CN115895021B - Nanocellulose/graphene/epoxy resin composite material and preparation method thereof - Google Patents
Nanocellulose/graphene/epoxy resin composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nano composite materials, and particularly relates to a nano cellulose/graphene/epoxy resin composite material and a preparation method thereof. According to the invention, the environment-friendly nanocellulose and the high-performance graphene which are rich in sources are adopted as the modifier of the epoxy resin, meanwhile, the dispersion effect of the nanocellulose on the graphene is ingeniously utilized, the nanocellulose/graphene composite aerogel material with a porous structure is prepared, and then the epoxy resin is introduced to prepare the composite material, so that the agglomeration problem of the nanocellulose and the graphene is effectively solved. In the composite material, graphene is uniformly distributed in a resin matrix by means of the pore walls of aerogel, so that a heat conduction network is effectively established, and phonon conduction is facilitated. The composite material prepared by the invention has excellent thermo-mechanical property and higher thermal conductivity, and expands the application range of epoxy resin; the preparation process is simple, does not need organic solvent, is environment-friendly and can be produced in large scale.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to a nano cellulose/graphene/epoxy resin composite material and a preparation method thereof.
Background
The epoxy resin has good processing manufacturability, is the thermosetting resin with the most wide application, and has excellent mechanical properties after curing, excellent insulating properties, flame retardance, corrosion resistance and other excellent properties. However, epoxy resin materials are easily brittle due to the fact that molecules are crosslinked into a three-dimensional net-shaped structure after being cured, and the epoxy resin materials are easily broken when being subjected to external force. The epoxy resin has low thermal diffusivity and poor heat conduction property, and limits the application of the epoxy resin to a certain extent. With the development of nano technology, it is found that the comprehensive performance of the epoxy resin can be obviously improved by introducing nano materials into the epoxy resin. Meanwhile, people notice that the simultaneous use of two or more nano materials can exert the synergistic enhancement effect among the nano materials, and better modification effect is obtained.
Renewable biomass cellulose is getting more and more attention under the strategic objective tasks of the national "carbon peak, carbon neutralization". Cellulose is a green, renewable and easily degradable natural resource widely existing in nature, and the annual natural regeneration amount of cellulose reaches trillion tons worldwide. The one-dimensional product nanocellulose of the cellulose has more ideal geometric structure and excellent performance. Nanocellulose is generally divided into two main categories: the nano cellulose fiber (CNF) prepared by a physical mechanical force method has the diameter of 10-100nm, the length of micron level, the tensile strength of up to 3GPa and the Young's modulus of 160GPa, and can be used as an epoxy resin reinforcing material; the other is nano Cellulose Nanocrystalline (CNC) prepared by a chemical method, the diameter of the nano cellulose nanocrystalline is 5-50nm, the length of the nano cellulose nanocrystalline is 100-500nm, the nano cellulose nanocrystalline can be uniformly dispersed in an aqueous solution, and the two-dimensional nano material can be effectively dispersed. The mechanical and thermal stability and other performances of the epoxy resin can be obviously improved by adding a small amount of CNF or CNC into the epoxy resin.
The graphene has excellent mechanical, thermal, electrical and other properties, and is considered as the most ideal two-dimensional modified material of the polymer. The graphene can be prepared by a top-down method and a bottom-up method, wherein the top-down method is to prepare the graphene by taking graphite rich in resources as a raw material through a series of chemical and physical treatments. The preparation method is simple in process and low in cost, can realize large-scale production, and lays a road for large-scale application of the graphene in the polymer matrix composite.
In the existing preparation process of nano-cellulose or graphene modified epoxy resin composite materials, the nano-materials are generally dispersed in a solvent to obtain a suspension of the nano-materials, then the suspension is mixed with epoxy resin and a curing agent, and the solvent is removed after uniform dispersion and then the suspension is cured. Conventional preparation methods generally require the use of large amounts of solvents, increasing costs and environmental pollution. At the same time, it is difficult to completely remove the solvent used, and the solvent remains in the composite material, which can seriously affect the overall properties of the material. In addition, the nano material is easy to agglomerate after exceeding a certain content in the matrix, and the modification effect of the nano material can not be effectively exerted.
The compound use of the one-dimensional nano material and the two-dimensional nano material can exert the synergistic modification effect between the nano materials and improve the comprehensive performance of the composite material. However, how to uniformly disperse the nanomaterial in the resin and realize the large-scale preparation of the polymer-based nanomaterial is a great problem to be solved by the invention.
Disclosure of Invention
The invention aims to provide a preparation method of a nano-cellulose/graphene/epoxy resin composite material, wherein a three-dimensional porous nano-cellulose/graphene composite aerogel reinforcement is prepared by a solution mixing-freeze drying method, nano-cellulose and graphene are introduced into epoxy resin in the form of aerogel, so that the dispersion problem and solvent residue problem of the nano-cellulose and graphene are effectively solved, and the thermo-mechanical property and the heat conductivity of the composite material are improved.
In order to achieve the above purpose, the invention provides a preparation method of a nanocellulose/graphene/epoxy resin composite material, which specifically comprises the following steps:
(1) Dispersing graphene into a nano Cellulose Nanocrystalline (CNC) aqueous solution, and performing high-speed shearing and dispersing treatment for 3-10min to form CNC/graphene dispersion liquid;
(2) Adding nano cellulose fiber (CNF) slurry into the CNC/graphene dispersion liquid prepared in the step (1), performing ultrasonic dispersion treatment for 3-10min under the power of 50-300W to obtain CNF/CNC/graphene mixed dispersion liquid, and drying the CNF/CNC/graphene mixed dispersion liquid to prepare nano cellulose/graphene composite aerogel;
(3) Preparing epoxy resin/curing agent glue solution, soaking the nano cellulose/graphene composite aerogel with the epoxy resin/curing agent glue solution by adopting a vacuum infusion process, and curing to obtain the nano cellulose/graphene/epoxy resin composite material.
Further, the graphene in the step (1) is single-layer or multi-layer graphene, and the plane diameter is 0.5-50 μm.
Further, CNC in the step (1) is nanocrystalline prepared by acidolysis or enzymolysis of cellulose, the diameter is 10-30nm, and the length is less than 1 mu m.
Further, the rotating speed of the high-speed shearing dispersion treatment in the step (1) is 6000-15000 r/min.
Further, the concentration of CNC in the nano-cellulose nanocrystalline aqueous solution in the step (1) is 5-20 mg/ml.
Further, the concentration of graphene in the CNC/graphene dispersion liquid in the step (1) is 1-25 mg/ml.
Further, the nano cellulose fiber slurry in the step (2) is a mixed solution of nano cellulose fibers and water, the solid content is 0.5-5 wt%, the diameter of CNF is 10-60 nm, and the length of CNF is more than 1 μm.
Further, the concentration of CNF in the CNF/CNC/graphene mixed dispersion liquid in the step (2) is 5-50 mg/ml, the concentration of CNC is 2-20 mg/ml, and the concentration of graphene is 0.1-8 mg/ml. The mass ratio of CNF to CNC is 7/3, and the mass ratio of CNF and CNC to graphene is 7/5-20/1.
Further, the mass fraction of graphene in the nanocellulose/graphene composite aerogel of the step (2) is 5-40wt.%.
Further, the drying mode in the step (2) is selected from any one of freeze drying, supercritical drying and spray drying.
Further, the epoxy resin in the step (3) is a low-viscosity bisphenol A type epoxy resin or a bisphenol F type epoxy resin, and the room temperature viscosity of the epoxy resin is 200-2000 mPa.s; the curing agent is an amine curing agent, and the mass fraction of the curing agent in the epoxy resin/curing agent glue solution is 25 wt%.
Further, the vacuum infusion process conditions in the step (3) are as follows: the vacuum degree is 0.01-0.1 MPa, and the filling environment temperature is 40-60 ℃.
Further, the curing conditions in the step (3) are as follows: curing for 1-2 h at 60-80 ℃ and post-curing for 1-2 h at 100-160 ℃.
Further, the mass fraction of the nanocellulose/graphene composite aerogel in the nanocellulose/graphene/epoxy resin composite material in the step (3) is 5-20 wt.%.
The invention also provides the nanocellulose/graphene/epoxy resin composite material prepared by the preparation method.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the environment-friendly nanocellulose and the high-performance graphene which are rich in sources are adopted as the modifier of the epoxy resin, meanwhile, the dispersion effect of the nanocellulose on the graphene is ingeniously utilized, the nanocellulose/graphene composite aerogel material with a porous structure is prepared, and then the epoxy resin is introduced to prepare the composite material, so that the agglomeration problem of the nanocellulose and the graphene is effectively solved.
(2) In the prepared nanocellulose/graphene/epoxy resin composite material, graphene is uniformly distributed in a resin matrix by means of the pore wall of aerogel, so that a heat conduction network is effectively established, and phonon conduction is facilitated. The prepared composite material has excellent thermo-mechanical property and higher thermal conductivity, and expands the application range of the epoxy resin.
(3) The preparation process of the invention has simple process, no need of organic solvent, environmental protection and large-scale production.
Drawings
FIG. 1 is a cross-sectional, low-magnification SEM photograph of an epoxy resin composite material prepared according to example 1 of the present invention.
FIG. 2 is a cross-sectional high-magnification SEM photograph of an epoxy resin composite material prepared according to example 1 of the present invention.
Fig. 3 is a photograph of a nano-cellulose/(15 wt.%) graphene composite aerogel prepared in example 4 of the present invention.
Fig. 4 is an SEM photograph of the nano cellulose/(15 wt.%) graphene composite aerogel prepared in example 4 of the present invention.
Detailed Description
The technical scheme of the invention is further described in detail below through the specific embodiments and the attached drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
The planar diameter of graphene in all examples and comparative examples is 0.5 to 50 μm; CNC diameter is 10-30nm, length is less than 1 μm; CNF has a diameter of 10-60 nm and a length of more than 1 μm.
Example 1
The preparation method of the nanocellulose/graphene/epoxy resin composite material comprises the following steps:
(1) Dispersing 2.22g of graphene with a multilayer average plane diameter of 25 μm into 100ml of enzymolysis nanocellulose nanocrystalline (with an average diameter and length of CNC of 20nm and 500 nm) solution, and carrying out high-speed shearing and dispersing treatment at 12000r/min for 5min to form CNC/graphene dispersion, wherein the concentration of the graphene is 22.2mg/ml;
(2) Adding 70g of nano cellulose fiber (CNF with average diameter and length of 50nm and 200 mu m respectively) slurry with solid content of 1% into 30g of CNC/graphene dispersion liquid in the step (1), carrying out ultrasonic dispersion treatment for 5min under 150W power to obtain CNF/CNC/graphene mixed dispersion liquid (CNF, CNC and graphene concentration are 7mg/ml, 3mg/ml and 6.7mg/ml respectively), and preparing nano cellulose/(40 wt.%) graphene composite aerogel through freeze drying;
(3) Preparing bisphenol A epoxy resin LY1564 (with the room temperature viscosity of 1300 mPa.s)/amine curing agent Aradur 22962 glue solution according to the mass ratio of 4/1, soaking aerogel (0.1 MPa,50 ℃) with the glue solution by adopting a vacuum infusion process, curing for 1h at 80 ℃, and curing for 2h at 150 ℃ to obtain the nano-cellulose/(40 wt.%) graphene/epoxy resin composite material. The mass fraction of aerogel in the composite was about 10wt.%.
Example 2
The preparation method of the nanocellulose/graphene/epoxy resin composite material comprises the following steps:
(1) Dispersing 1.43g of graphene with a multilayer average plane diameter of 25 μm into 100ml of enzymolysis nanocellulose nanocrystalline (with an average diameter and length of CNC of 20nm and 500 nm) solution, and carrying out high-speed shearing and dispersing treatment at 12000r/min for 5min to form CNC/graphene dispersion, wherein the concentration of the graphene is 14.3mg/ml;
(2) Adding 70g of nano cellulose fiber (CNF with average diameter and length of 50nm and 200 mu m respectively) slurry with solid content of 1% into 30g of CNC/graphene dispersion liquid in the step (1), carrying out ultrasonic dispersion treatment for 5min under 150W power to obtain CNF/CNC/graphene mixed dispersion liquid (CNF, CNC and graphene concentration of 7mg/ml, 3mg/ml and 4.3mg/ml respectively), and preparing nano cellulose/(30 wt.%) graphene composite aerogel through freeze drying;
(3) Preparing bisphenol A epoxy resin LY1564 (with the room temperature viscosity of 1300 mPa.s)/amine curing agent Aradur 22962 glue solution according to the mass ratio of 4/1, soaking aerogel (0.1 MPa,50 ℃) with the glue solution by adopting a vacuum infusion process, curing for 1h at 80 ℃, and curing for 2h at 150 ℃ to obtain the nano-cellulose/(30 wt.%) graphene/epoxy resin composite material. The mass fraction of aerogel in the composite was about 8.6wt.%.
Example 3
The preparation method of the nanocellulose/graphene/epoxy resin composite material comprises the following steps:
(1) Dispersing 0.83g of graphene with a multilayer average plane diameter of 25 μm into 100ml of enzymolysis nanocellulose nanocrystalline (with an average diameter and length of CNC of 20nm and 500 nm) solution, and carrying out high-speed shearing and dispersing treatment at 12000r/min for 5min to form CNC/graphene dispersion, wherein the concentration of graphene is 8.3mg/ml;
(2) Adding 70g of nano cellulose fiber (CNF with average diameter and length of 50nm and 200 mu m respectively) slurry with solid content of 1% into 30g of CNC/graphene dispersion liquid in the step (1), carrying out ultrasonic dispersion treatment for 5min under 150W power to obtain CNF/CNC/graphene mixed dispersion liquid (CNF, CNC and graphene concentration of 7mg/ml, 3mg/ml and 2.5mg/ml respectively), and preparing nano cellulose/(20 wt.%) graphene composite aerogel through freeze drying;
(3) Preparing bisphenol A epoxy resin LY1564 (with the room temperature viscosity of 1300 mPa.s)/amine curing agent Aradur 22962 glue solution according to the mass ratio of 4/1, soaking aerogel (0.1 MPa,50 ℃) with the glue solution by adopting a vacuum infusion process, curing for 1h at 80 ℃, and curing for 2h at 150 ℃ to obtain the nano-cellulose/(20 wt.%) graphene/epoxy resin composite material. The mass fraction of aerogel in the composite was about 7.5wt.%.
Example 4
The preparation method of the nanocellulose/graphene/epoxy resin composite material comprises the following steps:
(1) Dispersing 0.60g of graphene with a multilayer average plane diameter of 25 μm into 100ml of enzymolysis nanocellulose nanocrystalline (with an average diameter and length of CNC of 20nm and 500 nm) solution, and carrying out high-speed shearing and dispersing treatment at 12000r/min for 5min to form a CNC/graphene dispersion, wherein the concentration of the graphene is 6.0mg/ml;
(2) Adding 70g of nano cellulose fiber (CNF with average diameter and length of 50nm and 200 mu m respectively) slurry with solid content of 1% into 30g of CNC/graphene dispersion liquid in the step (1), carrying out ultrasonic dispersion treatment for 5min under 150W power to obtain CNF/CNC/graphene mixed dispersion liquid (CNF, CNC and graphene concentration are 7mg/ml, 3mg/ml and 1.8mg/ml respectively), and preparing nano cellulose/(15 wt.%) graphene composite aerogel through freeze drying;
(3) Preparing bisphenol A epoxy resin LY1564 (with the room temperature viscosity of 1300 mPa.s)/amine curing agent Aradur 22962 glue solution according to the mass ratio of 4/1, soaking aerogel (0.1 MPa,50 ℃) with the glue solution by adopting a vacuum infusion process, curing for 1h at 80 ℃, and curing for 2h at 150 ℃ to obtain the nano-cellulose/(15 wt.%) graphene/epoxy resin composite material. The mass fraction of aerogel in the composite was about 7.1wt.%.
Example 5
The preparation method of the nanocellulose/graphene/epoxy resin composite material comprises the following steps:
(1) Dispersing 0.37g of graphene with a multilayer average plane diameter of 25 μm into 100ml of enzymolysis nanocellulose nanocrystalline (with an average diameter and length of CNC of 20nm and 500 nm) solution, and carrying out high-speed shearing and dispersing treatment at 12000r/min for 5min to form CNC/graphene dispersion, wherein the concentration of the graphene is 3.7mg/ml;
(2) Adding 70g of nano cellulose fiber (CNF with average diameter and length of 50nm and 200 mu m respectively) slurry with solid content of 1% into 30g of CNC/graphene dispersion liquid in the step (1), carrying out ultrasonic dispersion treatment for 5min under 150W power to obtain CNF/CNC/graphene mixed dispersion liquid (CNF, CNC and graphene concentration are 7mg/ml, 3mg/ml and 1.1mg/ml respectively), and preparing nano cellulose/(10 wt.%) graphene composite aerogel through freeze drying;
(3) Preparing bisphenol A epoxy resin LY1564 (with the room temperature viscosity of 1300 mPa.s)/amine curing agent Aradur 22962 glue solution according to the mass ratio of 4/1, soaking aerogel (0.1 MPa,50 ℃) with the glue solution by adopting a vacuum infusion process, curing for 1h at 80 ℃, and curing for 2h at 150 ℃ to obtain the nano-cellulose/(10 wt.%) graphene/epoxy resin composite material. The mass fraction of aerogel in the composite was about 6.7wt.%.
Example 6
The preparation method of the nanocellulose/graphene/epoxy resin composite material comprises the following steps:
(1) Dispersing 0.18g of graphene with a multilayer average plane diameter of 25 μm into 100ml of nanocellulose nanocrystalline (CNC with average diameter and length of 20nm and 500 nm) solution with a concentration of 10mg/ml, and carrying out high-speed shearing dispersion treatment at 12000r/min for 5min to form a CNC/graphene dispersion, wherein the concentration of the graphene is 1.77mg/ml;
(2) Adding 70g of nano cellulose fiber (CNF with average diameter and length of 50nm and 200 μm respectively) slurry with solid content of 1wt.% into 30g of CNC/graphene dispersion liquid in the step (1), carrying out ultrasonic dispersion treatment for 5min under 150W power to obtain CNF/CNC/graphene mixed dispersion liquid (CNF, CNC and graphene concentration of 7mg/ml, 3mg/ml and 0.53mg/ml respectively), and preparing nano cellulose/(5 wt.%) graphene composite aerogel through freeze drying;
(3) Preparing bisphenol A epoxy resin LY1564 (with the room temperature viscosity of 1300 mPa.s)/amine curing agent Aradur 22962 glue solution according to the mass ratio of 4/1, soaking aerogel (0.1 MPa,50 ℃) with the glue solution by adopting a vacuum infusion process, curing for 1h at 80 ℃, and curing for 2h at 150 ℃ to obtain the nano-cellulose/(5 wt.%) graphene/epoxy resin composite material. The mass fraction of aerogel in the composite was about 6.3wt.%.
Comparative example 1
The preparation method of the epoxy resin material comprises the following steps:
preparing a curing agent Aradur 22962 glue solution of bisphenol A epoxy resin LY1564 (with the room temperature viscosity of 1300 mPa.s)/an amine curing agent according to the mass ratio of 4/1, pouring the glue solution into a polytetrafluoroethylene mold, curing for 1h at 80 ℃ and then curing for 2h at 150 ℃ to obtain the pure epoxy resin material.
Comparative example 2
The preparation method of the nano cellulose/epoxy resin composite material comprises the following steps:
(1) Measuring 100ml of nano-cellulose nanocrystalline (CNC average diameter and length are 20nm and 500 nm) solution with concentration of 1mg/ml, and performing high-speed shearing dispersion treatment for 5min at 12000r/min to form CNC dispersion;
(2) Adding 70g of nano cellulose fiber (CNF with average diameter and length of 50nm and 200 μm respectively) slurry with solid content of 1% into 30g of CNC dispersion liquid in the step (1), carrying out ultrasonic dispersion treatment for 5min under 150W power to obtain CNF/CNC mixed dispersion liquid, and preparing a nano cellulose gel reinforcement by freeze drying;
(3) Preparing bisphenol A epoxy resin LY1564 (with the room temperature viscosity of 1300 mPa.s)/amine curing agent Aradur 22962 glue solution according to the mass ratio of 4/1, soaking aerogel (0.1 MPa,50 ℃) with the glue solution by adopting a vacuum pouring process, curing for 1h at 80 ℃, and curing for 2h at 150 ℃ to obtain the nano cellulose/epoxy resin composite material. The mass fraction of nanocellulose in the composite is about 6.0wt.%.
Comparative example 3
(1) Dispersing 0.11g of graphene with a multilayer average plane diameter of 25 μm into 100g of nano cellulose fiber (CNF with average diameter and length of 50nm and 200 μm respectively) slurry with a solid content of 1wt.%, and performing ultrasonic dispersion treatment for 5min under 150W power to obtain CNF/graphene mixed dispersion liquid (CNF and graphene with concentration of 10mg/ml and 1.1mg/ml respectively), and preparing nano cellulose/(10 wt.%) graphene composite aerogel by freeze drying;
(2) Preparing bisphenol A epoxy resin LY1564 (with the room temperature viscosity of 1300 mPa.s)/amine curing agent Aradur 22962 glue solution according to the mass ratio of 4/1, soaking aerogel (0.1 MPa,50 ℃) with the glue solution by adopting a vacuum infusion process, curing for 1h at 80 ℃, and curing for 2h at 150 ℃ to obtain the nano-cellulose/(10 wt.%) graphene/epoxy resin composite material. The mass fraction of aerogel in the composite was about 6.7wt.%.
Comparative example 4
The preparation method of the nanocellulose/graphene/epoxy resin composite material comprises the following steps:
(1) Dispersing 3.33g of graphene with a multilayer average plane diameter of 25 μm into 100ml of enzymolysis nanocellulose nanocrystalline (with an average diameter and length of CNC of 20nm and 500 nm) solution, and carrying out high-speed shearing and dispersing treatment at 12000r/min for 5min to form CNC/graphene dispersion, wherein the concentration of the graphene is 33.3mg/ml;
(2) Adding 70g of nano cellulose fiber (CNF with average diameter and length of 50nm and 200 mu m respectively) slurry with solid content of 1% into 30g of CNC/graphene dispersion liquid in the step (1), carrying out ultrasonic dispersion treatment for 5min under 150W power to obtain CNF/CNC/graphene mixed dispersion liquid (CNF, CNC and graphene concentration of 7mg/ml, 3mg/ml and 10mg/ml respectively), and preparing nano cellulose/(50 wt.%) graphene composite aerogel through freeze drying;
(3) Preparing bisphenol A epoxy resin LY1564 (with the room temperature viscosity of 1300 mPa.s)/amine curing agent Aradur 22962 glue solution according to the mass ratio of 4/1, soaking aerogel (0.1 MPa,50 ℃) with the glue solution by adopting a vacuum infusion process, curing for 1h at 80 ℃, and curing for 2h at 150 ℃ to obtain the nano-cellulose/(50 wt.%) graphene/epoxy resin composite material. The mass fraction of aerogel in the composite was about 12wt.%.
Comparative example 5
The preparation method of the nano cellulose/epoxy resin composite material comprises the following steps:
(1) Measuring 100ml of nanocellulose nanocrystalline (CNC with average diameter and length of 20nm and 500 nm) solution with concentration of 2mg/ml, and performing high-speed shearing dispersion treatment at 12000r/min for 5min to form CNC dispersion;
(2) Adding 70g of nano cellulose fiber (CNF with average diameter and length of 50nm and 200 μm respectively) slurry with solid content of 2% into 30g of CNC dispersion liquid in the step (1), carrying out ultrasonic dispersion treatment for 5min under 150W power to obtain CNF/CNC mixed dispersion liquid, and preparing a nano cellulose gel reinforcement by freeze drying;
(3) Preparing bisphenol A epoxy resin LY1564 (with the room temperature viscosity of 1300 mPa.s)/amine curing agent Aradur 22962 glue solution according to the mass ratio of 4/1, soaking aerogel (0.1 MPa,50 ℃) with the glue solution by adopting a vacuum pouring process, curing for 1h at 80 ℃, and curing for 2h at 150 ℃ to obtain the nano cellulose/epoxy resin composite material. The mass fraction of nanocellulose in the composite is about 24wt.%.
Performance test:
for examples 1-6, the nanocomposites prepared in comparative examples 1-5 were subjected to thermal mechanical performance testing according to ASTM E2254, thermally conductive testing according to ASTM-E1461, storage modulus at 35℃and thermal conductivity at room temperature are shown in Table 1.
TABLE 1 comparison of the Properties of the composite materials prepared in examples and comparative examples of the present invention
As can be seen from examples and comparative examples in table 1, the nanocellulose/graphene/epoxy composite material has excellent properties when the composite aerogel and the graphene content in the composite aerogel are within a certain range. Compared with the pure epoxy resin of comparative example 1 and the nanocellulose/epoxy resin composite material of comparative example 2, when the graphene content in the composite aerogel used is 5 to 40wt.% (examples 1 to 6), the storage modulus and the thermal conductivity of the nanocellulose/graphene/epoxy resin composite material prepared by the invention are increased with the increase of the graphene content, but when the graphene content in the composite aerogel used exceeds 40wt.% (comparative example 4), the storage modulus and the thermal conductivity of the composite material are reduced, because the agglomeration in the aerogel is caused due to the excessively high graphene content, and the nano effect of the graphene and the formation of a heat conducting network are affected.
Comparative example 5 is a composite material having an aerogel content of more than 20wt.% and a storage modulus lower than that of the composite materials having an aerogel content of 5 to 20wt.% prepared in examples 1 to 6, because an excessively high aerogel content in the composite material may cause the aerogel to be insufficiently infiltrated with the dope, causing an increase in porosity and a decrease in storage modulus.
Comparative example 3 is a CNF/(10 wt.%) graphene/epoxy composite material without added CNC, which has a lower storage modulus and thermal conductivity than the CNC-containing nanocellulose/(10 wt.%) graphene/epoxy composite material prepared in example 5, which illustrates that the present invention can effectively disperse graphene using CNC, fully exert the modification effect of the nanomaterial, and embody the technical advantages of the present invention.
Fig. 1 and 2 are a physical image and a scanning electron micrograph of the nanocellulose/(15 wt.%) graphene composite aerogel prepared in example 4, respectively, and fig. 3 and 4 are low-power and high-power scanning electron micrographs of the composite aerogel modified epoxy composite, respectively. As can be seen from fig. 1 and fig. 2, the composite aerogel is a three-dimensional porous material, and as can be seen from fig. 3 and fig. 4, micropores of the aerogel in the epoxy resin composite material are completely filled with resin, which indicates that the wettability of the glue solution to the aerogel is good. The graphene in the composite material is uniformly distributed, a heat conduction network is formed, and the heat conductivity of the composite material is effectively improved.
Claims (13)
1. The preparation method of the nanocellulose/graphene/epoxy resin composite material is characterized by comprising the following steps of:
(1) Dispersing graphene into a nano-cellulose nanocrystalline aqueous solution, and performing high-speed shearing and dispersing treatment for 3-10min to form nano-cellulose nanocrystalline/graphene dispersion;
(2) Adding the nano cellulose fiber slurry into the nano cellulose nanocrystalline/graphene dispersion liquid prepared in the step (1), performing ultrasonic dispersion treatment for 3-10min under the power of 50-300W to obtain nano cellulose fiber/nano cellulose nanocrystalline/graphene mixed dispersion liquid, and drying the nano cellulose fiber/nano cellulose nanocrystalline/graphene mixed dispersion liquid to prepare nano cellulose/graphene composite aerogel;
(3) Preparing epoxy resin/curing agent glue solution, soaking the nano cellulose/graphene composite aerogel with the epoxy resin/curing agent glue solution by adopting a vacuum infusion process, and curing to obtain a nano cellulose/graphene/epoxy resin composite material;
the mass ratio of the nano cellulose fiber to the nano cellulose nanocrystalline in the step (2) is 7:3, and the ratio of the total mass of the nano cellulose fiber and the nano cellulose nanocrystalline to the mass of the graphene is 7/5-20/1;
the mass fraction of graphene in the nano cellulose/graphene composite aerogel in the step (2) is 5-40 wt%;
the mass fraction of the nanocellulose/graphene composite aerogel in the nanocellulose/graphene/epoxy resin composite material in the step (3) is 5-20 wt%.
2. The preparation method of claim 1, wherein the graphene in the step (1) is single-layer or multi-layer graphene, and the plane diameter is 0.5-50 μm.
3. The method according to claim 1, wherein the nanocellulose nanocrystals in step (1) are nanocrystals prepared by acidolysis or enzymolysis of cellulose, and have a diameter of 10-30nm and a length of less than 1 μm.
4. The method according to claim 1, wherein the high-speed shearing dispersion treatment in the step (1) is carried out at a rotational speed of 6000 to 15000r/min.
5. The method according to claim 1, wherein the concentration of nanocellulose nanocrystals in the nanocrystallines aqueous solution in step (1) is 5-20 mg/ml.
6. The method according to claim 1, wherein the concentration of graphene in the nanocellulose nanocrystalline/graphene dispersion of step (1) is 1 to 25mg/ml.
7. The method according to claim 1, wherein the solid content of the nanocellulose fiber slurry in the step (2) is 0.5-5 wt%, the diameter of the nanocellulose fiber is 10-60 nm, and the length of the nanocellulose fiber is greater than 1 μm.
8. The preparation method according to claim 1, wherein the concentration of the nanocellulose fibers in the nanocellulose fiber/nanocellulose nanocrystalline/graphene mixed dispersion liquid in the step (2) is 5-50 mg/ml, the concentration of the nanocellulose nanocrystalline is 2-20 mg/ml, and the concentration of the graphene is 0.1-8 mg/ml.
9. The method according to claim 1, wherein the drying in the step (2) is any one of freeze drying, supercritical drying and spray drying.
10. The method according to claim 1, wherein the epoxy resin in the step (3) is a low-viscosity bisphenol a type epoxy resin or bisphenol F type epoxy resin, and the epoxy resin has a room temperature viscosity of 200 to 2000 mPa-s; the curing agent is an amine curing agent, and the mass fraction of the curing agent in the epoxy resin/curing agent glue solution is 25wt percent.
11. The method according to claim 1, wherein the vacuum infusion process conditions in step (3) are: the vacuum degree is 0.01-0.1 MPa, and the filling environment temperature is 40-60 ℃.
12. The method according to claim 1, wherein the curing conditions in the step (3) are: curing for 1-2 h at 60-80 ℃ and post-curing for 1-2 h at 100-160 ℃.
13. A nanocellulose/graphene/epoxy composite material made by the method of any one of claims 1-12.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106187269A (en) * | 2016-07-19 | 2016-12-07 | 青岛科技大学 | A kind of controlled amphiphilic graphene aerogel of intensity and preparation method thereof |
| CN108276615A (en) * | 2017-12-29 | 2018-07-13 | 华中科技大学 | A kind of high heat conduction stratiform graphene composite material and preparation method |
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| CN106187269A (en) * | 2016-07-19 | 2016-12-07 | 青岛科技大学 | A kind of controlled amphiphilic graphene aerogel of intensity and preparation method thereof |
| CN108276615A (en) * | 2017-12-29 | 2018-07-13 | 华中科技大学 | A kind of high heat conduction stratiform graphene composite material and preparation method |
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| 木质纳米纤维素为基质制备柔性透明导电膜和电极材料的硏究;郭晓宇;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第1期);14-15、23-27 * |
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