CN111777728B - Preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material - Google Patents
Preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material, which comprises the following steps of carrying out hydrothermal reaction by taking a glucose solution as a carbon source to obtain carbon microspheres; dissolving carbon microspheres in a mixed solution of deionized water and absolute ethyl alcohol, adding a mixed solution of a silane coupling agent and absolute ethyl alcohol, and reacting under the heating condition of condensation reflux to obtain modified carbon microspheres; preparing a solution from the modified carbon microspheres, water and methyl methacrylate, recording the solution as a solution A, introducing nitrogen and continuously stirring; preparing a graphene oxide aqueous solution, marking as a solution B, and continuously stirring; adding the uniformly stirred solution B into the uniformly stirred solution A to obtain a solution C, and continuously stirring until the solution C is uniformly mixed; and adding sodium dodecyl benzene sulfonate into the solution C, heating for reaction, filtering, centrifuging, washing and drying a product to obtain the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a preparation method of a graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material.
Background
With the rapid development of nanotechnology, the research, development and application of nano-materials as lubricant additives have become one of the hot spots of domestic and foreign research. Among them, the assembly of organic-inorganic nanocomposites and related nanotechnology are receiving increasing attention from researchers in the preparation of new nanocomposites. The polymer/inorganic nano composite material has many novel characteristics such as excellent mechanical property, thermal property and stability due to the synergistic effect between the nano inorganic substance and the polymer matrix, and has great application value in the field of high-performance lubricating oil. The polymer is coated on the particle surface in the form of chemical bonds through the action of the polymer monomer and the chemical groups on the surface of the inorganic particle, so that the acting force between the polymer monomer and the particle can be enhanced, and different polymers can be selected according to actual requirements to stably exist in different solutions. However, a pure polymer shell is usually composed of a single chemical crosslink, which makes it susceptible to internal softening at high temperatures, thereby affecting performance.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material, which overcomes the defects in the prior art, the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material is prepared under the condition of not adding an initiator and a cross-linking agent, the preparation process is simple, and no harmful substance is generated; in addition, the high-performance nano composite material prepared by the invention can reduce the friction coefficient and the wear rate of machinery in the friction process, thereby prolonging the service life of the machinery, and has low cost and certain commercial prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material comprises the following steps:
1) carrying out hydrothermal reaction by taking a glucose solution as a carbon source, washing a product for a plurality of times after the reaction is finished, and then carrying out suction filtration and drying to obtain carbon microspheres;
2) dissolving dried carbon microspheres in a mixed solution of deionized water and absolute ethyl alcohol, adding a mixed solution of a silane coupling agent and absolute ethyl alcohol, reacting under the conditions of condensation, reflux and heating, washing a product for a plurality of times after the reaction is finished, and then performing suction filtration and drying to obtain modified carbon microspheres;
3) preparing a solution from the dried modified carbon microspheres, water and methyl methacrylate, recording the solution as a solution A, introducing nitrogen and continuously stirring until the mixture is uniformly mixed;
4) preparing a graphene oxide aqueous solution, marking as a solution B, and continuously stirring until the graphene oxide aqueous solution and the solution B are uniformly mixed;
5) adding the uniformly stirred solution B into the uniformly stirred solution A to obtain a solution C, and continuously stirring until the solution C is uniformly mixed;
6) adding sodium dodecyl benzene sulfonate into the uniformly stirred and mixed solution C, heating for reaction, and continuously introducing nitrogen and stirring in the whole process;
7) and after the reaction is finished, filtering, centrifuging, washing and drying the product to obtain the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material.
Further, the concentration of the glucose solution in the step 1) is 40 mg/mL; the temperature of the hydrothermal reaction in the step 1) is 180 ℃, and the time is 12 h.
Further, the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solution of the deionized water and the absolute ethyl alcohol in the step 2) is 5:4, and 0.2g of carbon microspheres are added into every 90mL of the mixed solution of the deionized water and the absolute ethyl alcohol.
Further, the silane coupling agent in the step 2) is KH550, and the mixed solution of the silane coupling agent and the absolute ethyl alcohol is specifically: every 20mL of absolute ethanol was added with 5mL of silane coupling agent.
Further, the volume ratio of the mixed solution of the deionized water and the absolute ethyl alcohol in the step 2) to the mixed solution of the silane coupling agent and the absolute ethyl alcohol is 18: 5.
Further, the heating conditions of condensation reflux in the step 2) are specifically as follows: reflux was condensed at 60 ℃ for 12 h.
Further, the concentration of the modified carbon microspheres in the solution A in the step 3) is 5mg/mL-8mg/mL, and the adding amount of the methyl methacrylate is 0.2 wt% of the mass of the modified carbon microspheres.
Further, the mass ratio of the graphene oxide to the modified carbon microspheres in the solution C in the step 5) is 1: 5.
Further, the volume ratio between the solution a and the solution B in the step 5) was 2: 1.
Further, the mass ratio of the added sodium dodecyl benzene sulfonate in the step 6) to the modified carbon microspheres is 1:40, the reaction temperature in the step 6) is 60 ℃, and the reaction time is 12 hours.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts a chemical method to modify carbon microspheres and then prepares a mixed solution of the modified carbon microspheres and polymethyl methacrylate (PMMA). Preparing a Graphene Oxide (GO) aqueous solution, uniformly stirring, adding the graphene oxide aqueous solution into a mixed solution of modified carbon microspheres and PMMA (polymethyl methacrylate), adding sodium dodecyl benzene sulfonate, and adding the mixture into N2And heating in the atmosphere to obtain the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material. Through observation and analysis, the PMMA polymer shell is coated on the surface of the carbon microsphere, and GO is used as a physical crosslinking point in the PMMA network to enhance the mechanical property of the polymer network. In the friction process, small-size particles can be stably deposited in a friction area, the roughness of the surface of a friction pair is reduced, direct contact between sliding surfaces is avoided, the effect of repairing the surface of the friction pair is achieved to a certain extent, and meanwhile, the polymer shell can promote the formation of a lubricating oil film in the friction process so as to reduce abrasion. The large-sized particles act as bearings, so that the sliding friction device is changed into rolling friction, and GO helps to enhance the strength of the friction film, prevent the friction film from cracking and improve the friction stability. The method fully exerts the synergistic effect of the carbon microspheres, PMMA and GO, and effectively solves the problems of poor mechanical property and poor dispersibility of the composite material. Greatly reduces the friction coefficient and the wear rate, improves the stability and prolongs the service life of the machine.
The invention prepares the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material for the first time. Firstly, the carbon microspheres are modified by adopting a silane coupling agent, so that a prerequisite condition is provided for the subsequent compounding with Methyl Methacrylate (MMA) and Graphene Oxide (GO), and meanwhile, long alkane chains are grafted, so that the carbon microspheres have good dispersibility in an organic solvent, and the carbon microspheres have the characteristics of simplicity in operation, low equipment requirement and the like. And then, combining MMA (methyl methacrylate) and carbon microspheres through amido bonds, and initiating the double bond opening of MMA molecules and the reaction of MMA molecules and Graphene Oxide (GO) nanosheets under the action of sodium dodecyl benzene sulfonate and heating conditions to form a polymethyl methacrylate shell containing graphene oxide. Due to the flexible molecular chain of PMMA, the composite material is more stable in the friction process. Moreover, GO has excellent mechanical properties, the wear resistance and stability of PMMA are enhanced, the thermal conductivity of the composite material is improved, the surface of a friction pair is well protected, the wear rate is greatly reduced, and the service life performance of machinery is favorably improved. The hydrothermal carbon spheres are used as raw materials, so that the raw materials are wide in source and more environment-friendly. No toxic substance is added in the whole preparation process, so that the preparation method is green and controllable in process.
Drawings
FIG. 1 is a SEM photograph of carbon microspheres before and after modification of example 1, wherein (a) is the microstructure of unmodified carbon microspheres, (b) is the microstructure of modified carbon microspheres, and (c) and (d) are the microstructures of composite materials;
fig. 2 shows raman spectra of carbon microspheres, modified carbon microspheres, graphene oxide, and the graphene oxide-reinforced polymethylmethacrylate/carbon microsphere composite material obtained in example 1.
Fig. 3 is a graph of the dynamic friction coefficients of the raw oil, the carbon microspheres, and the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite obtained by example 1, wherein (a) is a graph of the dynamic friction coefficient at 8N, and (b) is a graph of the dynamic friction coefficient at 30N;
Detailed Description
Embodiments of the invention are described in further detail below:
a preparation method of a graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material comprises the following steps:
1) taking a glucose solution as a carbon source, carrying out hydrothermal reaction at 180 ℃ for 12 hours, washing the product for multiple times after the hydrothermal reaction is finished, carrying out suction filtration, and drying to obtain the carbon microspheres, wherein the concentration of the glucose solution is 40 mg/mL;
2) dissolving the dried carbon microspheres in a mixed solution of water and absolute ethyl alcohol (the volume ratio of deionized water to absolute ethyl alcohol is 5:4), adding 0.2g of carbon microspheres in every 90mL of the mixed solution of deionized water and absolute ethyl alcohol, and then adding a mixed solution of a silane coupling agent and absolute ethyl alcohol (the silane coupling agent adopts KH550, and the mixed solution of the silane coupling agent and absolute ethyl alcohol is specifically: adding 5mL of silane coupling agent into every 20mL of absolute ethyl alcohol), condensing and refluxing for 12 hours at the temperature of 60 ℃, washing the product for multiple times, performing suction filtration, and drying to obtain modified carbon microspheres;
3) preparing the dried modified carbon microsphere water and methyl methacrylate into a solution A, wherein the concentration of the modified carbon microsphere in the solution A is 5mg/mL-8mg/mL, the addition amount of the methyl methacrylate is 0.2 wt% of the mass of the carbon microsphere, introducing nitrogen and continuously stirring;
4) and preparing a graphene oxide aqueous solution, and marking as a solution B, wherein the mass ratio of the graphene oxide to the modified carbon microspheres in the solution A is 1: 5.
5) Adding the solution B into the solution A (the volume ratio of the solution A to the solution B is 2:1), adding sodium dodecyl benzene sulfonate, and heating to 70 ℃, wherein the mass ratio of the added sodium dodecyl benzene sulfonate to the modified carbon microspheres is 1: 40. And (3) condensing and refluxing for 12 hours, continuously introducing nitrogen and stirring in the whole process, repeatedly washing the product with ethanol, performing suction filtration, and drying to obtain the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material.
The method adopts a soap-free polymerization method, and the composite material prepared under the condition of not using an emulsifier and a cross-linking agent has good dispersibility and stability in an organic solvent, and has degradability, greenness and no pollution. The nano lubricant is dispersed in lubricating oil as a lubricating oil additive, can effectively reduce the friction coefficient, reduce the wear rate, effectively prolong the service life of equipment, has controllable preparation process, can prepare products with different proportions and sizes according to different requirements, and provides diversity for the preparation of high-performance nano lubricants. According to the invention, graphene oxide is added into a polymer network to serve as a physical crosslinking site, and the physical and chemical crosslinking network is constructed to enhance the mechanical property of the polymer.
Example 1
1) Preparing a glucose solution with the concentration of 40mg/mL, carrying out hot water thermal reaction for 12 hours at 180 ℃, washing and filtering the product for multiple times, and drying in an oven at 80 ℃ for 12 hours to obtain carbon microspheres;
2) dissolving 0.2g of dried carbon microspheres in a mixed solution of 50ml of deionized water and 40ml of absolute ethyl alcohol, adding a mixed solution prepared from 5ml of silane coupling agent and 20ml of absolute ethyl alcohol, reacting for 12 hours at the temperature of 60 ℃ under a condensing reflux condition, washing and filtering products for multiple times, and drying in an oven at the temperature of 80 ℃ for 12 hours to obtain modified carbon microspheres;
3) preparing the dried modified carbon microspheres, water and methyl methacrylate into a solution A, wherein the concentration of the modified carbon microspheres in the solution A is 5mg/mL, the addition amount of the methyl methacrylate is 0.2 wt% of the mass of the modified carbon microspheres, introducing nitrogen and continuously stirring;
4) preparing a graphene oxide aqueous solution, recording as a solution B, wherein the mass ratio of the graphene oxide to the modified carbon microspheres is 1: 5;
5) adding the solution B into the solution A (the volume ratio of the solution A to the solution B is 2:1), adding sodium dodecyl benzene sulfonate, and heating to 70 ℃, wherein the mass ratio of the added sodium dodecyl benzene sulfonate to the modified carbon microspheres is 1: 40. And (3) condensing and refluxing for 12 hours, continuously introducing nitrogen and stirring in the whole process, repeatedly washing the product with ethanol, performing suction filtration, and drying to obtain the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material.
Example 2
1) Preparing a glucose solution with the concentration of 40mg/mL, carrying out hot water thermal reaction for 12 hours at 180 ℃, washing and filtering the product for multiple times, and drying in an oven at 80 ℃ for 12 hours to obtain carbon microspheres;
2) dissolving 0.2g of dried carbon microspheres in a mixed solution of 50ml of deionized water and 40ml of absolute ethyl alcohol, adding a mixed solution prepared from 5ml of silane coupling agent and 20ml of absolute ethyl alcohol, reacting for 12 hours at the temperature of 60 ℃ under a condensing reflux condition, washing and filtering products for multiple times, and drying in an oven at the temperature of 80 ℃ for 12 hours to obtain modified carbon microspheres;
3) preparing the dried modified carbon microspheres, water and methyl methacrylate into a solution A, wherein the concentration of the modified carbon microspheres in the solution A is 6mg/mL, the addition amount of the methyl methacrylate is 0.2 wt% of the mass of the modified carbon microspheres, introducing nitrogen and continuously stirring;
4) preparing a graphene oxide aqueous solution, marking as a solution B, wherein the mass ratio of the graphene oxide to the modified carbon microspheres is 1: 5;
5) adding the solution B into the solution A (the volume ratio of the solution A to the solution B is 2:1), adding sodium dodecyl benzene sulfonate, and heating to 70 ℃, wherein the mass ratio of the added sodium dodecyl benzene sulfonate to the modified carbon microspheres is 1: 40. And (3) condensing and refluxing for 12 hours, continuously introducing nitrogen and stirring in the whole process, repeatedly washing the product with ethanol, performing suction filtration, and drying to obtain the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material.
Example 3
1) Preparing a glucose solution with the concentration of 40mg/mL, carrying out hot water thermal reaction for 12 hours at 180 ℃, washing and filtering the product for multiple times, and drying in an oven at 80 ℃ for 12 hours to obtain carbon microspheres;
2) dissolving 0.2g of dried carbon microspheres in a mixed solution of 50ml of deionized water and 40ml of absolute ethyl alcohol, adding a mixed solution prepared from 5ml of silane coupling agent and 20ml of absolute ethyl alcohol, reacting for 12 hours at the temperature of 60 ℃ under a condensing reflux condition, washing and filtering products for multiple times, and drying in an oven at the temperature of 80 ℃ for 12 hours to obtain modified carbon microspheres;
3) preparing the dried modified carbon microspheres, water and methyl methacrylate into a solution A, wherein the concentration of the modified carbon microspheres in the solution A is 7mg/mL, the addition amount of the methyl methacrylate is 0.2 wt% of the mass of the modified carbon microspheres, introducing nitrogen and continuously stirring;
4) preparing a graphene oxide aqueous solution, marking as a solution B, wherein the mass ratio of the graphene oxide to the modified carbon microspheres is 1: 5;
5) adding the solution B into the solution A (the volume ratio of the solution A to the solution B is 2:1), adding sodium dodecyl benzene sulfonate, and heating to 70 ℃, wherein the mass ratio of the added sodium dodecyl benzene sulfonate to the modified carbon microspheres is 1: 40. And (3) condensing and refluxing for 12 hours, continuously introducing nitrogen and stirring in the whole process, repeatedly washing the product with ethanol, performing suction filtration, and drying to obtain the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material.
Example 4
1) Preparing a glucose solution with the concentration of 50mg/mL, carrying out hot water thermal reaction for 12 hours at 180 ℃, washing and filtering the product for multiple times, and drying in an oven at 80 ℃ for 12 hours to obtain carbon microspheres;
2) dissolving 0.2g of dried carbon microspheres in a mixed solution of 50ml of deionized water and 40ml of absolute ethyl alcohol, adding a mixed solution prepared from 5ml of silane coupling agent and 20ml of absolute ethyl alcohol, reacting for 12 hours at the temperature of 60 ℃ under a condensing reflux condition, washing and filtering products for multiple times, and drying in an oven at the temperature of 80 ℃ for 12 hours to obtain modified carbon microspheres;
3) preparing the dried modified carbon microspheres, water and methyl methacrylate into a solution A, wherein the concentration of the modified carbon microspheres in the solution A is 8mg/mL, the addition amount of the methyl methacrylate is 0.2 wt% of the mass of the modified carbon microspheres, introducing nitrogen and continuously stirring;
4) preparing a graphene oxide aqueous solution, marking as a solution B, wherein the mass ratio of the graphene oxide to the modified carbon microspheres is 1: 5;
5) adding the solution B into the solution A (the volume ratio of the solution A to the solution B is 2:1), adding sodium dodecyl benzene sulfonate, and heating to 70 ℃, wherein the mass ratio of the added sodium dodecyl benzene sulfonate to the modified carbon microspheres is 1: 40. And (3) condensing and refluxing for 12 hours, continuously introducing nitrogen and stirring in the whole process, repeatedly washing the product with ethanol, performing suction filtration, and drying to obtain the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material.
From fig. 1 comparing the original carbon microsphere obtained in example 1 with the carbon microsphere modified by silane coupling agent, it can be seen that the modification method successfully grafts the silane coupling agent to the surface of the carbon microsphere; according to the method for preparing the composite material, the carbon microspheres, the methyl methacrylate and the graphene oxide are successfully combined together, and the graphene oxide is introduced into a polymethyl methacrylate network.
As can be seen from fig. 2, a characteristic peak of graphene oxide appears in the Raman spectrum, indicating that graphene oxide exists in the composite material.
From fig. 3, it can be seen that the rotation speed is 400R, and the pressure changes, the (a)8N (b)30N lubricating oil with carbon microspheres added alone and the original oil are more obvious, and the friction coefficient of the composite material prepared by the invention in example 1 is lower after being added into the lubricating oil, which shows that the composite material has better antifriction performance.
Claims (10)
1. A preparation method of a graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material is characterized by comprising the following steps:
1) carrying out hydrothermal reaction by taking a glucose solution as a carbon source, washing a product for a plurality of times after the reaction is finished, and then carrying out suction filtration and drying to obtain carbon microspheres;
2) dissolving dried carbon microspheres in a mixed solution of deionized water and absolute ethyl alcohol, adding a mixed solution of a silane coupling agent and absolute ethyl alcohol, reacting under a condensing reflux heating condition, washing a product for a plurality of times after the reaction is finished, and then performing suction filtration and drying to obtain modified carbon microspheres;
3) preparing a solution from the dried modified carbon microspheres, water and methyl methacrylate, recording the solution as a solution A, introducing nitrogen, and continuously stirring until the mixture is uniformly mixed;
4) preparing a graphene oxide aqueous solution, marking as a solution B, and continuously stirring until the graphene oxide aqueous solution and the solution B are uniformly mixed;
5) adding the uniformly stirred solution B into the uniformly stirred solution A to obtain a solution C, and continuously stirring until the solution C is uniformly mixed;
6) adding sodium dodecyl benzene sulfonate into the uniformly stirred and mixed solution C, heating for reaction, and continuously introducing nitrogen and stirring in the whole process;
7) and after the reaction is finished, filtering, centrifuging, washing and drying the product to obtain the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material.
2. The method for preparing the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, wherein the concentration of the glucose solution in the step 1) is 40 mg/mL; the temperature of the hydrothermal reaction in the step 1) is 180 ℃, and the time is 12 h.
3. The method for preparing the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, wherein the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solution of the deionized water and the absolute ethyl alcohol in the step 2) is 5:4, and 0.2g of carbon microspheres are added in every 90mL of the mixed solution of the deionized water and the absolute ethyl alcohol.
4. The preparation method of the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, wherein the silane coupling agent in the step 2) is KH550, and the mixed solution of the silane coupling agent and absolute ethyl alcohol is specifically: every 20mL of absolute ethanol was added with 5mL of silane coupling agent.
5. The preparation method of the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material as claimed in claim 1, wherein the volume ratio of the mixed solution of deionized water and absolute ethyl alcohol to the mixed solution of the silane coupling agent and absolute ethyl alcohol in the step 2) is 18: 5.
6. The preparation method of the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, wherein the heating conditions of the condensation reflux in the step 2) are as follows: reflux was condensed at 60 ℃ for 12 h.
7. The preparation method of the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, wherein the concentration of the modified carbon microspheres in the solution A in the step 3) is 5mg/mL-8mg/mL, and the addition amount of the methyl methacrylate is 0.2 wt% of the mass of the modified carbon microspheres.
8. The preparation method of the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, wherein the mass ratio of the graphene oxide to the modified carbon microspheres in the solution C in the step 5) is 1: 5.
9. The method for preparing the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, wherein the volume ratio of the solution A to the solution B in the step 5) is 2: 1.
10. The preparation method of the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, wherein the mass ratio of the added mass of the sodium dodecyl benzene sulfonate to the modified carbon microsphere in the step 6) is 1:40, the reaction temperature in the step 6) is 60 ℃, and the reaction time is 12 hours.
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| WO2017186127A1 (en) * | 2016-04-26 | 2017-11-02 | 复旦大学 | Method for preparing graphene-modified polymethyl methacrylate composite material having ultra-high conductivity |
| CN109913289A (en) * | 2019-03-25 | 2019-06-21 | 陕西科技大学 | A kind of preparation method of graphene oxide cladding carbosphere composite material |
| CN110628158A (en) * | 2019-09-27 | 2019-12-31 | 陕西科技大学 | Aqueous phase free radical polymerization preparation method of polymethyl methacrylate/carbon microsphere nano composite material with core-shell structure |
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| CN105062621A (en) * | 2015-08-17 | 2015-11-18 | 武汉理工大学 | Graphene oxide-polymeric microsphere water-based lubricant additive and preparation method thereof |
| WO2017186127A1 (en) * | 2016-04-26 | 2017-11-02 | 复旦大学 | Method for preparing graphene-modified polymethyl methacrylate composite material having ultra-high conductivity |
| CN109913289A (en) * | 2019-03-25 | 2019-06-21 | 陕西科技大学 | A kind of preparation method of graphene oxide cladding carbosphere composite material |
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