are greatly improved.
According to yet another particular embodiment of the invention, the carbon fibres are carbon fibre filaments.
According to still another embodiment of the present invention, referring to fig. 2, the mixing the cellulose-carbon nanotubes, the second solvent and the carbon fibers comprises: s310: mixing the cellulose-carbon nanotubes with the second solvent, and performing ultrasonic dispersion for 20-40min to fully disperse the cellulose-carbon nanotubes in the second solvent to obtain a mixed solution; s320: and immersing the carbon fiber filaments from one end of the mixed solution, and drawing the carbon fiber filaments to advance in the mixed solution until the carbon fiber filaments are taken out from the other end of the mixed solution. Therefore, the single-layer adsorption of the carbon nanotubes on the carbon fibers can be effectively controlled, and the distribution form of the carbon nanotubes can be favorably controlled.
According to a further embodiment of the invention, the carbon fiber filaments are immersed in the mixed solution for a time of 30-150s, thereby allowing sufficient adhesion of the cellulose-carbon nanotubes to the carbon fibers while avoiding excessive adhesion.
According to another embodiment of the present invention, the second solvent is a second mixed solution of a second organic solvent and water, and the volume fraction of the second organic solvent in the second mixed solution is 5% to 15% (e.g., 5%, 8%, 10%, 15%, etc.), so that the carbon nanotubes can be better dispersed in the mixed solution and the surface tension can be kept suitable. In the embodiment of the present invention, the specific kind of the second organic solvent is not particularly limited, and may be arbitrarily selected by those skilled in the art according to practical circumstances, and as a preferable embodiment, the second organic solvent is at least one selected from ethanol, ethylene glycol, propanol, tetrahydrofuran, and pyridine, and more preferably ethanol.
According to still another embodiment of the present invention, the mass ratio of the cellulose-carbon nanotubes to the carbon fibers is (0.1-1):10, such as 0.1/0.3/0.5/0.7/1:10, etc., thereby limiting the mass-to-volume ratio of the cellulose-carbon nanotubes to the second solvent to the above range, further allowing uniform and controllable adhesion of the carbon nanotubes to the carbon fibers; the inventor finds that if the content of the cellulose-carbon nanotubes is too low, the carbon nanotubes cannot be effectively and sufficiently adsorbed on the carbon fibers, and the adsorption efficiency is affected; if the content of the cellulose-carbon nano tubes is too high, excessive paving on the surfaces of the carbon nano tubes can be caused, creeping overlapping can be caused, the arrangement of the carbon nano tubes on the surfaces of the carbon fibers is influenced, accumulation is caused, and the mechanical property of the carbon nano tube-carbon fiber composite material is finally influenced.
According to another embodiment of the present invention, the mass-to-volume ratio of the cellulose-carbon nanotubes to the second solvent is (0.1-1) g/100mL, such as 0.1g/100mL, 0.3g/100mL, 0.5g/100mL, 0.7g/100mL, 1g/100mL, etc., thereby ensuring a suitable carbon nanotube surface coating speed and establishing an adsorption-coating dynamic balance by controlling the concentration of the carbon nanotube solution within the above range, thereby ensuring the coating effect of the carbon nanotubes on the carbon fiber surface.
As a specific example, the carbon fiber filament attached with the carbon nano tube is dried in vacuum at 60-80 ℃.
S400: and (3) carrying out compression molding on the product obtained in the step (S300) and epoxy resin so as to obtain the epoxy resin-based composite material
In the step, the product obtained in the step S300 and epoxy resin are subjected to compression molding so as to obtain the epoxy resin-based composite material, wherein the carbon fibers can greatly enhance various mechanical properties of the composite material, and the carbon nanotubes and the carbon fibers form a microscopic I-shaped structure, so that various properties of the carbon fiber nanocomposite material are further improved.
According to another embodiment of the present invention, in the epoxy resin-based composite material, the volume content of the carbon fiber is 50% to 70%, thereby greatly improving the mechanical properties of the epoxy resin-based composite material, such as bending strength and modulus.
According to the method for preparing the epoxy resin-based composite material, carboxyl, hydroxyl and other groups in the carbon nano tube react with hydroxyl in the cellulose nano crystal in the solution to form molecular bonds, so that the carbon nano tube is attached to the cellulose nano crystal; the cellulose nanocrystals are used as carriers of the carbon nanotubes, so that the dispersibility of the carbon nanotubes in a solution is greatly improved, and the agglomeration phenomenon of the carbon nanotubes is avoided, so that the carbon nanotubes are uniformly and controllably attached to carbon fibers to form a microscopic I-shaped structure, and the bonding of a fiber resin microscopic interface is improved, thereby greatly improving the mechanical properties, such as bending strength, modulus and the like, of the epoxy resin-based composite material.
In a second aspect of the invention, an epoxy-based composite is provided. According to the embodiment of the invention, the epoxy resin-based composite material is prepared by adopting the method in the embodiment. Therefore, the mechanical properties of the epoxy resin-based composite material, such as bending strength, modulus and the like, are greatly improved, and the composite material is applied to automobile parts and can better improve the light weight effect.
In a third aspect of the invention, an automotive component is provided. According to the embodiment of the invention, the automobile part is prepared by adopting the epoxy resin-based composite material prepared in the embodiment or the epoxy resin-based composite material prepared by adopting the method in the embodiment as a production raw material. Therefore, the composite material is applied to automobile parts, the mechanical properties of the automobile parts, such as bending strength, modulus and the like, are greatly improved, and the light weight effect can be better improved.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
The embodiment provides a method for preparing an epoxy resin-based composite material, which comprises the following steps:
1. cellulose nanocrystal preparation
200g of 1% dissociated fiber slurry was charged into a 500ml vessel, 0.1g of NaBr and 0.02g of TEMPO reagent were added, the reaction was stirred under magnetic stirring, 0.5ml of a 2% by mass NaClO solution was further added, and the pH of the reaction solution was continuously adjusted to 10.0 with NaOH. The reaction temperature is maintained at 0-5 ℃ and the reaction time is 12 h. And after the reaction is finished, performing membrane filtration on the reaction product, and washing the reaction product to be neutral to obtain the cellulose nanocrystal.
2. Cellulose-carbon nanotube preparation
Dissolving 0.2g of cellulose nanocrystals in 100mL of tetrahydrofuran aqueous solution with volume fraction of 10%, adding 0.5g of p-toluenesulfonic acid, fully dispersing and dissolving, then adding 0.1g of carbon nanotubes, reacting at 60 ℃ for 1h, and then performing membrane filtration to obtain the cellulose-carbon nanotubes.
3. Carbon nanotube-carbon fiber preparation
Dissolving 2g of cellulose-carbon nano tube in 500mL of ethanol aqueous solution with volume fraction of 10%, fully dispersing for 30min by ultrasonic waves, immersing 50g of carbon fiber silk thread into the solution from one end, and gradually drawing the silk thread to move forwards in the solution until the silk thread is taken out from the other end of the solution. And immersing each section of the silk thread in the solution for 30s, and then drying the carbon fiber silk attached with the carbon nano tubes in vacuum at 60 ℃.
4. And carrying out compression molding on the obtained carbon nanotube-carbon fiber and epoxy resin to obtain a carbon fiber composite board with the thickness of 2mm, wherein the volume content of the carbon fiber is 60%.
Example 2
The procedure for the preparation of cellulose nanocrystals-carbon nanotubes and the processing of carbon filaments was the same as in example 1, except that the amount of TEMPO reagent added during the preparation of cellulose nanocrystals was 0.04g and the reaction time was extended to 18 h.
Example 3
The same process as in preparation example 1 was conducted, except that the amount of cellulose nanocrystals used in the preparation of the cellulose-carbon nanotubes was 0.5 g.
Example 4
The same process as in preparation example 1 was conducted, except that the amount of the cellulose carbon nanotubes used in the carbon nanotube-carbon fiber preparation process was 3 g.
Comparative example
Directly carrying out compression molding on the carbon fiber and the epoxy resin to prepare the carbon fiber composite board with the thickness of 2mm, wherein the volume content of the carbon fiber is 60%. Except that cellulose-carbon nanotubes were not added.
The composite materials prepared in examples 1-4 and comparative example were tested according to GB-T1449-2005 method for testing the bending properties of fiber reinforced plastics, and the test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the flexural strength and flexural modulus of examples 1-4 are significantly greater than those of the comparative examples, and it can be seen that the flexural strength and flexural modulus of the epoxy resin-based composite material are greatly improved by adopting the technical scheme of the invention.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of preparing an epoxy resin-based composite, comprising:
(1) preparing cellulose nanocrystals;
(2) mixing the cellulose nanocrystals, a first solvent, a surfactant and carbon nanotubes, and reacting to obtain cellulose-carbon nanotubes;
(3) mixing the cellulose-carbon nanotubes, a second solvent and carbon fibers so as to attach the cellulose-carbon nanotubes to the carbon fibers, and drying;
(4) and (4) carrying out compression molding on the product obtained in the step (3) and epoxy resin so as to obtain the epoxy resin-based composite material.
2. The method according to claim 1, wherein in the step (2), the first solvent is a first mixed solution of a first organic solvent and water, and the volume fraction of the first organic solvent in the first mixed solution is 5% to 15%;
optionally, the first organic solvent is selected from at least one of tetrahydrofuran, pyridine, and diethyl ether;
optionally, the surfactant is a sulfonic acid surfactant or a quaternary ammonium salt surfactant;
optionally, the sulfonic acid surfactant is selected from at least one of sodium benzenesulfonate, sodium dodecylsulfate and sodium sulfosuccinate.
3. The method according to claim 1, wherein in the step (2), the mass ratio of the carbon nanotubes to the cellulose nanocrystals is 1 (1-5);
optionally, in the step (2), the mass ratio of the surfactant to the cellulose nanocrystals is 5 (1-5);
optionally, in step (2), the mass to volume ratio of the cellulose nanocrystals to the first solvent is (0.1-0.5) g/100 mL;
optionally, in the step (2), the reaction temperature is 40-60 ℃, and the reaction time is 30min-2 h.
4. The method according to claim 1, wherein in step (3), the mass ratio of the cellulose-carbon nanotubes to the carbon fibers is (0.1-1): 10;
optionally, in step (3), the mass-to-volume ratio of the cellulose-carbon nanotubes to the second solvent is (0.1-1) g/100 mL.
5. The method according to claim 1, wherein in the step (3), the second solvent is a second mixed solution of a second organic solvent and water, and the volume fraction of the second organic solvent in the second mixed solution is 5% to 15%;
optionally, the second organic solvent is selected from at least one of ethanol, ethylene glycol, propanol, tetrahydrofuran, and pyridine.
6. The method according to claim 1, wherein in step (3), the carbon fibers are carbon fiber filaments;
optionally, in step (3), the mixing the cellulose-carbon nanotubes, the second solvent and the carbon fibers comprises:
(3-1) mixing the cellulose-carbon nanotubes with the second solvent, and ultrasonically dispersing for 20-40min to obtain a mixed solution;
(3-2) immersing the carbon fiber filaments from one end of the mixed solution and pulling the carbon fiber filaments to advance in the mixed solution until being taken out from the other end of the mixed solution;
optionally, in the step (3-2), the immersion time of the carbon fiber filament in the mixed solution is 30 to 150 s.
7. The method according to any one of claims 1 to 6, wherein the specific process of step (1) is as follows:
mixing the dissociated fiber slurry, NaBr and TEMPO, adding NaClO solution under stirring, reacting, and keeping the pH of the reaction solution at 9.0-11.0;
optionally, the reaction temperature is 0-20 ℃, and the reaction time is 6-48 h;
optionally, the mass ratio of NaBr, TEMPO and NaClO is 1 (0.05-1) to (0.01-0.2);
optionally, the mass ratio of the fiber slurry to the TEMPO is 2000 (0.05-1);
optionally, the fiber slurry has a degree of dissociation of 1% to 3%.
8. The method according to any one of claims 1 to 6, wherein in step (4), the carbon fiber is contained in an amount of 50 to 70% by volume in the epoxy resin-based composite material.
9. An epoxy resin-based composite material, which is characterized by being prepared by the method of any one of claims 1 to 8.
10. An automobile part, characterized in that the automobile part is prepared by using the epoxy resin-based composite material according to claim 9 or the epoxy resin-based composite material prepared by the method according to any one of claims 1 to 8 as a production raw material.
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| CN105778424A (en) * | 2016-04-22 | 2016-07-20 | 武汉理工大学 | Carbon nanotube and carbon fiber synergistically modified epoxy resin composite material and preparation method thereof |
| CN109867916A (en) * | 2019-02-18 | 2019-06-11 | 昆明理工大学 | Plant fiber reinforced resin based composites and preparation method thereof |
| WO2020110090A1 (en) * | 2018-11-30 | 2020-06-04 | Sabic Global Technologies B.V. | Polymer compositions including functionalized carbon nanotubes and crystalline cellulose material |
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| CN105778424A (en) * | 2016-04-22 | 2016-07-20 | 武汉理工大学 | Carbon nanotube and carbon fiber synergistically modified epoxy resin composite material and preparation method thereof |
| WO2020110090A1 (en) * | 2018-11-30 | 2020-06-04 | Sabic Global Technologies B.V. | Polymer compositions including functionalized carbon nanotubes and crystalline cellulose material |
| CN109867916A (en) * | 2019-02-18 | 2019-06-11 | 昆明理工大学 | Plant fiber reinforced resin based composites and preparation method thereof |
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